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Measurement of nickel, cobalt and chromium in toy make-up by atomic absorption spectroscopy

https://www.medicaljournals.se/acta/content/html/10.2340/00015555-0595

Materials

Seven toy make-up kits, numbered 1–7, were bought in different shops (e.g. toy shops, hypermarkets, tobacconists, newsagents (as gifts in children magazines) and bazaars). Each box included various cosmetics (e.g. eye shadows, lip gloss, lipsticks, nail polish, lip pencil, lip balm).

A total of 52 cosmetics were analysed: 29 eye shadows, 15 lip glosses, 5 lipsticks, one nail polish, one lip pencil and one lip balm. The samples were processed by acid digestion in a microwave oven. A 0.2–0.4 g weight of each cosmetic was taken and 6 ml concentrated nitric acid, 2 ml concentrated hydrofluoric acid and 2 ml 30% hydrogen peroxide were added. The samples underwent a specific microwave program using a ETHOS 900 microwave oven (Milestone, FKV, Sorisole, Italy) equipped with a six-position mono-bloc high pressure rotor.

After cooling, the samples were transferred to 50 ml volumetric flasks and diluted to the mark with MilliQ water (Millipore Corporation, Bedford, USA). When necessary, samples were filtered through N41 ash-less filters (Whatman International Ltd, Maidstone, UK).

Method of analysis

All measurements were carried out with a model analyst 800 atomic absorption spectrometer (Perkin-Elmer, Shelton, USA) equipped with a Zeeman background correction system and an electro-thermal atomizer with a transversely heated graphite tube.

Atomic absorption spectroscopy was performed at a wavelength of 236.0 nm for nickel, 356.9 nm for chromium and 242.5 nm for cobalt. Matrix modifier was applied for chromium and cobalt (Mg(NO3)2). The volume of each analysed sample was 20 μl. Each sample was prepared twice, two different analyses were performed, and the mean value calculated.

The detection limits were defined as the analyte concentration corresponding to 3 times the standard deviation of 10 consecutive blank sample runs, using 200 mg of the solid sample in a final volume of 50 ml. This value was 0.1 μg/g for chromium and nickel, and 0.2 μg/g for cobalt.

The accuracy of the analysis was demonstrated to be between 95% and 105%, by the recovery data observed for spiked real samples (6, 7).

The quantities (mean values) of nickel, chromium and cobalt detected in each toy make-up are shown in Table I. The number of samples of each type of make-up, grouped by metal content, are shown in Table II. Values are grouped as 1–10 ppm, 10–100 ppm, 100–1000 ppm, and more than 1000 ppm.

Table I. Quantities (mean values) of chromium, nickel and cobalt in toy make-ups

Toy make-up type and colour

Nickel

μg/g (ppm)

Chromium

μg/g (ppm)

Cobalt

μg/g

Box/kit 1

Eye shadows

lavender

lilac

262

320

203

290

12.0

12.5

Lipsticks/mallow

1.23

2.89

< 0.2

Box/kit 2

Eye shadows

dark green

light green

pale green

dark salmon

pale salmon

blue

sky blue

light violet

magenta

pink

grass green

yellow

1.8

1.9

10.1

4.4

1.4

2.5

2.0

10.1

10.2

11.2

6.9

9.5

1580

106

47.7

30.4

16.7

61.8

35.5

41.3

26.3

23.3

32.3

37.2

0.99

0.99

1.04

1.2

1.13

0.61

0.86

1.2

1.1

1.3

1.5

0.84

Lipsticks/red

0.14

1.33

< 0.2

Box/kit 3

Eye shadows

apricot

lavender

pink

grey

yellow

2.33

2.96

2.65

5.47

2.52

1.61

3.03

2.72

3620

19.3

1.26

1.25

1.45

5.46

1.14

Lipsticks/red

< 0.1

1.1

< 0.2

Box/kit 4

Eye shadows

light pink

lemon green

light blue

yellow

pink

lavender

violet

2.96

13.5

7.45

6.46

3.89

4.0

4.83

33.5

1579

23.8

20.4

33.5

28.7

26.0

0.47

12.0

0.65

2.98

0.57

0.54

0.52

Lipsticks

pink

light pink

< 0.1

2.35

2.99

5.05

< 0.2

< 0.2

Lip gloss

pink

red

lilac

< 0.1

< 0.1

< 0.1

0.64

5.48

2.16

< 0.2

< 0.2

< 0.2

Box/kit 5

Lip balm/brown

< 0.1

0.6

< 0.2

Lip pencil/pink

1.41

1.69

0.48

Box/kit 6

Lip gloss/all 7 coloursa

< 0.1

< 0.1

< 0.2

Box/kit 7

Lip gloss/all 5 coloursb

< 0.1

< 0.1

< 0.2

aDark silver, light silver, dark magenta, light magenta, dark orange, light orange, dark pink.

bLight pink, vermilion, glittery pink, glitter only, silver.

Table II. Number of samples containing amounts of nickel (Ni), chromium (Cr) and cobalt (Co) in 4 different ranges

Quantity (ppm)

Eye shadows

(n = 29)

Lipsticks

(n = 5)

Lip gloss

(n = 15)

Ni

Cr

Co

Ni

Cr

Co

Ni

Cr

Co

> 1000

0

3

0

0

0

0

0

0

0

> 100 ≤ 1000

3

5

0

0

0

0

0

0

0

> 10 ≤ 100

5

18

4

0

0

0

0

0

0

> 1 ≤ 10

21

3

15

2

5

0

0

3

0

For the 29 eye shadows (total number of analyses performed = 87), in 3 cases the presence of chromium was a lot higher than 1000 ppm (1580 ppm, 3620 ppm and 1579 ppm). In 38 out of 87 tests, nickel, chromium and cobalt were more than 10 ppm. In 39 analyses the quantity of metals was between 1 and 10 ppm.

For the 5 lipsticks, no values higher than 10 ppm were detected. Levels between 1 and 10 ppm of nickel and chromium were obtained in 5 and 2 samples, respectively.

For the 15 lip glosses, no values higher than 10 ppm were detected. In 3 samples chromium was in the range 1–10 ppm.

Table III shows the values of the three metals in the range 0–5 ppm. The results for the 29 eye shadows show that this amount of nickel, chromium and cobalt was present in 15, 3 and 24 samples, respectively.

All 15 lip glosses contained quantities of nickel and cobalt between 0 and 5 ppm. Only one had higher quantities of chromium. The quantity of chromium exceeded 5 ppm in 1 of the 5 lipsticks, while all the other metals were in the range 0–5 ppm.

Table III. Number of samples of toy make-up containing amounts of nickel, chromium and cobalt in the ranges less than 5 ppm and less than 1 ppm

Toy make-up type (number of samples)

Metal (≤ 5 ppm)

Metal (≤ 1 ppm)

Nickel

Chromium

Cobalt

Nickel

Chromium

Cobalt

Eye shadows (29)

15/29

3/29

24/29

0/29

0/29

10/29

Lip gloss (15)

15/15

14/15

15/15

15/15

12/15

15/15

Lipsticks (5)

5/5

4/5

5/5

3/5

0/5

5/5

Lip balm (1)

1/1

1/1

1/1

1/1

1/1

1/1

Nail polish (1)

1/1

1/1

1/1

1/1

1/1

1/1

Lip pencil (1)

1/1

1/1

1/1

0/1

0/1

1/1

None of the 29 eye shadows met the amount of 1 ppm or below for nickel and chromium, 10 contained an amount of cobalt no higher than 1 ppm. All 15 lip glosses were in this range for nickel and cobalt; 3 lip glosses contained more than 1 ppm of chromium. The 5 lipsticks contained over 1 ppm chromium, while the amount of cobalt was always lower.

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