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REVIEWARTICLE Kakoli et.al / IJIPSR / 6 (01), 2018, 14-31 Department of Chemistry ISSN (online) 2347-2154

DOI: 10.21276/IJIPSR.2018.06.01.251

Available online: www.ijipsr.com January Issue 14

COSMETICS –CARE, CONCERNS and CAUTION

Kakoli Banerjee * Assistant Professor, Department of Chemistry, Prabhu Jagatbandhu College, Howrah,

West Bengal, INDIA

Corresponding Author: Kakoli Banerjee Department of Chemistry Prabhu Jagatbandhu College Andul-Mouri, Howrah- 711 302, West Bengal, INDIA E-mail: [email protected] Phone: +91-9830040709

International Journal of Innovative Pharmaceutical Sciences and Research

www.ijipsr.com

Abstract Cosmetics are chemical substances which serve the purpose of enhancing personal beauty, caring and rejuvenating human skin and its appendages. They are deliberately applied external reagents which find their pathway into the human body through the process of contact, ingestion and inhalation. In some cases, cosmetics are applied as a necessary socio religious custom. It is essential therefore to have an insight into the most commonly used cosmetics from its manufacture to application. This review serves to summarize and interpret the data available regarding common cosmetic products and their safety and efficacy. Keywords: Cosmetics, exposure, health implications, precautions, future trends


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INTRODUCTION Cosmetics can be defined as any preparation intended to be applied to the human body for the purpose of enhancing beauty or camouflaging the appearance without affecting the body’s structure and function [1]. Although the main purpose of cosmetics is to rectify skin imperfections, it has certain related functions like cleansing and protection of skin from external agents. From the consumers perspective, cosmetics can be categorized primarily into two broad categories a) ones that give instantaneous results which we often term as “make up” and the b) ones that enhances beauty by repeated and prolonged use which are also termed “functional cosmetics”. Both have an impact on the human body as it is being exposed deliberately to foreign ingredients. Even in mid twentieth century it was generally believed that cosmetic products will always remain on the surface of the human body. However, with passage of time, the concept of cosmetics have undergone paradigm shift. Gradually a range of products evolved which popularly came to be known as ‘care cosmetics’. Application of the products no longer dwelled on the skin surface but penetrated the skin barrier. Variation in Cosmetics

a) Colour cosmetics are used to change appearance of skin and hair. These include: Lip cosmetics (lipsticks, Lipglosses, Lipliners, Lipbalms etc.) Nail polishes Eye cosmetics (Kohl, eyeliners, eye shadows, mascara) Hair cosmetics ( Hair dyes) Skin cosmetics (liquid foundation, talcum powder and face powder) b) Body care products ( Skin and Hair) –Moisturizers, Sunscreen lotions, Fairness creams,

Ant wrinkle/ anti-aging creams and Hair gels and shampoos, conditioners, growth stimulators

c) Traditional &Religious cosmetics – Kohl, Sindoor, Altaa, Mehndi d) Others – Removers of all kinds ( Make up, Nail polish, Hair) e) Perfumes

In this review, the discussions will be related to use and its consequences of products which fall under the above mentioned categories from a) to e). It is very important to note the application sites of different categories of cosmetics because this eventually decides the pathway (ingestion, inhalation or contact) of potential harmful substances into our body system [Table 1].


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Table 1: Common chemical ingredients in cosmetics and possible concerns Chemical name of

Ingredient Found in Purpose Concerns Butylatedhydroxyanisole

(BHA) and butylatedhydroxytoluene

(BHT) lipstick, eye shadow, some

petroleum products antioxidant, preservative,

stabilizer, fragrance ingredient

skin irritation, hormone disruption

Diethanolamine (DEA)

variety of face makeup and hair products

pH adjuster, foaming agent

skin irritation, possible organ

system toxicity, contamination

concerns Phthalates dibutyl phthalate (DBP), dimethyl phthalate

(DMP), and diethyl phthalate (DEP)

nail polish, hair sprays, perfumes, lotions, soaps,

shampoos plasticizer, solvent, fragrance ingredient

male reproductive system damage

Formaldehyde (formaldehyde releasers: bronopol, DMDM hydantoin, diazolidinyl urea,

imidazolidinyl urea, and quaternium-15)

nail products, eyelash glue, hair gel, hair-

smoothing products, baby shampoo, body soap, color

cosmetics

Preservative

carcinogenic impurity, skin

irritations, high rates of skin allergy

reactions, rashes

Fragrance (perfume, parfum, essential oil blend, and

aroma) most personal skincare

products

chemical combination of a possible 3,000

ingredients to create scents

skin irritation, allergic reactions,

cancer or reproductive toxicity

with long-term exposure

PEGs (polyethylene glycol or

ceteareth)

variety of skin-care and makeup products

conditioning and cleaning agents

contamination

concerns Parabens (specifically propyl-

, isopropyl-, butyl-, and isobutyl- parabens)

makeup, moisturizers, shampoos, conditioners,

lotions, facial and shower cleansers, shaving

products, and scrubs

Preservative

hormone-disrupters

Sodium laureth sulfate and sodium lauryl sulfate

toothpaste, shampoo, and hand soap

cleansing and

emulsifying agent

skin irritation, possible impurity

contamination Synthetic colors all product types Colorants unapproved colors

used in products Siloxane (ingredients ending in -siloxane or -methicone) hair products, deodorants

softening, smoothing, moisturizing

hormone disrupter

Triclosan

oral products, shaving products, creams, and

color cosmetics antimicrobial agent

disrupt thyroid and reproductive

hormones, bacterial resistance

development


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Colour Cosmetics Without colorants most cosmetic formulas would be yellow or brown. Color cosmetics would not exist. Pigmented cosmetics used by women and several men have the following possibilities

Lip products like lipsticks, lip glosses or lip balms which can be inadvertently ingested Eye makeups like eyepencils, eyeshadows, liquid eyeliners and mascaras apart from

allergic reactions are sources of periocular exposure Nail polishes have a high risk of oral ingestion specially in countries where the social

custom is to have food with hands Face powders and liquid foundation which are applied to facial and other exposed parts of

the skin leads to topical adsorption Hair dyes applied may often lead to scalp allergies The human skin, which is the largest organ of the body, is in direct contact with cosmetics

and therefore its structure is most decisive when contemplating the application of cosmetic products.

Fig.1a: Cross sectional structure of the skin


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Fig. 1b: Structure of the Eye

Skin provides a protective barrier against harmful microbes, chemicals and UV radiation [Fig 1a]. The outermost layer of the skin, the stratum corneum, has layers of tough, fibrous protein called keratin derived from flattened keranocytes which makes penetration of foreign particles difficult. Colour cosmetics are mostly applied very close to the region of mucous membranes - the lips and eye. Eye makeup is easily absorbed as the stratum corneum of the eyelid is thin and metal diffusion is more rapid [Fig 1b]. Coloured cosmetics applied to lips are directly ingested through the oral cavity. The most toxic ingredients detected in these cases are the heavy metals Lead, Chromium, Nickel and Cadmium [2-4]. Heavy metals are frequently found in makeup because natural colorants come from the earth, and in the ground, heavy metals are present and may randomly attach to the intentionally mined ingredients. The accumulation of heavy metals has been established to be toxic and have serious health implications [5, 6]. The highest concentration of Lead was found in shimmering and brown colours while the red colour lipsticks contained Chromium and Nickel [7]. Trace metal contents in colored makeup other than lipstick have been extensively studied by several research groups [8-11]. Use of natural hair colouring agents like Henna (Lawsoniainermis), black walnut (JuglansNigra) shells although used frequently have the disadvantage of being washed off with shampoos or are allergic to certain skin types. They work by colouring the hair shaft however the effect is temporary. Hair is mainly keratin, the same protein found in skin and fingernails. The natural color of hair depends on the ratio and quantities of two other proteins, eumelanin, and pheomelanin. Eumelanin is responsible for brown to black hair shades while pheomelanin is responsible for golden blond, ginger, and red colors. The


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absence of either type of melanin produces white/gray hair. Basic difference between the temporary and permanent hair dyes is that in the former case the hair shaft may or may not be opened with peroxide. Deposition of the acidic dye on the outer shaft or the use of peroxide allows colorant to enter the hair shaft resulting in complexation giving colour. This can be lost with several washes with shampoos. In case of permanent hair colour, the outer layer of the hair shaft, its cuticle, must be opened [Fig 2]. Once the cuticle is open, the dye reacts with the inner portion of the hair, the cortex, to deposit or remove the color.

Fig. 2: Cross section of the hair shaft

Ammonia is used to open up the cuticle which then and allows the hair color to penetrate the cortex of the hair. It also acts as a catalyst when the permanent hair color comes together with the peroxide. In both cases utmost care should be taken that there is no contact with the skin. Body care products The stratum corneum is an effective barrier to trans epidermal water loss (involuntary loss of water from inside a body through the skin to the surrounding atmosphere via diffusion and evaporation processes) and to penetration of extraneous substances. Topical application of most skin care preparations leads to local effects only. There are three entry sites into the sub cutaneous layer: a) skin pores b) hair follicles and c) spaces between cells that contain an oil/ water fluid matrix [Fig 3]. Since the border of the skin


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cells is composed of lipid soluble membranes, a small molecular weight hydrophobic compound is more likely to penetrate through the skin than a high molecular weight hydrophilic compound. The interior on the contrary is mostly water soluble. For a cosmetic ingredient to arrive at a tissue type where it will reside, the ingredients must get inside the cell and be a part of a cellular metabolism. So an emulsion must be designed which will either be an oil in water (o/w) or water in oil (w/o) to pass through the cell membranes and thereby assist in cellular metabolism [Fig 4]. Recent studies on microemulsions and nanoemulsions have had a considerable impact on the skin permeation process leading to effective therapeutic outcome [12]. Alcohols like phenoxymethanol (serum) and butylene glycol (moisturizing) act as penetration enhancers.

Fig. 3: Skin penetration pathways (intracellular, intercellular, and follicular) by which a molecule can cross the stratum corneum


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Fig. 4: Schematic representation of emulsions used in manufacture of cosmetics Anti-aging creams With aging process, the complex cellular pathways become less accurate and the vibrant and elastic collagen cells responsible for youth are less produced. This leads to wrinkled skin structure. Melanin also gets unevenly deposited leading to age spots or liver spots technically known as chloasma or melisma [13], Main function of anti-aging cream is to improve the functioning and texture of the skin by encouraging collagen growth and preventing generation of free radicals.The alpha hydroxyl acids (AHA) reduce calcium ion concentration in the epidermis by process of chelation. The presence of calcium leads to cell adhesion and desquamation is stopped. On removal of calcium ions, desquamation is facilitated and cell from within results in younger looking skin [14].Retinoids which are natural and synthetic derivatives of vitamin A inhibit enzymes from breaking down collagens. Moisturizers Moisturizers keep the skin soft and supple. Humectants are frequently used in cosmetics as a way of increasing and maintaining moisture in the skin and hair. As hygroscopic moisturizers, humectants work by attracting water to the upper layer of the skin –the stratum corneum [15]. These are polyhydric alcohols having common hydroxyl groups which allow them to participate in hydrogen bonding and attract water [Fig 5]. The capacity of holding moisture depends on the particular humectants in use [16].


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D-sorbitol triethylene glycol

Tripropylene glycol Glycerol

Fig. 5 Humectants containing polyhydric groups responsible for water attraction via

hydrogen bonding Sun screens UV light generates free radicals and reactive oxygen that result in tissue damage and subsequent inflammatory responses [17]. Sunscreens provide broad spectrum coverage that includes both UVA and UVB blocking agents to photo aging. Free radicals are highly reactive species as they are missing an electron. These electron deficient species then tend to capture electrons from neighboring molecules thereby causing a chain reaction within the body leading to damage. Antioxidants [Fig. 6] are classes of compounds which prevent such a process. They not only inhibit free radical generation but also enable living cells to repair and renew. The end result is skin that looks and feels younger.

Kojic Acid Hydroquinone Ferulic acid Fig.6: Structure of commonly used chemicals in sunscreens


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Fairness creams and Exfoliants Hydroquinone is the most popularly used skin lightening agents [18,19]. All fairness creams target at reducing melanin formation. The adverse effect may be hyper pigmentation or irregular pigmentation patterns and thinning of skin have been reported by Kooyers et al [20].Exogenous ochronosis (EO) is a cutaneous disorder characterized by blue-black pigmentation resulting as a complication of long-term application of skin-lightening creams containing hydroquinone but may also occur due to topical contact with phenol or resorcinol in dark-skinned individuals [21]. Mercury is a heavy metal which is often found in fairness creams since it inactivates tyrosinase, the main melanin forming enzyme tyrosinase. The electrophilic nature of the metal ion also leads to local deposition in the dermal tissues. Factors determining percutaneous absorption have been studied by several researchers [22]. Exfoliants removes adherent cells in the stratum corneum and helps in the rejuvenating process. However, repeated use may lead to UV penetration process. Salicylic acid, glycolic acid and lactic acid are constitutes these kinds of products. Socio-Religious Cosmetics There are a quite a few cosmetics whose usage is mainly based on socio-religious customs. These are mainly indigenous products like vermillion (Sindoor), kumkum, kohl/ kajal, Henna, Alta etc. However, in present day due to migration and sharing of cultures it is vital for the dermatologists to be familiar with these coloring products. Vermillion “Sindoor” is usually smeared on the hair parting line of Hindu married women and also smeared on the forehead of men in Indian temples. Kohl or Kajal is a cosmetic predominantly used as an eye makeup. It is used for a variety of reasons other than mere beautification like to ward off evil, as tradition with Islamic religion and belief that it is medically beneficial to the eyes. Henna is a natural dye obtained from the leaves and flowers of plant Lawsoniainermis, family Lythraceae which grows in hot climates of northern Africa and western and southern Asia. It is popularly used for tattoos. Alta is a red coloured dye in liquid form applied by women hailing from West Bengal, India to the border of their feet during religious and social functions. These products are used on the skin for a prolonged period of time or repeatedly so skin interactions are of concern. Harmful ingredients have been detected in several of these cosmetics and research is still going on. For example, Henna is often mixed with coloring agents like para- phenylenediamine (PPD), diaminotoluenes and diaminobenzenes which are added to pure henna for quicker drying and deeper color intensity. Heavy metals like nickel, cobalt, mercury, lead, chromium have been sought out for several of these cosmetics [23-26].


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Removers of Cosmetics Make up: For any removal of cosmetics, the chemical principle involved is “like dissolves like.” In other words, oils will dissolve other materials that have a similar chemical structure. The liquid cleansers are pure oil while the creams are oils mixed with water, emulsifiers and thickeners. The oil breaks the oils and waxes in the makeup. Primary cleansing agents are Mineral oil, Isopropyl Palmitate. The oil based make up removers are especially good for removal of water-proof cosmetics however they are usually comedogenic i.e they tend to clog pores. So a thorough wash must be ensured after they are used. The common ingredient in water based removers is micellar water. These are often packed with soothing agents like aloe vera, chamomile or green tea. The latest trend is the bi-phasic make up remover where two separate oily and water-based layers are present. The ground rule is after using a makeup remover, always wash your face. Nail Polish: Nail polish removers contain acetone which is primarily a solvent. Inhaling a large quantity or accidentally swallowing may lead to unconsciousness and develop tissue damage in the mouth. Hair Removal: Hair removal products, also called depilatories, are creams and gels which dissolve the protein structure (keratin) of hair so it separates from the skin. Calcium thioglycolate is an active ingredient in some hair removal products. Calcium thioglycolate is a harsh chemical, but is included in very low amounts to prevent side effects like itchiness, rashes and dryness. Severe chemical burns can occur with the use of hair-removal creams. Both hair and skin are made up of the same proteins and amino acids. Hair breaks down much more quickly than skin, which makes it possible to remove hair without removing skin. However, if the product is allowed to remain on the skin for too long, or if it is not rinsed away completely, the skin will begin to break down, resulting in a chemical burn. So a patch test is necessary before application of these creams to check out if the skin is allergic to the chemical. Perfumes Some of the most common chemicals in perfumes are ethanol, acetaldehyde, benzaldehyde, benzyl acetate, a-pinene, acetone, benzyl alcohol, ethyl acetate, linalool, a-terpinene, methylene chloride, styrene oxide, dimenthylsulphate, a-terpineol, camphor, and limonene. Some of these chemicals cause irritability, mental vagueness, muscle pain, asthma, bloating, joint aches, sinus pain, fatigue, sore throat, eye irritation, gastrointestinal problems, laryngitis, headaches, dizziness, swollen lymph nodes, spikes in blood pressure, coughing, and burning or itching skin irritations. Perfumes contain neurotoxins, which have a causal link to central nervous system disorders,


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headaches, confusion, dizziness, short-term memory loss, anxiety, depression, disorientation, and mood swings. Upon inhalation of a fragrance, the odor molecules travel up the nose where they are captured by the olfactory membrane. Each odor molecule fits into specific receptor cell lining the olfactory epithelium. There are hundreds of millions of nerve cells and they are each replaced every 28 days. Odor molecules stimulate the lining of nerve cells which trigger electrical impulses to the olfactory bulb, which then transmits impulses to the gustatory center (where the sensation of taste is perceived), the amygdala (where emotional memories are stored), and other parts of the limbic system of the brain that controls stress levels, heart rate, blood pressure and breathing. Essential oils can have some very profound physiological and psychological effects because the limbic system is directly connected to those parts of the brain that control heart rate, blood pressure, breathing, stress levels, hormone balance, and memory [27,28]. Fear, anxiety, depression, anger, and joy all emanate from this region of the brain. A particular scent or fragrance can evoke memories and emotions before we are even consciously aware of them. The limbic lobe, which encompasses a group of brain structures including the hippocampus, can also directly activate the hypothalamus, one of the most important parts of the brain, which serves as our hormonal control center. The hypothalamus is responsible for the production of growth hormones, sex hormones, thyroid hormones, and neurotransmitters such as serotonin. Fragrance is used in almost all kinds of cosmetics and therefore special attention must be given to them. Recent studies show that this system allows many environmental toxins including those found in perfumes and other scented products access to the delicate brain, and that once found in the brain can take decades to eliminate – decades that can result in substantial damage in the form of inflammation and plaque buildup in the brain – two of the precursors to serious brain disorders like Alzheimer’s and Parkinson’s. PENETRATION Vs ABSORPTION The distinction between penetration and absorption is a crucial one where measurement of chemical risk due to cosmetics is concerned.

Skin Penetration represents the amount of a topically applied chemical that exists between the top layer (stratum corneum) and the bottom layer (stratum basale). During penetration, the body does not yet absorb the chemical, and it cannot affect the body systems.

Skin Absorption occurs when the topically applied chemical breaks the skin barrier to reach the bloodstream. Whether this chemical becomes a risk is determined by what


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occurs after absorption. Human body can either filter out the chemical via bodily fluids, or bioaccumulation occurs.

Many variables affect the speed (or probability) of penetration and absorption. First, the composition of the chemical to which skin is exposed. Second, the area of skin that is exposed (thinner-skinned areas especially mucous membranes and periocular areas are more susceptible to penetration and thicker skin is less). Finally, the condition of the skin (i.e broken or inflamed) is a significant factor.

The design of cosmetic and skin care formulas is to benefit the outer layer of skin— absorption into the body would waste the effects of these products. Majority of cosmetics are not soluble in skin (i.e. lipid, or fat-soluble) and are too large in molecule to fit through the stratum corneum. Precisely because of these qualities, some skin care formulas require specially developed “penetration enhancers” to deliver ingredients like vitamin C or retinol.

Absorption into the body doesn’t equate to bodily harm. Risk assessment evaluates how (duration and pathway) we are exposed. Composition and howthe ingredient behaves once inside the body are also important tools for risk assessment studies.

The toxicity of an ingredient is in the amount absorbed and accumulated. At the dose in which a chemical becomes harmful (toxic) is the threshold, less than this amount is safe, and more becomes a danger. Our body is designed to break down chemicals into other forms that are easily excreted via fluids. The threshold is the over/under amount of our bodies ability to process a chemical and still keep the body healthy.

Absorption rates vary among individuals and even for the same individual over time. Variables such as age, sex, ratio of body fat, previous exposure, nutrition, type and amount of skin exposed as well as the specific conditions of exposure will all affect actual absorption. Rates obtained from healthy adults will again tend to underestimate absorption for younger or more sensitive populations.

RISK ANALYSIS [29] Various ingredients are used in the design of cosmetics. Individually they have a different role to play in the final product so none of them can be avoided. However, most of them have an adverse effect if studied separately and can be a cause for concern (Table 1). There are several risk factors involved in the regular use of cosmetics of which primary are:


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contact dermatitis or skin irritation birth defects in pregnant women disrupted hormones in children and adolescents

Risk factors for a cosmetic ingredient are calculated in terms of Margin of Safety (MoS), Systemic Exposure Dosage (SED) and Life time cancer risk. NO(A)EL or the No Observed (Adverse) Effect Level is the outcome of long-term toxicity studies, such as 28-day, 90-day tests . SED: The Systemic Exposure Dosage of a cosmetic ingredient is the amount expected to enter the blood stream (and therefore be systemically available) per kg body weight and per day. It is expressed in mg/kg body weight/day. The MoS value is used to extrapolate from a group of test animals to an average human being and subsequently from an average human being to sensitive subpopulation

= / SED SED (mg/kg bw/day) = Systemic Exposure Dosage DAa(μg/cm2) = Dermal Absorption reported as amount/cm2 SSA (cm2) = Skin Surface Area expected to be treated with the finished cosmetic product F (day-1) = Frequency of application of the finished product 60 kg = Default human body weight DERMAL ABSORPTION IN PERCENTAGE Calculations of the SED may also be based on the percentage dermally absorbed, lowest concentration anticipated.

SED (mg/kg bw/day) = Systemic Exposure Dosage A (g/day) = Amount of the cosmetic product applied daily C (%) = Concentration of the ingredient under study in the finished cosmetic product on the application site DAp (%) = Dermal Absorption expressed as a percentage 60 kg = Default human body weight


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FUTURE TRENDS Cosmetics making therapeutic claims function by combating harmful effects of free radicals subsequently encouraging collagen growth. Such new age cosmetics are often termed as ‘cosmeceuticals’ as they are intended towards healing. Cosmeceutical products contain ‘active ingredients’ that act on the skin cellular level via topical application Future trends in cosmetic would therefore be focused on the design of cosmetics having medicinal effects. Examples of products that are both cosmetics and drugs are shampoos that treat dandruff, fluoride toothpastes to prevent dental decay and sunscreens-sun blocking cosmetics, including foundations that contain sunscreens. Phytosomes are a class of compounds which encases bioactive molecules having cosmetic as well as medicinal values. They are easily absorbed owing to lipophilic characteristics and can deliver the active ingredient to the targeted tissues [30]. Nanotechnology based cosmeceuticals are an upcoming area of interest. Several modifications may be achieved owing to their smaller size of nanoparticles [31]. Government regulatory systems may inhibit the use of drugs and pharmaceuticals after certain permissible limits; however; these category of products have not been considered under regulatory aspects. Further research on pharmaceutical and drugs need to be conducted on the mechanism of action and their efficacy on topical application vis-à-vis oral intake. CONCLUSION The mere presence of a particular ingredient does not make a cosmetic harmful. Toxicity studies on various types of cosmetics are still a relatively large domain yet to be explored. Apart from skin disorders which are applicable to all users, special attention should be given in the case of pregnant women and adolescents particularly, when cosmetics containing chemicals known to be hormone disrupters are used as ingredients. Since federal laws are different for different countries, regulations concerning permissible limits of cosmetics will also be varied. In the US, it is the Federal Food, Drug and Cosmetic Act (FDCA) while European Union cosmetic legislations are based on Council Directive 76/768/EEC, Health Canada regulated by Canadian Food and drugs Act while cosmetic products in India are regulated under Drugs and cosmetics Act 1940 and Rules 1945 and labeling declarations by Bureau of Indian Standards (BIS). In the context of heavy metals it can be stated that the usage of a metal is prohibited does not mean that this element cannot be present in the final product in detectable amount as unavoidable contamination through production route. Thus, assessment of heavy metals in trace concentrations (parts per


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million and parts per billion) as contaminants in commercially available cosmetics is required. These are carried out by highly advanced analytical methods like Atomic Absorption Spectrometry and Inductively Coupled Plasma Mass Spectrometry to certify them as ‘safe’ to use. Much of the adverse effects from these constituents can be eliminated through good practices during its use and proper removal after application. To maintain ‘Cosmetic Hygiene’ is utmost essential. The bodily intake either on penetration after topical application or through ingestion/inhalation processes may not necessarily lead to absorption. In conclusion it may be definitely said that “Everything is a Risk, but Not Necessarily a Harm”. Conflict of Interests The author declares that there is no conflict of interests regarding publication of this paper. REFERENCES

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