Survey of chemical substances in kohl and henna products

4 Analyses results

4.1 Kohl products

4.1.1 Analysis results - screening

The analysis results from the screening of kohl products are listed in the tables below.

Table 1. Kohl products, Inorganic analysis – screening analyses

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Table 1. continued

Analyte DL
µg/g
%RSD Sample no.: 31341-
52 56 59 60 61 62 64 65 66
µg/g µg/g µg/g µg/g µg/g µg/g µg/g µg/g µg/g
Li 0.5 4.6% 24 12 - 1.2 - - - - -
Be 1 14% 1.9 - - - - - - - -
B 5 4.6% 9.2 - - 34000 44 - - - 9.1
Na 1 1.9% 350 43 70 2400 54 32 43 52 150
Mg 1 1.7% 4000 3300 15 830 27 13 21 17 120
Al 1 4.7% 12000 470 52 3500 95 58 38 30 190
Si 10 6.3% 2900 5000 70 360 170 99 110 95 600
K 5 2.8% 5700 290 16 6400 29 19 14 17 360
Ca 5 2.8% 170 130 70 110000 200 54 78 64 410
Sc 0.5 4.1% 1.9 1.8 - 1.2 - - - - -
Ti 0.5 6.5% 76 59 3.5 15 7.6 3.0 1.9 1.7 13
V 0.5 4.4% 0.86 - 5.2 75 64 15 16 12 1.3
Cr 0.5 2.2% 3.2 8.2 13 3.6 1.6 0.88 2.2 1.5 1.1
Mn 0.1 0.99% 330 280 170 180 1.4 1.5 0.87 0.60 12
Fe 10 8.2% 150000 150000 56000 490 81 41 47 27 270
Co 0.1 5.6% 31 27 1.8 3.6 3.3 0.96 - - 0.11
Ni 0.5 4.4% 39 41 18 56 54 21 13 9.9 1.4
Cu 0.1 3.6% 0.48 2.0 8.9 880 3.5 1.7 1.4 5.6 3.7
Zn 0.5 6.8% 16 12 12 120000 36 5.0 3.3 11 13
Ga 0.1 8.0% 5.1 0.21 0.38 0.81 0.13 - - - 0.16
As 1 17% - - - 6.1 - - - - -
Se 1 29% - - - 8.5 - - - - -
Rb 0.1 2.9% 79 3.0 - - - - 0.12 - 0.83
Sr 0.1 2.1% 2.9 1.3 58 280 0.60 0.40 0.69 0.62 2.7
Y 0.1 2.4% - 0.29 - 12 - - - - 0.12
Zr 0.1 11% 7.2 18 0.27 0.83 0.43 0.18 - - -
Nb 0.1 3.1% 3.7 - 0.70 - - - - - -
Mo 0.1 4.9% 0.39 0.28 0.14 0.92 0.57 - 0.17 - 0.19
Ru 0.1 - - - - - - - - - -
Pd 0.1 - - - - - - - - - -
Ag 0.1 1.8% - - - - - - - - 1.1
Cd 0.05 12% - - 0.06 1.8 - - - - 0.08
In 0.05 19% - - - 0.07 - - - - -
Sn 0.5 4.8% 4.3 3.3 0.52 - - - - - 1.8
Sb 0.05 6.0% - - 0.09 0.15 - - - - -
Te 0.1 30% - - - - - - - - -
Cs 0.1 5.3% 8.2 0.33 - 0.39 - - - - -
Ba 0.1 4.8% 38 1.4 5500 11 2.7 1.2 1.5 1.5 88
La 0.05 2.1% - 0.08 0.08 1.0 0.31 0.25 0.16 0.12 0.15
Ce 0.05 3.1% 0.06 0.16 0.06 1.7 0.24 0.20 0.11 0.09 0.29
Pr 0.05 2.5% - - - 0.28 - 0.05 - - -
Nd 0.05 2.3% - 0.1 - 1.5 0.11 0.12 0.08 0.06 0.16
Sm 0.05 11% - - - 0.57 - - - - -
Eu 0.05 10% - - 0.52 0.12 - - - - -
Gd 0.05 10% - - - 0.91 - - - - -
Tb 0.05 3.6% - - - 0.14 - - - - -
Dy 0.05 3.6% - - - 1.0 - - - - -
Ho 0.05 5% - - - 0.30 - - - - -
Er 0.05 4.9% - - - 1.1 - - - - -
Tm 0.05 7.3% - - - 0.20 - - - - -
Yb 0.05 7.1% - - - 1.6 - - - - -
Lu 0.05 5.5% - - - 0.33 - - - - -
Hf 0.05 8.7% 0.08 0.25 - - - - - - -
Ta 0.05 16% - - - - - - - - -
W 0.05 20% 3.4 - - - - - - - -
Os 0.05 - - - - - - - - - -
Ir 0.05 - - - - - - - - - -
Pt 0.05 - - - - - - - - - -
Au 0.05 - - - - - - - - - -
Hg 0.5 - - - - - - - - - -
Tl 0.05 11% 0.28 - - 0.05 - - - - -
Pb 0.05 4.1% 3.1 0.43 0.76 280 3.8 2.9 0.48 0.75 4.0
Bi 0.05 9.6% 4.9 0.7 - 0.11 - - 0.14 0.1 0.32
Th 0.05 5.5% - - - 0.06 - - - - -
U 0.5 - - - - - - - - - -

DL : Detection limit
%RSD presents the percentage relative standard deviation made as common estimate based on the relative standard deviation from duplicate determinations.

4.1.2 Analysis results – quantitative measurements

The analyses results from the quantitative measurements for inorganic substances in the selected kohl products is presented in the tables below.

It should be noticed that deviations may occur when comparing the quantitative results with the screening results. In that case the quantitative results are the preferred values as they consider circumstances that may affect the analysis which is not the case to the same extent in the screening.

Table 2. Quantitative measurements of lead (Pb) in kohl products

Sample number Pb
mg/kg
25 0.30
30 0.31
31 -
33 -
35 0.81
42 0.71
43 0.39
49 -
51 0.86
52 2.8
56 0.36
59 0.78
60 280
61 4.2
62 3.1
64 0.53
65 0.84
66 4.2
%RSD 6.6

”-” denotes measurement below detection limit of 0.1 mg/kg.

%RSD presents the percentage relative standard deviation made as common estimate based on the relative standard deviation from duplicate determinations.

Further quantitative determinations on elements were performed when a content higher than 10 mg/kg were observed in the screening with the exception of normally occurring elements such as aluminium, calcium, iron, magnesium, silicon and titanium and the alkali metals. The results are listed in the table below.

Table 3. Quantitative measurements of other elements in kohl products

Sample number B
mg/kg
Ba
mg/kg
Bi
mg/kg
Co
mg/kg
Cu
mg/kg
25 420 - - 28 -
30 - - - 30 -
31 - - - 47 -
33 - - - 28 -
35 - - - 13 -
42 - - - 26 -
43 - - - 37 -
49 - - - - -
51 - - 74900 - -
52 - 53 - 33 -
56 - - - 25 -
59 - 6700 - - -
60 32000 14,5 - - 950
61 NA - - - -
62 - - - - -
64 - - - - -
65 - - - - -
66 NA NA - - -
%RSD 3.1 3.7 0.6 3.5 7.3

Table 3. continued

Sample number Mn
mg/kg
Ni
mg/kg
Sr
mg/kg
V
mg/kg
Zn
mg/kg
25 465 31 - - -
30 377 33 - - -
31 710 23 - - -
33 334 29 - - -
35 270 37 - - -
42 344 26 - - -
43 421 41 - - -
49 554 15 - - -
51 490 - - - -
52 474 38 - - -
56 363 39 - - -
59 297 17 120 - -
60 190 65 280 74 115000
61 - 55 - 62 -
62 - 24 - - -
64 - 16 - - -
65 - - - - -
66 - - NA - -
%RSD 1.6 7.6 2.3 1.4 1.1

-: Below detection limit
NA: Not analysed
%RSD presents the percentage relative standard deviation made as common estimate based on the relative standard deviation from duplicate determinations.

It is noticed that:

  • Lead (Pb) occurs in 15 out of 18 products above the detection limit of 0.1 mg/kg. The concentrations ranges 0.3 to 280 mg/kg. Lead occurs at the highest concentration in product no. 60 (280 mg/kg), cf. table 2.
  • Boron (B) occurs in 2 products and at the highest concentration in product no. 60 (32000 mg/kg corresponding to 3.2%), cf. table 3.
  • Barium (Ba) occurs in 3 products but only at high concentration in product no. 59 (6700 mg/kg).
  • Bismuth (Bi) occurs in product no. 51 at high concentration (74900 mg/kg corresponding to 7.5%).
  • Cobalt (Co) occurs in 9 out of 18 analysed products at the range 13 to 47 mg/kg.
  • Manganese (Mn) occurs in 13 out of 18 products at the range 190 to 710 mg/kg.
  • Nickel (Ni) occurs in 15 out of 18 products at the range 15 to 65 mg/kg.
  • Strontium (Sr) occurs in 2 products at the range 120 to 280 mg/kg.
  • Vanadium (V) occurs in 2 products at the range 62 to 74 mg/kg.
  • Zinc (Zn) occurs in product no 60 at a high concentration (115000 mg/kg corresponding to 11.5% m/m).

4.2 Henna products

4.2.1 Analysis results – screening of inorganic substances

The inorganic analysis results from the screening of henna products are listed in the tables below.

Table 4. Henna products, inorganic analysis – screening analyses

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Ana-
lyte
DL
µg/g
%RSD Sample no.: 31341-
11 12 14 20 21 23 57 58 63
µg/g µg/g µg/g µg/g µg/g µg/g µg/g µg/g µg/g
Li 0.5 4.6% - 2.9 - 2.3 - 5.9 1.5 1.4 1.6
Be 1 14% - - - - - - - - -
B 5 4.6% - 31 - 30 - 63 42 25 22
Na 1 1.9% 3900 1200 > 2900 4100 3600 3000 3600 1200
Mg 1 1.7% 1.3 4100 22 2700 1.3 5600 5500 8600 2600
Al 1 4.7% 4.5 1300 2.5 1400 7.8 3400 770 510 460
Si 10 6.3% 13 710 11 720 12 1000 380 330 580
K 5 2.8% 20 > 74 5800 41 7300 2800 2600 5700
Ca 5 2.8% 13 15000 10 11000 6.2 16000 7500 6700 12000
Sc 0.5 4.1% - - - 0.53 - 1.1 - - -
Ti 0.5 6.5% - 57 - 56 - 160 27 29 29
V 0.5 4.4% - 2.9 - 2.5 - 8.7 2.3 2.0 1.5
Cr 0.5 2.2% - 3.3 - 10 - 6.0 3.2 5.7 5.7
Mn 0.1 0.99% - 78 - 68 - 170 35 46 95
Fe 10 8.2% - 1500 - 1600 - 2400 810 640 600
Co 0.1 5.6% - 0.90 - 0.7 - 2.0 0.59 0.62 0.78
Ni 0.5 4.4% - 3.9 - 3.0 - 8.7 2.1 1.9 1.9
Cu 0.1 3.6% 0.20 7.8 0.14 4.9 0.17 12 4.4 5.1 8.1
Zn 0.5 6.8% 1.4 20 19 11 3.0 22 76 71 14
Ga 0.1 8.0% - 0.45 - 0.47 - 0.97 0.30 0.21 0.22
As 1 17% - - - - - 2.3 - - -
Se 1 29% - - - - - - - - 2.4
Rb 0.1 2.9% - 5.1 - 9.6 - 3.3 2.3 1.5 9.6
Sr 0.1 2.1% - 180 0.13 91 - 210 180 210 120
Y 0.1 2.4% - 0.62 - 0.80 - 1.5 1.1 0.89 0.36
Zr 0.1 11% - - - 0.68 - 0.60 0.20 - 0.14
Nb 0.1 3.1% - 0.19 - 0.26 - 0.20 - - -
Mo 0.1 4.9% - 1.7 - 0.75 - 0.60 0.17 0.15 0.29
Ru 0.1 - - - - - - - - - -
Pd 0.1 - - - - - - - - - -
Ag 0.1 1.8% - - - - - - - - -
Cd 0.05 12% - 0.06 - - - 0.07 - - 0.07
In 0.05 19% - - - - - - - - -
Sn 0.5 4.8% - - - - - - - - -
Sb 0.05 6.0% - - - - - - - - -
Te 0.1 30% - - - - - - - - -
Cs 0.1 5.3% - 0.30 - 0.43 - 0.46 0.28 0.21 0.19
Ba 0.1 4.8% 0.61 32 0.30 15 0.32 15 160000 140000 51
La 0.05 2.1% - 0.72 - 1.6 - 1.3 1.3 1.1 0.43
Ce 0.05 3.1% - 1.6 - 3.2 - 2.8 1.3 0.86 0.88
Pr 0.05 2.5% - 0.20 - 0.38 - 0.36 0.17 0.11 0.11
Nd 0.05 2.3% - 0.84 - 1.5 - 1.6 0.7 0.46 0.45
Sm 0.05 11% - 0.19 - 0.31 - 0.36 0.71 0.65 0.11
Eu 0.05 10% - - - - - 0.09 12 12 -
Gd 0.05 10% - 0.21 - 0.30 - 0.42 0.17 0.12 0.11
Tb 0.05 3.6% - - - - - 0.06 - - -
Dy 0.05 3.6% - 0.14 - 0.19 - 0.33 0.12 0.08 0.08
Ho 0.05 5% - - - - - 0.06 - - -
Er 0.05 4.9% - 0.06 - 0.09 - 0.16 0.06 - -
Tm 0.05 7.3% - - - - - - - - -
Yb 0.05 7.1% - - - 0.06 - 0.14 0.05 - -
Lu 0.05 5.5% - - - - - - - - -
Hf 0.05 8.7% - - - - - - - - -
Ta 0.05 16% - - - - - - - - -
W 0.05 20% - 0.1 - 0.17 - - - - -
Os 0.05 - - - - - - - - - -
Ir 0.05 - - - - - - - - - -
Pt 0.05 - - - - - - - - - -
Au 0.05 - - - - - - - - - -
Hg 0.5 - - - - - - - - - -
Tl 0.05 11% - - - - - - - - -
Pb 0.05 4.1% - 1.1 - 1.3 - 1.5 0.62 0.46 1.3
Bi 0.05 9.6% - 0.09 - - - - - - -
Th 0.05 5.5% - 0.51 - 1.8 - 0.43 0.55 0.36 0.32
U 0.5 - - - - - - - - - -

DL: Detection limit
%RSD presents the percentage relative standard deviation made as common estimate based on the relative standard deviation from duplicate determinations.

4.2.2 Inorganic quantitative measurements

The quantitative measurements of inorganic substances in the selected henna products are shown in the tables below.

Table 5. Quantitative measurements of lead (Pb) in henna products

Sample number Pb
mg/kg
1 -
2 1.37
3 0.89
4 -
5 2.0
8 1.5
9 -
10 -
11 -
12 1.24
14 -
20 1.5
21 -
23 1.7
57 0.57
58 0.47
63 1.3
%RSD 6.7

”-” denotes measurement below detection limit of 0.1 mg/kg.
%RSD presents the percentage relative standard deviation made as common estimate based on the relative standard deviation from duplicate determinations.

Correspondingly, quantitative determinations of elements, which at the screening were measured at a concentration above 10 mg/kg, were performed. However with the exception of normally occurring elements such as aluminium, calcium, iron, magnesium, silicon and titanium and the alkali metals, which were included. The results are listed in the tables below.

Table 6. Quantitative measurements of other elements in henna products

Sample number B
mg/kg
Ba
mg/kg
Mn
mg/kg
Sr
mg/kg
1 - - - -
2 112 37 189 407
3 157 47 230 710
4 - - - -
5 110 31 144 406
8 48 24 78 219
9 - - - -
10 - - - -
11 - - - -
12 60 49 104 272
14 - - - -
20 57 26 91 145
21 - - - -
23 111 24 234 307
57 53 178000 45 296
58 35 170000 65 357
63 43 65 122 180
%RSD 3.0 6.7 2.2 2.1

”-” denotes measurement below detection limit of 0.1 mg/kg.
%RSD presents the percentage relative standard deviation made as common estimate based on the relative standard deviation from duplicate determinations.

It is noted that:

  • Lead (Pb) occurs in 10 out of 17 products at the range 0.5 to 2.0 mg/kg.
  • Boron (B) occurs in 10 out of 17 products at the range 35 to 157 mg/kg.
  • Barium (Ba) occurs in 10 out of 17 products at the range 24 to 178000 mg/kg. Barium was found at high concentration in product no. 57 (178000 mg/kg corresponding to 17.8% m/m) and at almost the same concentration in product no 58. The remaining products were found at the range 24 to 65 mg/kg.
  • Manganese (Mn) occurs in 10 out of 17 products at the range 45 to 234 mg/kg.
  • Strontium (Sr) occurs in 10 out of 17 products at the range 145 to 710 mg/kg.

4.2.3 Organic quantitative measurements

The primarily selected 17 henna products were analysed quantitatively for the content of para-phenylenediamine and lawsone.

p-Phenylenediamine was found in 3 products: In product no. 58 at a low concentration near the detection limit. In product no. 11 in a tube containing paste, p-phenylenediamine was found at 5000 mg/kg corresponding to 0.5% m/m. In product no. 57, 170000 mg/kg was found, corresponding to 17% m/m, cf. table 7.

Based on the results of the lawsone analyses, the Danish Environment Protection Agency decided that also the remaining henna products should be analysed for lawsone.

The results are presented below.

Table 7. Quantitative measurements of p-phenylenediamine and Lawsone in henna products

Sample number p-phenylenediamine
mg/kg
Lawsone
mg/kg
1 < 20 < 20
2 < 2 310
3 < 2 40
4 < 2 < 20
5 < 2 3300
8 < 2 1300
9 < 2 < 20
10 < 2 < 20
11a (bag with paste) < 2  
11b (tube with paste) 5000 < 20
12 < 10 1100
14 < 2 390
20 < 20 160
21 < 2 < 20
23 < 20 1500
57 170000 50
58 27 190
63 < 20 3400
%RSD* 11 26
Supplementary measurements for lawsone:
4   < 20
6   2100
7   730
13   < 20
15   < 20
17   < 20
18   91
22   < 20
%RSD   11

*: %RSD presents the percentage relative standard deviation made as common estimate based on the relative standard deviation from duplicate determinations.

Lawsone was found in 11 out of the 17 initially analysed products above the detection limit of 20 µg/g (= mg/kg). The 16 of the 17 samples had declared to contain lawsone (Lawsonia inermis). Only product no. 3 had not declared to contain lawsone or Lawsonia inermis but a different plant species (Indigofera tinctoria).

The highest concentration of lawsone was found in product no. 63 that was a foreign import from India and without an ingredients list. The highest found concentration was 3400 mg/kg corresponding to 0.34% (m/m). The next highest concentration of lawsone was found in product no. 5 manufactured in the United Kingdom. The product contained 3300 mg/kg corresponding to 0.33% (m/m). The remaining products contained lawsone below the detection limit (6 products) or had concentrations between 38 and 1500 mg/kg, i.e. between 0.004 and 0.15% of the product.

In the supplementary analyses, a further 8 products were analysed. Five of the products contained lawsone below the detection limit while 3 products were above the detection limit containing 91, 730 and 2100 mg/kg, respectively, cf. table 7. The concentration of lawsone in product no. 6 of 2100 mg/kg corresponds to 0.21% (m/m). Product no. 6 is produced by the same manufacturer in United Kingdom as the aforementioned product no. 5.

 



Version 1.0 September 2005, © Danish Environmental Protection Agency