Sudan University of Science and Technology College of Graduate Studies Investigation the Elemental Composition of Some ‘‘Kohl’’ Samples ﺗﻘﺼﻲ اﻟﺘﻜﻮﯾﻦ اﻟﻌﻨﺼﺮي ﻟﺒﻌﺾ اﻟﻌﯿﻨﺎت ﻣﻦ اﻟﻜﺤﻞ A Thesis Submitted in Partial Fulfilment of the Requirements of theDegree of Master in Chemistry By Balsam Abdalhadi Fadlallah Abdalgader (B.Sc. Honours, Scientific Laboratories, chemistry) Supervised by: Dr. Omer Adam Mohamed Gibla January 2019 إﺳﺘﮭﻼل ﺑﺴﻢ ﷲ اﻟﺮﺣﻤﻦ اﻟﺮﺣﯿﻢ (أﻟﻢ ﺗﺮ أن ﷲ أﻧﺰل ﻣﻦ اﻟﺴﻤﺎء ﻣﺎءً ﻓﺄﺧﺮﺟﻨﺎ ﺑﮫ ﺛﻤﺮات ﻣﺨﺘﻠﻔﺎً أﻟﻮاﻧﮭﺎ وﻣﻦ اﻟﺠﺒﺎل ﺟﺪد ﺑﯿﺾ وﺣﻤﺮ ﻣﺨﺘﻠﻒ أﻟﻮاﻧﮭﺎ وﻏﺮاﺑﯿﺐ ﺳﻮد) ﺳﻮرة ﻓﺎطﺮ(آﯾﺔ27) ﺻﺪق ﷲ اﻟﻌﻈﯿﻢ I Dedication To my parents, my brothers and sister And to my husband Abdullah Ali. II Acknowledgment My endless praise is due to Almighty, Allah for giving me healthand strength to perform this work. My great thanks go to my supervisor Dr. Omer Adam Mohamed Gibla for his continuous encouragement, help and support during his supervision of this work. I would like to thank my father for his financial support. My thanks would also extend tothe membersof Sudanese Petroleum Corporation (SPC)and Khartoum University Laboratories for their help during the analysis of the samples. My thanks also go to Mr.Amin Eldin Issa. I would also like to thank my colleges and my friend rowida abbas for their support. III Abstract This study was aimed to investigate the most major elements, in kohl, as a traditional cosmetic material used by Sudanese. Eight Kohl samples from different sources were purchased from Khartoum state markets, and subjected to elaborate analysis by inductively coupled plasma Optical Emission Spectrometry, to detect the presence of a wide range of minerals. The analysis showed the occurrence of twenty seven elements. The lowest concentrations were shown by Boron (<0.001875 ppm) and Lithium (<0.000387ppm). Very higher concentrations were shown by Lead, Iron, Zinc and Manganese. Calcium, Sodium, Magnesium and Potassium contents, were relatively high. Molybdenum, Phosphors and Aluminium showed various concentrations in the eight samples. IV اﻟﻤﺴﺘﺨﻠﺺ ﺗﮭﺪف ھﺬه اﻟﺪراﺳﺔ إﻟﻰ ﻹﺳﺘﻘﺼﺎء أﻛﺜﺮ اﻟﻌﻨﺎﺻﺮ اﻟﻤﺘﻮﻓﺮة ﻓﻲ اﻟﻜﺤﻞ ﻛﻤﺎدة ﺗﺠﻤﯿﻠﯿﺔ ﺗﻘﻠﯿﺪﯾﺔ اﻟﺘﻲ ﯾﺴﺘﺨﺪﻣﮭﺎ اﻟﺴﻮداﻧﯿﻮن.ﺗﻢ ﺷﺮاء ﺛﻤﺎﻧﯿﺔ ﻋﯿﻨﺎت ﻣﻦ اﻟﻜﺤﻞ ﻣﻦ ﻣﺼﺎدر ﻣﺨﺘﻠﻔﺔ ﻣﻦ أﺳﻮاق وﻻﯾﺔ اﻟﺨﺮطﻮم . ﺗﻢ ﺗﺤﻠﯿﻞ اﻟﻌﯿﻨﺎت ﺑﻤﻄﯿﺎﻓﯿﺔ اﻹﻧﺒﻌﺎث اﻟﻀﻮﺋﻲ ﻟﺒﻼزﻣﺎ اﻟﺤﺚ اﻟﻤﺰدوج ﻟﻠﻜﺸﻒ ﻋﻦ وﺟﻮد ﻣﺪى واﺳﻊ ﻟﻠﻤﻌﺎدن. أظﮭﺮ اﻟﺘﺤﻠﯿﻞ وﺟﻮد ﺳﺒﻌﺔ وﻋﺸﺮﯾﻦ ﻋﻨﺼﺮا ً . أدﻧﻰ ﺗﺮاﻛﯿﺰ أظﮭﺮھﺎ اﻟﺒﻮرو(PPM 0.001875) واﻟﻠﯿﺜﯿﯿﻮم 0.000387PPM) ( أظﮭﺮ ﻛﻞ ﻣﻦ اﻟﺮﺻﺎص ،اﻟﺤﺪﯾﺪ،اﻟﺰﻧﻚ واﻟﻤﻨﻐﻨﯿﺰ ﺗﺮاﻛﯿﺰ ﻋﺎﻟﯿﺔ ﺟﺪا ً .ﻣﺤﺘﻮى اﻟﻜﺎﻟﺴﯿﻮم ،اﻟﺼﻮدﯾﻮم،اﻟﻤﺎﻏﻨﺴﯿﻮم واﻟﺒﻮﺗﺎﺳﯿﻮم ﻋﺎﻟﻲ ﻧﺴﺒﯿﺎ ً .أظﮭﺮ ﻛﻞ ﻣﻦ اﻟﻤﻮﻟﺒﯿﺪﯾﻮم ،اﻟﻔﺴﻔﻮرواﻷﻟﻤﻮﻧﯿﻮم ﺗﺮاﻛﯿﺰ ﻣﺨﺘﻠﻔﺔ ﻓﻲ اﻟﻌﯿﻨﺎت اﻟﺜﻤﺎﻧﯿﺔ . V List of Contents Subject No I إﺳﺘﮭﻼل Dedication II Acknowledgments III Abstract IV V اﻟﻤﺴﺘﺨﻠﺺ List of contents VI List of Tables IX List of Figure X Chapter One 1. Introduction 1 1.1 Kohl 1 1.1.1 Benefits of Kohl 2 1.1.2 Hazards of kohl 3 1.1.2.1 Lead 3 1.1.2.2 Sulphur 4 1.1.2.3 Zinc 4 1.1.2.4 Iron 4 1.1.2.5 Calcium 5 VI 1.1.2.6 Arsenic 5 1.1.3 Kohl in Sudan 5 1.1.4 Kohl in other countries 10 1.2 Inductively Coupled Plasma Optical Emission Spectrometer 12 1.2.1 Principle 12 1.2.2ICP Discharge 16 1.2.3 Nebulizers 17 1.2.4 ICP-OES Interferences-General Considerations 19 1.2.5 ICP-OES Applications 20 The aim of the study 20 Chapter two 2. Materials and Methods 21 2.1 Collection of samples 21 2.2 Chemicals 21 2.3Instruments 21 2.4 Methods of analysis 22 2.4.1 ICP analysis of kohl samples 22 Chapter three 3. Results and discussion 23 3.1.1 Macro minerals contents of kohl samples 23 3.2 Trace minerals contents of kohl samples 24 3.3 Risky minerals contents of kohl samples 26 3.4 Minerals with significantly high concentration in some samples 27 Conclusion 28 Recommendations 39 References 30 VII Tables VIII Page Table (1.1) Lead content of kohl in different countries 12 Table (2.1) Collection of samples 20 Table (3.1) Concentrations of macro minerals in kohl samples 23 Table (3.2) Concentrations of trace minerals in kohl samples (mg/L) 24 Table (3.3) Concentrations of the risky minerals in some kohl samples 26 Table (3.4) Minerals with significantly high concentrations in some kohl 27 samples List of Tables List of Figures Figure IX Page Fig 1.1 Many different shapes of copper abrasive 6 Fig 1.2 Some kohl samples available in Sudan. 7 Fig 1.3 A map of Sudan before , (2011) 8 Fig 1.4 Distribution of elements as the major components in the Sudan kohl 9 samples. Fig 1.5 Inductively Couple Plasma Optical Emission Spectrometer 13 Fig 1.6 Flow chart showing the methodology for a typical ICP-OES analysis 15 Fig 1.7 Periodic table with ICP-OES detection limits (side-on viewing). 17 Fig 1.8 Micro nebulizer used for ICP-OES 19 X CHAPTER ONE Introduction Chapter one 1. Introduction 1.1 Kohl Kohl or (Alkohol), is widely used in Sudan, for hundreds of years. It is one of the mostly known traditional cosmetics, as eyeliner. Kohl is used for a variety of reasons e.g. to make the eyes beautiful, to make the eyes appear larger, as an eye medicine for a variety of complaints, as a daily tradition from both cultural and religious backgrounds, and as a preventive for children. Women use kohl to outline the upper and lower lids of their eyes.A bridegroom may have kohl applied to his eyes for the wedding ceremony, and the same is often done to tiny/new-born babies in the early weeks of life. Black kohl is also used for staining tattoos and facial scars black. To date, no one has been able to identify the name of the person who invented the kohl, but according to the manuscripts collected from around the world and in different cultures, whether Arab, African or Asian, it was the most visible pharaonic civilization in ancient sculptures, extending from Sudan to the south of Egypt in the north. Some are thought to be important in transitional rituals such as circumcision, marriage, and for those new-borne. According to their beliefs, they are often used as a tool for decoration, since the time of the ancient kingdoms. Kohl as an ancient eye cosmetic, traditionally made by grinding stibnite (Sb2S3). It is widely used in South Asia, the Middle East, North Africa, the Horn of Africa, and parts of West Africa as eyeliner to contour and/or darken the eyelids and as mascarafor the eyelashes. It is worn mostly usedby women, but also by some men and children. Kohls are prepared in accordance with relevant health standards and can be classified to different types. For example Blue- Kohlis a dark-bluish black pigment composed of both lead-based compounds andantimony compounds. The lead-based compounds in kohl are galena (PbS), dark grey and gloss laurionite (PbCl (OH)), white phosgenite ((PbCl)2CO3),ancerussite (PbCO3) , blue. The antimony-based compound in kohl is stibnite (Sb2S3), blue (Abeer A. Ahmed et al; 2016). There is an evidence that, submicromolar concentrations of lead (Pb2+) can elicit overproduction of nitrous oxide (N2O). Kohl was used not only as a cosmetic but also as a medicinal collyrium. Two types of kohl's lead compounds are the lead chlorides laurionite and phosgenite; are not natural to the Nile valley (Abeer A. Ahmed et al; 2016). It is believed that they were intentionally synthesized by the ancient Egyptians for this purpose. The widespread use of kohl across the mediterranean and the Mid-east attests to its ability to protect the eye from infectious diseases and be used as a cosmetic (Abeer A. Ahmed et al; 2016). 1.1.1 Benefits of Kohl Regular use of Kohl will keep the eyes cool and clean from dust and pollution to which eyes may be exposed during the day. It should be noted that, after application of kohl at bedtime, in the morning, we may find some particles with Kohl collected at the corners of the eyes, this is all the dirt and dust particles and airborne substances that the Kohl has collected, and washed away. Some Kohl preparations contain very valuable ingredients which have a property of protection from the glare of Sun, as natural way for UV protection (Hashmi.et al; 2008). Some Kohl brands with the incorporation of high quality and unique ingredients can actually bring definite therapeutic effects while supplying nutrients to the cells, with healing properties, toning of muscles, maintain proper nerve and muscles functions, antioxidant, strengthening eyesight, ultimately resulting in the maintenance of healthy eyes and eyesight. Too much continuous stress on our eyes makes them feel burnt and tired, but regular use of a good quality Kohl with finest, hard-to-soft quality ingredients owning the properties to cool and relax2 down your eyes, thus easing out all the stress of a hectic day (Hashmi.et al; 2008). Regular use of /Kohl protects the eyes from dust and pollution and keeps them cool and clear, and also helps relief tired eyes, eye stress, dry and irritated eyes especially among the youngsters due to (Computer Vision Syndrome, CVS) caused by continuous emission of short wavelength X-rays by the computer screen. Kohl also helps eyes counter electro-magnetic pollution and other forms of harmful environmental energy (Hashmi.et al; 2008). 1.1.2 Hazards of kohl 1.1.2.1 Lead: Lead compounds are toxic by ingestion, inhalation andskin expire. Children are more susceptible, than adults, to leadpoisoning as adults absorb 5-15 percent of ingested lead, while,children can absorb as much as 41 percent.