cosmetic seaweeds of pakistan

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Int. J. Phycol. Phycochem. 8(2): 95-104, 2012 *Presented the paper on October 16, 2012 at Second National Phycological Conference. COSMETIC SEAWEEDS OF PAKISTAN Muhammad Afzal Rizvi 1 * & Ehsan Elahi Valeem 2 1 Hamdard Research Institute of Unani Medicine (HRIUM), Faculty of Eastern Medicine, Hamdard University, Karachi-74600 2 Institute of Marine Science, University of Karachi, Karachi-75270, Pakistan ABSTRACT In recent years, the importance of the oceans has become increasingly apparent. Throughout the passage of time, man relies on seas for sources of nutrition, medicine and general livelihoods. The vastness and depth of the oceans provide means for endless exploration and commerce. Seaweeds play a very important role in the direct economy of many countries. Pakistan has coastline that stretches to over 1040 km along northern boundary of the Arabian Sea. A variety of seaweeds have still not been used in cosmetic industry of Pakistan while agar – agar and alginates are used in skin preparation, lotions and shaving soaps. Many elements such as Ag, Bi, Ca, Cd, Co, Cr, Fe, K, Na, Ni and Zn etc. are used in therapeutic applications for a variety of skin ailments. Representative species of seaweeds collected from different localities of Karachi coast were investigated for their elemental composition through AAS. Eleven elements (Ca, Cd, Co, Cr, Fe, K, Mg, Na, Pb and Zn) were analyzed, which are essential constituents of products used for beauty. Results showed considerable variation in their concentrations. Keywords: Algae, Seaweeds, Elements in skin, Cosmetic industry, Utility. INTRODUCTION Oceans of this beautiful planet Earth cover more than 70 % and contain a variety of colourful algal species. Since the dawn of civilization man has been using oceans for various purposes. Women in ancient times were tinting their lips with red-coloured clay film, henna, seaweed etc. Ancient scholars conducted a vast research on food and medicine such as Hippocrates (460-377 B.C.) formulated the study of dermatology and recommended diet, baths, massage and beauty (Anjum et al. 2011). Galen (130-200 A.D.) is accredited with the invention of cold cream (Handa 2000). Abul Qasim Al- Zahrawi (936-1013 A.D.) is credited with creating the very first lipstick for beauty. Human beings are very conscious about their look and fitness. Skin is a reflection of health. Lifestyle and diet are the major contributors to skin’s appearance. Fifty seaweed species are available at Karachi coast, which can be added into our diet and bring health benefits for organ functions, hair, skin and nails (Shameel & Tanaka 1992, Rizvi & Shameel 2001, Valeem et al. 2011). Strong Yarrow infusion is good for oily, spotty skin. Marine algae contain more than 60 trace elements in concentration i.e. much higher than terrestrial plants (Kathiresan 1992, Rizvi & Shameel 2003a,b, 2004, 2005, 2010). Seaweed extracts such as agar, carrageenin and fucoidan have been used for nutritional and nutraceutical benefits and have provided the impetus for their inclusion in successful cosmetic formulations (Ahmad & Ali 1993, Ahmad & Perveen 1993, Rizvi et al. 2001a,b, 2002, 2011, Fitton et al. 2007). Thus marine or plant origin cosmetics are defined as the beauty products, which possess desirable physiological activities such as skin healing, smoothing, appearance, enhancing and conditioning properties because of natural ingredients (Kalia 2011). The golden rule is to avoid artificial aids to look beautiful. Health has no substitute. Natural resources are hidden in the Arabian Sea in the form of many seaweeds, which are naturally growing in Pakistan (Shameel 1996). A wise use and sound management base on scientific facts are thus needed to create awareness, exploring of marine algal resources and can save the foreign exchange for finished products from there to the other countries.

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Int. J. Phycol. Phycochem. 8(2): 95-104, 2012

*Presented the paper on October 16, 2012 at Second National Phycological Conference.

COSMETIC SEAWEEDS OF PAKISTAN Muhammad Afzal Rizvi1* & Ehsan Elahi Valeem2 1Hamdard Research Institute of Unani Medicine (HRIUM), Faculty of Eastern Medicine, Hamdard University, Karachi-74600 2Institute of Marine Science, University of Karachi, Karachi-75270, Pakistan

ABSTRACT

In recent years, the importance of the oceans has become increasingly apparent. Throughout the passage of time, man relies on seas for sources of nutrition, medicine and general livelihoods. The vastness and depth of the oceans provide means for endless exploration and commerce. Seaweeds play a very important role in the direct economy of many countries. Pakistan has coastline that stretches to over 1040 km along northern boundary of the Arabian Sea. A variety of seaweeds have still not been used in cosmetic industry of Pakistan while agar – agar and alginates are used in skin preparation, lotions and shaving soaps. Many elements such as Ag, Bi, Ca, Cd, Co, Cr, Fe, K, Na, Ni and Zn etc. are used in therapeutic applications for a variety of skin ailments. Representative species of seaweeds collected from different localities of Karachi coast were investigated for their elemental composition through AAS. Eleven elements (Ca, Cd, Co, Cr, Fe, K, Mg, Na, Pb and Zn) were analyzed, which are essential constituents of products used for beauty. Results showed considerable variation in their concentrations.

Keywords: Algae, Seaweeds, Elements in skin, Cosmetic industry, Utility.

INTRODUCTION

Oceans of this beautiful planet Earth cover more than 70 % and contain a variety of colourful algal species. Since the dawn of civilization man has been using oceans for various purposes. Women in ancient times were tinting their lips with red-coloured clay film, henna, seaweed etc. Ancient scholars conducted a vast research on food and medicine such as Hippocrates (460-377 B.C.) formulated the study of dermatology and recommended diet, baths, massage and beauty (Anjum et al. 2011). Galen (130-200 A.D.) is accredited with the invention of cold cream (Handa 2000). Abul Qasim Al- Zahrawi (936-1013 A.D.) is credited with creating the very first lipstick for beauty. Human beings are very conscious about their look and fitness. Skin is a reflection of health. Lifestyle and diet are the major contributors to skin’s appearance. Fifty seaweed species are available at Karachi coast, which can be added into our diet and bring health benefits for organ functions, hair, skin and nails (Shameel & Tanaka 1992, Rizvi & Shameel 2001, Valeem et al. 2011). Strong Yarrow infusion is good for oily, spotty skin. Marine algae contain more than 60 trace elements in concentration i.e. much higher than terrestrial plants (Kathiresan 1992, Rizvi & Shameel 2003a,b, 2004, 2005, 2010). Seaweed extracts such as agar, carrageenin and fucoidan have been used for nutritional and nutraceutical benefits and have provided the impetus for their inclusion in successful cosmetic formulations (Ahmad & Ali 1993, Ahmad & Perveen 1993, Rizvi et al. 2001a,b, 2002, 2011, Fitton et al. 2007). Thus marine or plant origin cosmetics are defined as the beauty products, which possess desirable physiological activities such as skin healing, smoothing, appearance, enhancing and conditioning properties because of natural ingredients (Kalia 2011). The golden rule is to avoid artificial aids to look beautiful. Health has no substitute. Natural resources are hidden in the Arabian Sea in the form of many seaweeds, which are naturally growing in Pakistan (Shameel 1996). A wise use and sound management base on scientific facts are thus needed to create awareness, exploring of marine algal resources and can save the foreign exchange for finished products from there to the other countries.

Rizvi MA & Valeem EE 96

Table I. Uses of seaweed phycocolloids. Uses Products Functions Phycocolloids Food Additives Dairy Products Gelation, foaming, suspension Agar, Carrageenan Baked food Improving, quality, controlling moisture Agar, Carrageenan Sweets Gelation, increase viscosity, suspension Agar, Carrageenan Juices and Sauces Viscosity, emulsifier Agar, Carrageenam Breweries Stabilizer Adhesion Alginate, Carrageenan Processed meat Adhesion Alginate Frozen Fish Adhesion & moisture retention Alginate Medicinal- Tablets Encapsulation Alginate/ Carrageenan pharmaceutics Laxatives Indigestibility & lubrication Alginate- Carrageenan Dental mould Form retention Alginate Metal poisoning Binds metal Alginate

Herpes Simplex Virus Inhibit virus Carrageenan

Cosmetics Shampoos Interface vitalization Alginate Toothpaste Increases viscosity Alginate Lotions Emulsification, elasticity & firmness Carrageenan-Alginate Lipstick Emulsification, viscosity Alginate

Seaweed status of Pakistan: Pakistan is known as variable emporium of cosmetic seaweeds. According to Shameel & Tanaka (1992) there are 177 genera and 475 species of marine planktonic and benthic algae occurring in the marine environment. Out of which many seaweeds can be used for making cosmetic products (Afaq-Husain et al. 2001). Elemental composition of skin: Elements form vital parts of our body. If they are not available to our bodies in the proper ratio, form and amount, our health suffers. Elemental composition of human skin, hair and sweat reveal the presence of at least 55 elements such as Ag, Al, As, Au, B, Ba, Be, Bi, Br, C, Ca, Cd, Cl, Co, Cr, Cs, Cu, F, Fe, Ga, Ge, H, Hg, I, K, La, Li, Mg, Mn, Mo, N, Na, Nb, Ni, O, P, Pb, Po, Ra, Rb, S, Sb, Sc, Se, Si, Sm, Sn, Sr, Te, Ti, Tl, V, W, Zn and Zr (Hameed & Vohra 2001). At least 26 elements Ag, Al, As, Au, Bi, Br, C, Ca, Cd, Cl, Cu, Hg, I, K, N, Na, Nb, Ni, O, Pb, Ra, S, Sb, Se, Si, Sn, Sr, Te, Th, Zn and Zr find therapeutic applications in a variety of skin ailments i.e. acne, boils, burns, eczema, itching, psoriasis, rash, scabies, vitiligo, warts and also cosmetic uses of these elements are made for deodorant, depilatory, antidandruff, hair dyeing purpose (Vohra 1986). The Ca deficiency may be manifested by itching and white spots on the skin. Rough skin is one of the symptoms of Zn deficiency (Hameed & Vohra 2001). Elements in seaweeds: Algae are simple autotrophic organisms occupying a primitive position in the living kingdom. Most of them are aquatic, both marine and freshwater show a wide range of organization, function and elemental composition (Ahmad et al. 1989, Rizvi & Shameel 2001, 2003a,b, 2004, 2005). Elements contained in seaweeds are beneficial for the human skin & easily absorbed by it. Analyses have revealed that seaweeds are rich in many elements (Mutaftchiev 2001) and they are very beneficial for good health of skin as well as cosmetic preparations (Rizvi et al. 2001a,b, 2002, 2011, Valeem et al. 2011). Iodine used for the treatment of minor wounds and abrasions. The Si barrier cream helps in prevention of contact dermatitis. Ointments of S are time honoured for the treatment of Acne vulgaris. Seaweed extracts are perfect skin humectants (or moisturizers) and boost circulation (Hameed & Vohra 2001).

Cosmetic seaweeds of Pakistan 97

Figs. 1-4. Some important beauty/ cosmetic products of seaweeds available in world market: 1. Revia’s all natural seaweed soap (vegetable base), 2. Pacific coast seaweed soap for exfoliation, 3. Seaweed facial mask, 4. Seaweed mild marine shampoo with sea silk extract.

1 2

 3

4

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Table II. Some of the common uses of seaweed species (arranged after Shameel 2012). No. Species Food Medicine Industrial uses

Chlorophycota: 1. Bryopsis pennata Lamouroux + + Emulsifiers, gelling

agents, stabilizers, medicine:

antibacterial, antifungal

2. Caulerpa racemosa (Forsskål) J. Ag. + + + 3. Caulerpa taxifolia (Vahl) C. Agardh + + + 4. Codium iyengarii Børgesen + + Pharmaceutical

products 5. Enteromorpha intestinalis

(Linnaeus) Nees + + +

6. Ulva lactuca Linnaeus + Reported as herbal medicine

+

Phaeophycota: 7. Cystoseira indica (Thivy et Doshi)

Mairh + + Alginate, Mannitol

8. lyengaria stellata (Børgesen) Børgesen

+ + Algin

9. Jolyna laminarioides Guimarăes - + Algin 10. Padina tetrastromatica Hauck - + Raw material for

industrial colloids. 11. Sargassum vulgare C. Agardh + + Herbal Medicine 12. S. swartzii C. Agardh + + Ca Alginate,

mannitol Rhodophycota: 13. Botryocladia leptopoda (J. Agardh)

Kylin Rich in protein, CHO

+ Agar-agar

14. Champia compressa Harvey + + Agar-agar 15. Gracilaria corticata (J. Agardh) J.

Agardh + Dentistry

medicine Agar industries

16. Hypnea musciformis (Wulfen) Lamouroux

+ + Agar-agar, Carageenan

17. Hypnea valentiae (Turner) Montagne

+ - Rich in Agar, Carageenan

Food industry 18. Sarconema furcellatum Zanard + + Food industry 19. Scinaia saifullahii Afaq-Husain et

Shameel + + Agar-agar.,

Carageenan 20. Solieria robusta (Greville) Kylin + + Carageenan

+ = Being utilized, - = utilization yet not reported.

Cosmetic seaweeds of Pakistan 99

Figs. 5-9. Some more important beauty/ cosmetic products of seaweeds available in world market: 5. Chestnut and seaweed toning cream, 6. Seaweed & Aloe eye gel for removing eye make-up and refreshing , 7. Dulse seaweed cream, 8. Seaweed mattifying drying cream, 9. Seaweed vitamin protein for spot

5 6

7 8

9

Rizvi MA & Valeem EE 100

lightening skin care facial mask. Table III. Instrument parameters.

Elements Symbol Wave Length (nm)

Slit width (nm)

Sensitivity (mg/L)

Calcium Ca 422.7 0.7 0.092 Cadmium Cd 228.8 0.7 0.016 Cobalt Co 240.7 0.2 0.078 Chromium Cr 357.9 0.7 0.041 Copper Cu 324.8 0.7 0.077 Iron Fe 248.3 0.2 0.039 Potassium K 766.5 0.7 0.043 Magnesium Mg 285.2 0.7 0.008 Sodium Na 589.0 0.2 0.012 Lead Pb 283.3 0.7 0.079 Zinc Zn 213.0 0.7 0.018

Cosmetic value of seaweeds: Agar – agar is a mixture of two polysaccharides, agrose & agropectin extracted from red seaweeds. It is used as a constituent of cosmetic skin preparation, lotions and shaving soaps (Baquar 2001). Gracilaria corticata, G. gracilis, Gelidium usmanghanii, Hypnea musciformis, Botryocladia leptopoda, Laurencia obtusa, Scinaia saifullahii are common seaweed species at the coast of Pakistan and can be used for exploitation of agar for commercial cosmetic products (Zahid et al. 2001). Algin – alginates: Algin is present in the cell walls of algal cells and extracted from brown seaweeds. It is present as mixed salt of sodium or potassium, calcium and magnesium. Calcium alginate is commercialized in the form of haemostatic wool or gauze. In Cosmo-pharmaceutical technology alginates are valued for their thickening and binding. The cosmetic industry takes advantage of their film forming, emollient and hydrating properties (Bruneton 1995). Alginate is the most useful seaweed derivative found in cosmetics (Table I). It is being used for making creams, gels, hair sprays, colorants, toothpaste, lotions and lipsticks etc. (Lewington 1990, Dhargalkar & Pereira 2005). Beauty/ cosmetic products made from seaweeds are available in world market (Figs. 1-9). Colpomenia sinuosa, Cystoseria indica, lyengaria stellata, Jolyna laminarioides, Sargassum ilicifolium, S. swartzii, S. tenerrimum together could support an alginate industry in Pakistan (Ismail & Usmani 1987, Afaq-Husain et al. 2001). Moisturizing face cream: Moisturizers keep skin moistened. They act as a barrier between skin and harmful bacteria and harsh elements. It is ideal for daily moisturizing, containing seaweed extracts, Aloe barbadensis and Ginkgo biloba. This unique formula helps to protect against pollution and other free radical damage, it reduces the appearance of fine lines and helps combat premature skin-wrinkling by restoring the skins’ natural moisture balance. Rich in vitamins, minerals and amino acids, seaweed extracts nourish dry or dehydrated skin and help combat premature skin-wrinkling (Figs. 1-9). They reduce UV damage, natural sunscreen protection and protect against UV7 gamma radiation. Laminaria digitata, Chondrus crispus, Fucus vesiculosus, Aloe barbadensis, Shea Butter (Mangifolia trees), Apricot Kernel Oil, Ginkgo biloba are key ingredients of moisturizing face cream. The smooth cream is applied to face and neck at morning and night time. All Rí Na Mara products incorporate the purest natural ingredients from seaweed or plant origin and are suitable for all ages and all skin types.

Cosmetic seaweeds of Pakistan 101

Table IV. Elemental composition of seaweeds from Karachi Coast (ppm). Marine algae Ca Cd Co Cr Cu Fe K Mg Na Pb Zn

Chlorophycota 32312.5 1.84 5.92 8.65 9.9 2186.25 54855 12366.58 67977.5 23.47 33.93 Bryopsis pennata Lamouroux 80800 3.15 8.05 9.925 12.9 3795 10855 6660 28535 43.875 37.425

Caulerpa racemosa (Forssk.) J. Agardh 70300 2.2 6.8 12.525 11.25 2542.5 19625 764.5 155950 23.675 21.725

Caulerpa taxifolia (Vahl) C. Agardh 14755 0.975 4.0 10.425 8.5 2840 15810 6870 110400 19.1 25.05

Codium iyengarii Børgesen 14730 1.925 9.55 2.825 5.65 862.5 231700 9605 169350 26.075 18.25

Enteromorpha intestinalis (L.) Nees 4745 0.5 3.675 23.325 14.0 2695 18590 13400 17470 19.6 81.55

Ulva lactuca L. 8545 2.3 3.05 1.85 7.125 382.5 32550 36900 25160 8.55 19.15

Phaeophycota 27351.6 2.67 6.16 7.01 9.7 673.5 68470.33 16030.33 36998.23 10.05 117.63Cystoseira indica (Thivy et Doshi) Mairh 19050 3.95 5.125 4.7 8.125 249 118125 9425 80562.5 8.1 33.62

Padina tetrastromatica Hauck 46950 2.875 6.375 16.15 12.375 3105 26620 24500 20530 15.25 44.47

Sargassum vulgare C. Agardh 16055 1.2 7 0.18 8.6 1740 60666 14166 9902.2 6.8 274.8

Rhodophycota 2452.81 2.24 6.78 5.99 9.66 944.78 74821.87 12553.43 118226.87 13.57 26.83 Botryocladia leptopoda (J. Ag.) Kylin 9055 2.9 8.05 3.4 13.6 499.5 65925 27040 202375 7.2 26.375

Champia compressa Harvey 10630 2.0 10.6 6.825 8.275 587.5 21475.0 7985 10085 22.55 15.05

Gracilaria corticata (J. Ag.) J. Agardh 11725 1.875 5.55 7.1 8.375 1105 114750 4580 26290 13.325 35.3

Hypnea musciformis (Wulf.) Lamouroux 7977.5 1.975 5.1 2.325 6.675 230.5 62125 4930 129687.5 3.85 15.675

Hypnea valentiae (Turn.) Montagne 10350 2.7 7.75 10.625 11.625 1825 112937.5 15260 154187.5 14.1 29.925

Sarconema furcellatum Zanard. 7447.5 2.55 7.45 5.425 12.7 340.75 136375 19820 220187.5 16.05 20.775

Scinaia saifullahii Afaq. et Shameel 8350 1.15 2.85 4.55 4.2 1070 14925 12350 18690 13.45 47.875

Solieria robusta (Greville) Kylin 34087.5 2.8 6.9 7.7 11.9 1900 70062.5 8462.5 184312.5 18.1 23.6

Average amount 4242.17 0.39 1.10 1.27 1.72 223.79 11655.71 2408.84 13129.56 2.77 10.49

MATERIALS & METHODS

Ashing and digestion of seaweeds: A variety of marine benthic algae were collected from Manora, Buleji and Paradise Point, the coastal areas near Karachi (Table II). Specimens were initially dried under shade at room temperature and later in an oven at 60-80º C (Memmert, Germany) for 1 h. The material was then powdered through a grinder. One g of the ground sample was taken in a porcelain crucible and ashed at 500º C in a muffle furnace to constant weight for 2 h as described earlier (Rizvi et al. 2000). The ash was cooled at room temperature, moistened with 10 drops of distilled water and carefully dissolved in 3 mL HNO3 (1:1) and 65 % RDH. The acid solution of each sample was then heated gently on a hot plate (IKAMAG, Germany) at 100-120º C till nearly dry. The crucible was returned to muffle furnace and ashed again for 1 h at 500º C. It was then cooled and dissolved in 10 mL HCl (1:1, 37 % RDH) and the solution was filtered through Whatman filter paper No. 42 (Schleicher & Schuell, Germany) into a 100 mL volumetric flask mixed well and made ready for the Atomic Absorption Spectrometry analysis (Jones 1984).

Rizvi MA & Valeem EE 102

Elemental assay: The flame Atomic Absorption Spectrometer (AAS, Model Perkin-Elmer USA) was used at Environmental Studies Centre, Hamdard University, Karachi for the purpose of estimating Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Na, Pb and Zn (Rizvi & Shameel 2005, Rizvi et al. 2011, Valeem et al. 2011). The various instrument parameters for these elements have been presented in Table III. Instructions for instrument setting calibration and assay for specific elements were strictly followed as laid down in the operational manual.

RESULTS & DISCUSSION

Rizvi et al. (2011) and Valeem et al. (2011) reported elemental composition in Jolyna laminarioides and Ulva fasciata. Many elements such as Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Na, Pb and Zn were detected quantitatively. Ca, Fe, K, Mg and Na were found in large amounts (223.79 - 13129.56 ppm), Cr, Cu, Pb and Zn were present in small quantities (1.27 - 10.49 ppm), while Cd and Co were detected in extremely small amounts (0.39 - 1.10 ppm; Table IV). Maximum sodium content was recorded for Sargassum swartzii from Okha Port, India in December and a minimum in January (Murthy & Radia 1978). It seems that the tropical seaweeds tend to accumulate more Fe than Mn, Zn (Marderosian 1972). Tuzen et al. (2009) also analyzed that Fe was the highest elemental concentration while Cd was the lowest in among these seaweeds. The average quantity of Na was found to be the highest among these algae (13129.56 ppm) followed by K (11655.71 ppm) and Ca (4242.17 ppm) with low quantity of Cr (1.27 ppm), Co (1.10 ppm) and Cd (0.39 ppm). Rizvi et al. (2000, 2011) determined the average amount Co as 4.3 ppm, Cr as 1.91 ppm and Cd as1.18 ppm in the seaweeds of Karachi. CONCLUSION

Pakistan coast has a variety of aromatic and cosmetic seaweeds. They may be used in the preparation of shampoos, soaps, perfumes dyes, lotions and skin cleansers etc. They impart many benefits such as pleasant aroma, especially in perfumes and to impart shine or conditioning in a hair and skin care product. Elements play an important role in natural beauty care products. In future, it is possible that many types of seaweeds will be identified, distilled and exploited for their commercial significance. This requires the collaboration of phycologists, botanists, biologists, chemists and elementologists to assess cosmetic value rather than performing bio-assays. ACKNOWLEDGEMENT

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