Peer-reviewed article

CONSUMER SAFETY & ANALYTICAL METHODS

Andrew D. Hardy

The chemical composition of traditional eye in Sudan ANDREW D. HARDY1*, PETER BARSS2, GAVYN ROLLINSON3, RAGINI VAISHNAV4 *Corresponding author 1. University of Exeter, Centre for Medical History, College of Humanities. Exeter, EX4 4RJ, Devon, United Kingdom 2. United Arab Emirates University, Department of Community Medicine, Faculty of Medicine and Health Sciences Box 17666, Al Ain, United Arab Emirates 3. University of Exeter in Cornwall, Camborne School of Mines, College of Engineering, Mathematics and Physical Sciences Tremough Campus, Penryn, TR10 9EZ, Cornwall, United Kingdom 4. Sultan Qaboos University, College of Medicine, Box 35, Al-Khod 123, Sultanate of

child not look attractive). Specifically in Sudan, adult females ABSTRACT: This study was undertaken in order to use to outline the upper and lower lids of their eyes, a determine the chemical composition of traditional eye bridegroom may have kohl applied to his eyes for the cosmetics (“kohls”) available in Sudan. A total of 21 kohl wedding ceremony and the same is often done to tiny/new- samples were purchased in local markets (“souks”). The born babies in the early weeks of life. Also, (black) kohl is used techniques of X-ray powder diffraction (XRPD) and low for staining tattoos and scars black. vacuum scanning electron microscopy (LVSEM) were To our current knowledge this study is the first to chemically used to analyse the samples. Overall, for the 21 samples, analyse modern-day traditional eye cosmetics available in Sudan. it was found that 7 (33 percent) contained a lead compound (, PbS) as the main component; with a further 1 sample having it present as a minor MATERIALS AND METHODS component. The other main components were found to be one of the following: amorphous carbon/a carbon- In both traditional and modern markets (“souks”), at nine based compound (6/1), iron compounds (goethite, locations, a total of 24 samples were purchased. These nine FeO(OH) and hematite, Fe2O3 mixtures) (3), calcite/ locations were: Al Ubayyid, Bahri, Kassala, Khartoum, Malakal, aragonite (CaCO3) (1/1), zincite (ZnO) (1) and halite Omduran, Port Sudan/Said , Wadi Halfa and Wadi Madani. (NaCl) (1). Eight of them are shown on the map of Sudan (Figure 1). The one location not shown, Bahri, is in fact a few kms. NE of Khartoum. INTRODUCTION

As part of our continuing study of traditional eye cosmetics (kohls) we have looked at the chemical composition of such cosmetics available in Sudan; with especial reference to determining the percentage of the samples purchased that contain a lead compound. For useful background information on traditional eye cosmetics in general, and on our previously studied ones in particular, the reader is referred to our previous publications on the kohls of Egypt (1-3), Oman (4), the United Arab Emirates (UAE) (5, 6), Qatar and (7), Morocco (8) and most recently Syria (9). Some recent relevant mentions of traditional eye cosmetics in the published literature are the elemental analyses of some kohl samples seized in France (10) - where most of the samples (14 of 18) contained lead, an analysis of a single lead-containing eyeliner and a study of its negative effects on rat liver and brain (11), and a study of elevated blood lead levels in children in where surma (an Indian name for traditional eye cosmetics) use was found to be a predictor of such elevated lead levels (12). Traditional eyeliner (i.e. kohl) is in general used for a variety of reasons: to make the eyes beautiful (e.g. to make the eyes appear larger); as an eye medicine for a variety of complaints (actual and as a preventive); as a daily tradition from both Figure 1. A map of Sudan before the indipendence of South Sudan cultural and religious backgrounds; and as a preventive for on July 9th, 2011. children against the “”/“the evil one” (i.e. making the

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On later inspection, two of these 24 samples were found to be with zincite (ZnO) and halite (NaCl) being the major medicines and were not in fact used as traditional eye components of the remaining 2 samples. Figure 3 shows the cosmetics. Also, two labelled samples (made in Saudi Arabia), distribution of the main element of the major component in all purchased in two different locations, were found to be the kohl samples studied. identical and so only one was included in those to be fully chemically characterised. These 21 samples are regarded as being representative of the kohl samples readily available in the various souks of Sudan. Of the 21 samples, 10 were made in Sudan and the other 11 were made abroad (6 in Saudi Arabia, 4 in India and 1 in Pakistan). Most (15) of the samples were black/grey-black/silvery-grey in colour; with 3 being various shades of red, 2 white/grey-white and 1 yellow. The price per kohl sample was between 2 and 14.5 SNP (Sudan New Pound), where 1 SNP was equivalent to 0.49 US$. A selection (5) of some of the kohl samples purchased are shown in Figure 2.

Figure 3. Distribution of the main element of the major component in the Sudan kohl samples.

A total of 6 samples were coloured (i.e. not black/grey-black/ silvery-grey). For the 3 shades-of-red samples the colourant was a mixture of iron compounds (goethite and hematite) and for the grey-white (1) and white (1) samples the colour was given by the presence of aragonite and halite. The one remaining coloured sample was yellow, where its colour arises from one or more of the currently unknown amorphous Figure 2. A selection (5) of the kohls purchased in Sudan. organic (i.e. carbon-based) major component(s). The sample has been tentatively identified as “Gum ” and it is assumed that it is burnt to give amorphous carbon --- for The 21 kohl samples were examined by the analytical making a black kohl. For the 15 samples that were black/grey- techniques of x-ray powder diffraction (XRPD) and low black/silvery-grey their colour was usually given by their major vacuum scanning electron microscopy (LVSEM) (with the latter components - that is amorphous carbon (6) and galena (7). technique having an energy dispersive x-ray (EDX) However, for two samples their colour - black - was given by a microanalyser attached). The latter technique was used to minor component. For one sample (based on zincite) the give quantitative elemental analysis for atomic number of 6 (black) minor components were amorphous carbon and

(i.e. carbon) and above; whilst the former technique was used magnetite (Fe2O3); and for the other sample (based on to identify crystalline compounds present and to give (semi- calcite) it was graphite. quantitatively) their percentages.

DISCUSSION RESULTS Toxicology of lead For the 21 kohl samples purchased it was found that 7 had As has been stated before by us in our previous publications galena (PbS) present as the main component, with a further 1 (1-9), lead compounds are toxic by ingestion, inhalation and by sample having it present as a minor component. Two of the 7 skin exposure. Children are more susceptible than adults to lead (galena-based) samples were matt in texture, and 4 of the poisoning as adults absorb 5-15 percent of ingested lead while remaining 5 samples are described (by us) as “shiny”, with the children can absorb as much as 41 percent. The toxic effects of remaining sample being described as “very shiny”. The lead form a continuum from clinical or overt effects to more meaning/importance of the texture of a galena-based subtle ones (13). The critical effects in infants and children sample is mentioned in the later Toxicology (sub)section. The involve the nervous system. Values in children, of their blood colours of these 7 samples varied between black (1), grey- lead levels (BLLs), that are greater than 10 µg/dl are now black (5) and silvery-grey (1). Also, six samples were based on considered abnormal (14, 15), and it has been shown that amorphous carbon and one was based on one or more significant intellectual impairment occurs in young children who unknown amorphous compound(s) - which were assumed to have blood lead levels below 10 µg/dl (16, 17). be carbon-based; and three samples were based on iron In a previous publication (1) we discussed galena’s (lead sulfide, compounds (being mixtures of goethite (FeO(OH)) and PbS) particle size with respect to the associated kohl powder hematite (Fe2O3)). One of the latter samples contained being “shiny” or “matt” in texture and with respect to its rate of galena as a minor component (at approx. 21 percent). dissolution in gastric fluid. It was found by us that at a mean Additionally, two samples had calcium carbonate as the particle size for galena of about 10 µm the kohl powder (with major component (once as calcite and once as aragonite); galena as the major component) became totally matt in

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texture. Above this particle size the sample becomes percent). Thus the first of these two samples could probably increasingly “shiny”. It had previously been found (18) that cause lead toxicity if ingested by a child, and the second reducing the particle size of galena leads to a significant sample could possibly cause such toxicity. increase in its rate of dissolution in gastric fluid. Thus a matt For the sample made in India (“Hind Ka Noor Eyeliner”, and galena-based powder would be much more easily dissolved in black in colour) the medicinal information given on the gastric fluid than a “shiny”/“very shiny” powder; with the latter enclosed leaflet stated: “Protects you permanently from perhaps going straight through the body with minimum diseases of the eye” and “Very advantageous against the absorption and negligible toxicity. Two such samples in this study weakness of the eye, or water in the eye, or dirt, or eye pain, or are described as “matt” and both were made abroad (Saudi inflammation”. This sample was found to be based on Arabia and Pakistan). Thus these two “matt” samples are more amorphous carbon, with minor components of

likely than the other galena-based samples to give rise to lead (Mg3Si4O10(OH)2) and quartz (SiO2). Thus whilst these ingredients toxicity. are unlikely to cause toxicity if ingested in small amounts, we feel the medicinal claims are excessive. Written information on the container/packaging Only one of the three samples with medicinal information given Four of the samples had written information on the sample’s in English had any details. This was the Indian-made sample, contents. These samples were made in India (3) and “Harmain’s Surma”, and on an enclosed leaflet was stated: Pakistan (1). “Most helpful in the treatment of all kinds of eye troubles such The sample made in Pakistan (“Hashmi Surmi Special”) as: Eye weakness, Haziness, Tears, Eye dirt, Burning Eyes, stated, in , that the sample contained (with our Scratching, Redishness Etc” and “Harmain’s SURMA strengthens interpretations/comments given in brackets in italics): “Stone the vision and gives a cooling effect to the eyes whilst it fights of Basra” (perhaps a calcium/iron/zinc-based mineral), disease”. This sample was found to be a “shiny” grey-black “Ground Zinc” (perhaps zincite), “Aniseed oil”, “A medical powder with galena as its major component and with talc,

root” (possibly a plant root) and “Black Surma” (a term anglesite (PbSO4) and cerussite (PbCO3) as the minor sometimes used to indicate the presence of galena). Its components. Thus its medicinal claims are unlikely at best and major component was in fact galena (and it was a black outrageous at worst. matt powder), but none of the other compounds listed on its The other two samples gave much less information (in English) packaging were in fact found by us. on their medicinal uses. One, “Khojati DeLux Surma with Almond One (“Hind Ka Noor Eyeliner”) of the three Indian-made oil”, merely stated: “Purely herbal. With a mild astringent effect. samples gave, in English on its container, qualitative information Unani medicine”. As it was found to be a black sample based on its contents: “Carbon Black” (i.e. amorphous carbon, which on zincite (with minor components of calcium carbonate, was found as its major component and which gave it a black amorphous carbon, quartz and magnetite) then its toxicity colour), “Camphor” and “Menthol” (both organic carbon- would be low if ingested. The last sample, “Khojati Surma Sada”, based compounds, neither of which was found in the sample). stated on its container: “Unani Medicine. For external use in the The other two Indian-made samples gave quantitative eye only”. However, on an enclosed leaflet was stated: “it does information, in English, on their packagings. One (“Khojati Surma not make the eyes water and can be used for children below 8 Sada”, a grey-black ‘shiny’ powder) merely said “Asmad (100)” years” (our italics). As this (“shiny”) grey-black sample was found and “Ground in natural extracts”. The word “Asmad” is usually to be based on galena (with minor components of anglesite taken to mean “a (crushed if powder) rock from Saudi Arabia” - and cerussite) then this suggested usage on young children, where the “rock” is often galena - and which was found to be even if only external, is to be challenged. the sample’s major component. The third Indian-made sample (“Khojati DeLux Surma with Almond oil”, and black in colour) Comparison with other studies gave the most detailed information on its contents (with our Of the 21 kohl samples studied here it was found that 8 (38 interpretations/comments given in brackets in italics): “Sang-e- percent) contain a lead compound (galena, PbS), either as a Basari (17.00) (soaked in 5 percent Almond oil)” (“Stone of major (7) or minor (1) component. This percentage is lower than Basra”, as before), “Gile Surkh (50.00)” (“red ochre”, that is some those found in several (6 of 10) of our other country studies (1-9 form of red iron oxide, possibly hydrated), and “Sufoof-e-Syah and see Figure 4). For the three other studies done on kohls (33.00)” (“Black from oil of Almond”, probably amorphous carbon). Zincite was found to be its major component, with minor components of calcium carbonate, amorphous carbon, quartz and magnetite. As regards data on the medicinal effects to be obtained from using a particular sample, six of our samples gave such information in writing - three in Arabic and three in English. Two of the former samples were from Saudi Arabia and one from India. The information given on the packagings of the two samples from Saudi Arabia were: “Refreshes and purifies the eye” and “Strengthens the muscles of the eye” for the “Kohl Original Stone” sample (which was found to be a galena-based grey-black matt powder); and “Sweetens the sight” for the “Asmad” named sample (which was found to be surprisingly based on a mixture of goethite and hematite, is red-brown in colour and contains galena as Figure 4. Previous XRPD data on kohls. only a minor component of approx. 21

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using XRPD (19-21 and Figure 4) our percentage lead value is main components found in our samples were: amorphous lower than that found for the samples purchased in the United carbon/a carbon-based organic molecule (6/1), iron Kingdom (55 percent) (19), and much lower than the values compounds (goethite and hematite) (3), calcium carbonate found in Kuwait (85 percent) (20) and Nigeria (100 percent) (21). (as calcite or aragonite) (2), zincite (1) and halite (1). There are other significant differences, and some similarities, This study shows that traditional eye cosmetics (“kohls”) were between the results obtained here and in our other country readily available in the various souks of Sudan, and about 1 in studies. For the kohls of Sudan we have found that six of twenty- any 3 purchased would contain a lead compound (galena). Of one (29 percent) samples were coloured (i.e. shades of red (3), the samples where labelling was present there would be no real grey-white/white (2) and yellow (1)), and all were being used by information of lead’s presence (though it was perhaps the local population. Only one of these six coloured samples “indicated” for two samples). Some (2 of 7) of the galena- contained a lead compound --- that is galena as a minor based kohls contain it in a form (i.e. small particle size) that component of a red-brown sample from Saudi Arabia. In some makes it more easily absorbed into the human gut. We can only of our other studies we have found coloured kohls, but usually reiterate that this element has no known biological value and is only for sale to the tourists (e.g. Egypt (1-3)). In one of the three an insidious cumulative poison having potentially devastating previous studies done by us on kohl samples from modern-day cognitive effects if applied regularly to young children. Egypt (3), we found that two of the five coloured samples studied contained lead compounds. However, a lead compound was found in five of the eight coloured samples ACKNOWLEDGEMENTS purchased in Syria (9); where these kohls were all used by the local inhabitants. We would like to thank the following people for their help in the Five the 21 samples studied here were made in India (4) or course of this study: Mr. Paul Auchterlonie (Librarian for Middle Pakistan (1). This is unlike the kohls from: Oman (17 of 39), Qatar East Studies, Exeter University, United Kingdom) for Arabic (17 of 19), the United Arab Emirates (16 of 18 in Abu Dhabi city translations and Prof. Sajjad Rizvi (Institute of Arab and Islamic and 38 of 53 in the other six Emirates); but similar to those from Studies, Exeter University, United Kingdom) for the Urdu Egypt (3 of 41), Yemen (3 of 9), Morocco (1 of 9) and Syria translations. Also, we would like to thank the staff of the (none). Also, like Egypt (34 of 41), Yemen (at least 4, and Chemical and Materials Analysis Unit (University of Newcastle, possibly 6, of 10), Syria (13 of 18) and Morocco (8 of 9); but United Kingdom) for the experimental LVSEM work mentioned in unlike Qatar (none) and the Emirates (1 found overall), the this article. number of samples made within the country of purchase (Sudan) is high (10 of 21). Also, the number of our samples found with no written (name) labels was high (13 of 21); which is slightly REFERENCES AND NOTES lower than that found in Morocco (6 of 9) and much lower than 1. A. D. Hardy, R. I. Walton et al, Int. J. Environ. Health Res., 14 (1), pp. in Syria (15 of 18), but higher than found in Oman (approx. half 83-91 (2004). of the samples) and Yemen (6 of 10) and much higher than 2. A. D. Hardy, R. I. Walton et al, “Egyptian Eye Cosmetics (“Kohls”): Past Egypt, Qatar and the Emirates (8 of 41, 1 of 19, and 7 of 71 and Present”, in: Physical Techniques in the Study of Art, Archaeology samples respectively). and Cultural Heritage Vol. 1, D. Bradley and C. Creagh (Eds.), Elsevier, For the 6 samples that were made in Saudi Arabia, 3 (50 pp. 173-203 (2006). percent) contained galena as the main component. The other 3. Andrew D. Hardy, Gavyn Rollinson et al, House. Pers. Care Today, 4 three (shades-of-red) samples made in Saudi Arabia (two of (Supple.), pp. 14-16 (2009). which were made in Medina) were all based on iron 4. A. D. Hardy, R. Vaishnav et al, J. Ethnopharmacol., 60, pp. 223-234 compounds (goethite and hematite mixtures). One of them, (1998). made in Medina, containing a significant amount of galena 5. A. D. Hardy, H. H. Sutherland et al, J. Ethnopharmacol., 80 (2-3), pp. 137-145 (2002). (approx. 21 percent) as a minor component. A recent study of 6. Andrew D. Hardy, Richard I. Walton et al, J. Cosmet. Sci., 57, pp. 107- the (elemental) composition of kohls purchased in Saudi Arabia 125 (2006). showed that 12 (75 percent), of the 16 samples purchased, 7. Andrew D. Hardy, Alexander J. Farrant et al, J. Cosmet. Sci., 59, pp. contained lead (range: 12 to 78 percent) (22). 399-418 (2008). The two white kohls purchased were found to consist of a 8. Gavyn Rollinson, Andrew D. Hardy et al, House. Pers. Care Today, 2, mixture of aragonite and halite. The source material for these pp.12-15 (2010). samples were cuttlefish bones; where cuttlefish are sea-water 9. Andrew D. Hardy, Gavyn Rollinson et al, House. Pers. Care Today, 4, molluscs. The local name for white kohl is kohl al-malayika (i.e. pp. 24-28 (2010). angels’ kohl), and is said to usually consist of sulphate 10. Catherine Sainte, Sophie Gille et al, Ann. Toxicol. Anal. , Published online (DOI: 10.1051/ata/2010029) (2011). (Sb2(SO4)3) --- although lead sulphate/oxide (PbSO4/PbO) are 11. R. O. Arise, A. C. Tella et al, Int. Res. J. Biotechnol. , 1 (4), pp. 59-64 said to sometimes be present as adulterants (23). None of these (2010). compounds were found in our samples. It is used as a medicine 12. A. Patel and A. Athawale, Ind. Paediatr. , 46, pp. 845-848 (2009). and also in averting the “evil eye”. White kohl samples have 13. R. A. Goyer, Environ. Health Perspect. , 86, pp. 177-181 (1990). been seen before by us; four were bought in the United Arab 14. R. P. Wedeen, Int. J. Occup. Environ. Med. , 2 (1), pp. 1-3 (2011). Emirates (5, 6), two in Oman (4) and one each in Egypt (2) and 15. C. D. Klaasen, Casarett and Doull’s Toxicology, the Basic Science of Qatar (7). The main components were found to be sassolite Poisons, 5th Ed., McGraw-Hill, pp. (1996).

(H3BO3) in five samples, calcite in two and talc in one sample. 16. R. L. Canfield, C. R. Henderson et al, New Eng. J. Med., 348 (16), pp. These samples were made in Pakistan, India and Pakistan, and 1517-1526 (2003). Egypt respectively. 17. M. M. Tellez-Rojo, D. C. Bellinger et al, Pediatrics, 118 (2), pp. 323-330 (2006). 18. M. A. Healy, P. G. Harrison et al, J. Clin. Hosp. Pharm., 7, pp. 169-173 (1982). CONCLUSIONS 19. M. Aslam, S. S. Davis et al, Pub. Health, 93, pp. 274-284 (1979). 20. N. P. Fernando, M. A. Healy et al, Pub. Health, 95, pp. 250-260 (1981). In the 21 kohl samples analysed in this study, 8 (38 percent) 21. M. A. Healy, M. Aslam et al, Pub. Health, 98, pp. 26-32 (1984). samples had galena (PbS) present to some degree (7 as the 22. O. M. Badeeb, R. S. Ajlan et al, JKAU: Med. Sci. , 15 (4), pp. 59-67 (2008). main component and 1 as a minor component). The other 23. See (under ‘K’): www.sudan-health.net/recipes/hs120.htm.

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