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Andrew D. Hardy

The chemical composition of traditional eye cosmetics in Syria ANDREW D. HARDY1*, GAVYN ROLLINSON2, RAGINI VAISHNAV3 *Corresponding author 1. University of Exeter, Centre for Medical History, College of Humanities, Exeter, EX4 4RJ, Devon, United Kingdom 2. University of Exeter in Cornwall, Camborne School of Mines, College of Engineering Mathematics and Physical Sciences, Tremough Campus, Penryn, TR10 9EZ, Cornwall, United Kingdom 3. Sultan Qaboos University, College of Medicine, Box 35, Al-Khod, 123, Sultanate of Oman

MATERIALS AND METHODS ABSTRACT: This study was undertaken in order to determine the chemical composition of potentially lead-toxic The main souk (Al Hamidiyeh, see Figure 1) in Damascus was traditional eye cosmetics (“kohls”) available in Syria visited several times and a total of 14 kohl samples purchased. (Damascus and Aleppo). A total of 18 kohl samples were A selection (4) of these samples are shown in Figure 2. A later, obtained: 14 in the main souk of Damascus and 4 in the old brief, visit to Aleppo’s old souk resulted in 3 such samples being souk of Aleppo. The techniques of X-ray powder diffraction purchased. Additionally, another kohl sample from Aleppo (XRPD) and low vacuum scanning electron microscopy souk (but purchased in c. 1976) was donated by a family (LVSEM) were used to analyse the samples. Overall, for the friend. These 18 samples are regarded as being representative 18 samples, it was found that 10 (56 percent) contained a of the kohl samples readily available in these two souks; lead compound (galena, PbS) as the main component; especially with regard to those made in Syria. Of the 18 with a further 5 samples having it present as a minor samples obtained overall, 13 were made in Syria and 8 were component. The other main components were found to be coloured (i.e. not black/grey-black/grey/silver-grey). The price one of the following: calcite (5) (CaCO3), sassolite (2) per kohl sample was usually between 0.5 and 1.5 US$, but (H3BO3) and goethite (1) (FeO(OH)). occasionally the price was higher and once as much as 6 US$. These 18 kohl samples were examined by the analytical techniques of x-ray powder diffraction (XRPD) and low INTRODUCTION vacuum scanning electron microscopy (LVSEM) (with the latter technique having an energy dispersive x-ray (EDX) As part of our continuing study of traditional eye cosmetics microanalyser attached). The latter technique was used to (kohls) we have looked at the chemical composition of such cosmetics available in Syria; with especial reference to determining those containing 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 Yemen (7), and, most recently, Morocco (8). Some recent relevant mentions of traditional eye cosmetics in the published literature are the chemical (elemental) analyses of samples purchased in Saudi Arabia (9) and Boston (Massachusetts, USA) (10), and a study of their usage in Delhi (India) (11). To our current knowledge this study is the first to chemically analyse modern-day traditional eye cosmetics available in Syria. Traditional eyeliner (i.e. kohl) is 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 cultural and religious backgrounds; and as a preventive for children against the “evil eye”/”the evil one” (i.e. making the child not look attractive). Thus, presented here, as part of our ongoing study into the presence of lead in traditional eye cosmetics (kohls) and as part of an ongoing education on the toxicity - especially for young growing children - of using such materials, is a chemical Figure 1. The main souk (Al Hamidiyeh) of Damascus (Syria). composition study of the kohls available in Syria.

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give quantitative elemental analysis for atomic number of 6 blue samples the colourant was a minor component of lazurite (i.e. carbon) and above; whilst the former technique was used (of formula Na8.16(Al6Si6O24)(SO4)1.14S0.86) in one sample to identify crystalline compounds present and to give (semi- and, in the other sample, an unknown (and again, probably quantitatively) their percentages. organic and of small amount) colourant. Only 5 of the 18 samples purchased were made outside Syria, with all five being made in Saudi Arabia.

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

DISCUSSION

Toxicology of lead As has been stated before by us in our previous publications (1-8), lead compounds are toxic by ingestion, inhalation and by skin exposure. Children are more susceptible than adults to lead intoxication. Adults absorb 5-15 percent of ingested Figure 2. A selection (4) of the kohls purchased in Damascus. lead while children can absorb as much as 41 percent of ingested lead. The toxic effects of lead form a continuum from clinical or overt effects to more subtle ones (12). The RESULTS critical effects in infants and children involve the nervous system. Blood lead levels (BLLs) once thought to be safe have For the 14 samples purchased in the main souk of Damascus it been shown to be associated with intelligence quotient was found that 9 had galena as the main component, with a deficits, behavioural disorders, slowed growth and impaired further 4 having it present as a minor component. For the four hearing (13, 14). Values in children, of their BLLs, that are samples purchased in Aleppo souk these numbers were 1 and greater than 10 µg/dl are now considered abnormal (15), 1 respectively. Five of the 10 (lead-based) samples were matt and recently it has been shown that significant intellectual in texture, and 3 of the remaining 5 samples are described (by impairment occurs in young children who have blood lead us) as only “slightly shiny”, with the levels below 10 µg/dl (16, 17). These remaining 2 samples being described as findings are of immediate concern for “shiny”. The meaning/importance of the Kohl highlights the eyes; those young children living in areas texture of a galena-based sample is but it can also lead- where significant kohl usage has been mentioned in the later Toxicology (sub) poison the body found (e.g. Delhi, India (11)). Also, very section. The colours of these 10 galena- recently, the composition (with regard based samples varied between black to their lead content) and usage of (6), grey-black (1), red-brown (1), green (1) and dark blue (1). Indian-made eye-liners (“Kajal”) available in Boston (USA) has Additionally, five samples had calcite (CaCO3) as the major been studied (10). This study showed that whilst the eye-liners component; with sassolite (H3BO3) and goethite (FeO(OH)) contained small amounts of lead (mean value: 7.6 ppm, and being the major components for 2 and 1 samples respectively a range of 1 to 41 ppm per sample, over 16 such samples), it of the remaining 3 samples (see Figure 3 for the distribution of was suggested by the paper’s authors that chronic exposure the main element of the major component in all the kohl to such samples may cause elevated BLLs in young children. samples studied). In a previous publication (1) we discussed galena’s (lead A total of 8 samples were coloured (i.e. not black/grey-black/ sulfide, PbS) particle size with respect to the associated kohl grey/silver-grey), and the nature of the colourant varied. For powder being ‘shiny’ or ‘matt’ in texture and with respect to the 4 green/dark green samples the colourant was an its rate of dissolution in gastric fluid. It was found by us that at unknown (and probably organic) minor component (though a mean particle size for galena of about 10 µm the kohl for one sample it could be an unidentified minor component powder (with galena as the major phase) became totally chromium compound); for the 2 red-brown/red-grey samples matt in texture. It had previously been found (18) that the red colour was given by one or more iron-based reducing the particle size of galena leads to a significant compounds(s) - that is goethite in one sample and hematite increase in its rate of dissolution in gastric fluid. Thus a matt and goethite in the other sample; and for the two blue/dark galena-based powder would be much more easily dissolved

26 Household and Personal Care TODAY - n 4/2010 CONSUMER SAFETY in gastric fluid than a “slightly shiny”/“shiny” powder; with the powder - “Kuhl Asmad”) and would probably arise from using latter perhaps going straight through the body with minimum the other sample (as it is a galena-based matt powder - absorption and negligible toxicity. Five such samples in this “Madani Al Ethmad”). study are described as “matt” and all were purchased in the main souk of Damascus. Their colours vary from green (1), to red-brown (1), to black (3) and all except one were made in COMPARISON WITH OTHER STUDIES Syria. This one exception sample was made in Saudi Arabia (Medina), was the most expensive kohl purchased (at 6 US$), Of the 18 kohl samples studied here overall it was found that 15 and the shop-keeper described it as “hot” (i.e. it could also (83 percent) contain a lead compound (galena, PbS), either as a be used as an eye medicine). Thus these five ‘matt’ samples major (10) or minor (5) component. This percentage is higher than are more likely than the other galena-based samples to give those found in all our other country studies (1-8 and Figure 4). For rise to lead toxicity, though the higher purchase price of one the three other studies done on kohls using XRPD (19-21 and Figure could deter its usage. 4) our percentage lead value above is larger than that found for the samples purchased in the United Kingdom (55 percent) (19), Written information on container/packaging but less than the values for those kohls purchased in Kuwait (85 Only three of the samples have any (qualitative) information on percent) (20) and Nigeria (100 percent) (21). the sample’s contents. These samples were all made in Saudi Arabia (Medina). All three have the same words (in Arabic) on their packaging (with our interpretations in brackets in italics): “100 percent Original”, “100 percent pure” and “With Zam Zem water” (i.e. holy water from Mecca, Saudi Arabia). As regards data on the medicinal effects to be obtained from using a particular sample; only these same three samples gave any (albeit vague) such information. Two of the samples have the same name (“Kuhl Asmad”; the bottom two samples shown in Figure 2), differing only in the colours of their packagings and of the powders inside their containers, and have (in English) the general phrase “Its increase Eyelight and Grows Eyelashes” on their packagings. The third sample (“Madani Al Ethmad”) has slightly more (medicinal) usage information than Figure 4. Previous XRPD data on kohls. the previous two samples: on the packaging, in Urdu, is stated “Clears the eye” and “Hot” (see below) and also, in English, is stated “It Clears the Eye’s Sight and Causes the There are other significant differences, and some similarities, Hair to Grow”. between the results obtained here and in our other country This last sample was specifically said to be “hot”, by both the studies. For the kohls of Syria we have found that not only were a shop-keeper and the manufacturer. This indicates that this kohl significant number (8 of 18) of coloured (i.e. shades of red, green can also be used as an eye medicine and so could sometimes and blue) samples available, but also that these were used by the be placed inside the eye. The “hot” kohl often contains, or was local population and were not just for sale to the tourists. In some thought to contain, a special ‘active ingredient’ that acts as of our other studies we have found coloured kohls, but only for the eye medicine. The word “Ethmed”/”Ethmad”/”Asmad” was often used to describe this “active ingredient”, which was quite often found to be the lead mineral galena. Galena was in fact the major component of this sample; as well as for one of the previously mentioned samples. The remaining sample with medicinal usage information has a major component of goethite; with no lead-based compounds present as minor components. Thus the limited claims made for this iron-based sample are unlikely to cause toxicity. However, for the other two samples where some form of medicinal usage is indicated by the manufacturer, it is likely that lead toxicity from such usage would possibly arise from using one sample (as it is a galena-based “shiny”

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sale to the tourists (i.e. Egypt (1-3)). Also, for the coloured kohls souk of Aleppo in Syria. If a kohl sample was bought in either of from the main souk of Damascus it was found that 5 of the 6 such these two souks, and especially in the Damascus souk, then there samples contained galena; but that would be a high probability that it would neither of the 2 coloured samples contain a lead compound. Also, on the obtained in Aleppo souk contained any Kohl samples analysed few samples where labelling was present lead compound. Whereas only two of the here had 15 (83 percent) there would be no information of lead’s coloured kohl samples, from one of three of 18 samples found to presence. Moreover, some of these kohls studies of samples from Egypt, contained not only contain lead, but contain it in a any lead compounds (3). Additionally, it contain galena (PbS) to form (i.e. small particle size) that makes it was found for the samples studied here some degree more easily absorbed into the human gut. that none were made in India or Pakistan. We can only reiterate, again, that this This is unlike the kohls from countries element has no known biological value studied by us previously: Oman (17 of 39), Qatar (17 of 19), the and is an insidious cumulative poison having potentially United Arab Emirates (16 of 18 in Abu Dhabi city and 38 of 53 in devastating cognitive effects if applied regularly to young the other six Emirates), Egypt (3 of 41), Yemen (3 of 9) and children. Morocco (1 of 9). Also, like Egypt (34 of 41), Yemen (at least 4, and possibly 6, of 10) and Morocco (8 of 9); but unlike Qatar (none) and the Emirates (1 found overall), the number of samples ACKNOWLEDGEMENTS made within the country of purchase (Syria) is high (13 of 18). The number of our samples found with no (name) labels was also We would like to thank the following people for their help in the high (15 of 18), which is higher than in Oman (approx. half of the course of this study: Mr. Paul Auchterlonie (Librarian for Middle samples), Yemen (6 of 10) and in Morocco (6 of 9); and much East Studies, Exeter University, UK) for translations and to Prof. higher than Egypt, Qatar and the Emirates Pamela Pattie for sample collection. Dr. (8 of 41, 1 of 19, and 7 of 71 samples Ghada Karmi (Visiting Professor to the respectively). Thus only a few of the Even some of the Institute of Arab and Islamic Studies, samples studied here have any data coloured kohls (5 of 8) Exeter University) also very kindly donated available on “contents” (3 of 18) or on contain galena a kohl sample, bought by her in Aleppo “medicinal usage” (the same 3 samples). souk in c. 1976. Mr. Peter Frost assisted us For the 5 samples that were made in Saudi with the XRPD data collection at the Arabia, 4 (80 percent) contained galena. For the 3 named Camborne School of Mines (University of Exeter in Cornwall). Also, samples purchased in Syria, but all made in Medina (Saudi we would like to thank the staff of the Chemical and Materials Arabia), 2 (67 percent) contained galena. In a previous study of Analysis Unit (University of Newcastle, UK) for the experimental kohl samples purchased solely in Saudi Arabia (22) it was found LVSEM work mentioned in this article. that 50 percent (3 of 6) of the Medina-made named samples contained a significant amount of lead, and that for the 13 named samples made in Saudi Arabia overall the percentage REFERENCES AND NOTES containing lead was 46 percent. Also, a more recent study of the (elemental) composition of kohls purchased in Saudi Arabia 1. A.D. Hardy, R.I. Walton et al, Int. J. Environ. Health Res., 14(1), pp. 83-91 showed that 12 (75 percent), of the 16 samples purchased, (2004). contained lead (range: 12 to 78 percent) (9). 2. A.D. Hardy, R.I. Walton et al, Physical Techniques in the Study of Art, A comparison of the chemical composition of black kohl bought Archaeology and Cultural Heritage, 1, D. Bradley and C. Creagh in Aleppo’s old souk over 30 years and in the present shows that (Eds.), Elsevier, pp. 173-203 (2006). both contain galena, but that the present-day sample only had it 3. A.D. Hardy, G. Rollinson et al, House. Pers. Care Today, 4(Supple.), pp. 14-16 (2009). present as a minor component (i.e. at approx. 13 percent) whilst 4. A.D. Hardy, R. Vaishnav et al, J. Ethnopharmacol., 60, pp. 223-234 the one of 30 years ago had it present as the major component (1998). (i.e. at approx. 71 percent). 5. A.D. Hardy, H.H. Sutherland et al, J. Ethnopharmacol., 80(2-3), pp. 137- 145 (2002). 6. A.D. Hardy, R.I. Walton et al, J. Cosmet. Sci., 57, pp. 107-125 (2006). CONCLUSIONS 7. A.D. Hardy, A.J. Farrant et al, J. Cosmet. Sci., 59, pp. 399-418 (2008). 8. G. Rollinson, A.D. Hardy et al, House. Pers. Care Today, 2, pp.12-15 In the 18 kohl samples analysed in this study, 15 (83 percent) (2010). samples had galena (PbS) present to some degree (10 as the 9. O.M. Badeeb, R.S. Ajlan et al, JKAU: Med. Sci., 15(4), pp. 59-67 (2008). main component and 5 as a minor component). For the two 10. C.G. Lin, L.A. Schaider et al, Pediatrics, 125(4), pp. 828-836 (2010). 11. A. Mohta, J. Oman, Ophthal., 3(2), pp. 100-101 (2010). souks visited these numbers become: Damascus main souk 13 (93 12. R.A. Goyer, Environ. Health Perspect., 86, pp. 177-181 (1990). percent) out of 14 and Aleppo’s old souk 2 (50 percent) of 4. 13. H.L. Needleman, A. Schell et al., New Engl. J. Med., 332, pp. 83-88 These galena-containing percentages are high. Higher in fact, for (1990). the Damascus souk, than for any other country or souk studied by 14. J. Schwartz, D. Otto, Arch. Environ. Health, 46, pp. 300-306 (1991). us over the last thirteen years. The other main components found 15. C.D. Klaasen, Casarett and Doull’s Toxicology, the Basic Science of in our samples were: calcite (5), sassolite (2) and goethite (1). Poisons, 5th Ed., McGraw-Hill, (1996). Also, for the Damascus souk, the coloured (i.e. red, green or blue) 16. R.L. Canfield, C.R. Henderson et al, New Eng. J. Med., 348(16), pp. kohls available were found to almost all (5 of 6, 83 percent) 1517-1526 (2003). contain galena and to be used by the local population. 17. M.M. Tellez-Rojo, D.C. Bellinger et al, Pediatrics, 118(2), pp. 323-330 Additionally, a large number (15 of 18, 83 percent) of the samples (2006). 18. M.A. Healy, P.G. Harrison et al, J. Clin. Hosp. Pharm., 7, pp. 169-173 for sale had no labelling whatsoever (and thus no written (1982). information on contents or possible medicinal usage), and these 19. M. Aslam, S.S. Davis et al., Pub. Health, 93, pp. 274-284 (1979). were often made in Syria. 20. N.P. Fernando, M.A. Healy et al., Pub. Health, 95, pp. 250-260 (1981). This study thus shows that traditional eye cosmetics (“kohls”) were 21. M.A. Healy, M. Aslam et al., Pub. Health, 98, pp. 26-32 (1984). readily available in the main souk of Damascus and in the old 22. R.M. Al-Ashban, M. Aslam et al., Pub. Health, 118(4), pp. 292-298 (2004).

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