Sunscreen


Sunscreen, also known as sunblock, is a lotion, spray, gel, foam, stick or other topical product that absorbs or reflects some of the sun's ultraviolet radiation and thus helps protect against sunburn. Diligent use of sunscreen can also slow or temporarily prevent the development of wrinkles, dark spots and sagging skin.
Depending on the mode of action, sunscreens can be classified into physical sunscreens or chemical sunscreens.
Medical organizations such as the American Cancer Society recommend the use of sunscreen because it aids in the prevention of squamous cell carcinomas. The routine use of sunscreens may also reduce the risk of melanoma. However, many sunscreens do not block UVA radiation, yet protection from UVA has been shown to be important for the prevention of skin cancer.
To provide a better indication of their ability to protect against skin cancer and other diseases associated with UVA radiation, the use of broad-spectrum sunscreens has been recommended.
Sunscreens are commonly rated and labeled with a sun protection factor that measures the fraction of sunburn-producing UV rays that reach the skin. For example, "SPF 15" means that of the burning radiation reaches the skin through the recommended thickness of sunscreen. Other rating systems indicate the degree of protection from non-burning UVA radiation.
Sunscreens are designed to remain effective at original strength for up to three years, and are typically of doubtful value after that period. Some sunscreens include an expiration date—a date indicating when they are no longer expected to be effective.

Health effects

Benefits

Sunscreen use can help prevent melanoma and squamous cell carcinoma, two types of skin cancer. There is little evidence that it is effective in preventing basal cell carcinoma.
A 2013 study concluded that the diligent, everyday application of sunscreen can slow or temporarily prevent the development of wrinkles and sagging skin. The study involved 900 white people in Australia and required some of them to apply a broad-spectrum sunscreen every day for four and a half years. It found that people who did so had noticeably more resilient and smoother skin than those assigned to continue their usual practices.
Minimizing UV damage is especially important for children and fair-skinned individuals and those who have sun sensitivity for medical reasons.

Potential risks

In 2009, the Therapeutic Goods Administration of Australia updated a review of sunscreen safety studies and concluded: "The potential for titanium dioxide and zinc oxide nanoparticles in sunscreens to cause adverse effects depend primarily upon the ability of the nanoparticles to reach viable skin cells. To date, the current weight of evidence suggests that TiO2 and ZnO nanoparticles do not reach viable skin cells." Sunscreen ingredients typically undergo extensive review by government regulators in multiple countries, and ingredients that present significant safety concerns tend to be withdrawn from the consumer market.
There is a risk of an allergic reaction to sunscreen for some individuals, as "Typical allergic contact dermatitis may occur in individuals allergic to any of the ingredients that are found in sunscreen products or cosmetic preparations that have a sunscreen component. The rash can occur anywhere on the body where the substance has been applied and sometimes may spread to unexpected sites."

Vitamin D production

Concerns have also been raised about potential vitamin D deficiency arising from prolonged use of sunscreen. Typical use of sunscreen does not usually result in vitamin D deficiency; however, extensive usage may. Sunscreen prevents ultraviolet light from reaching the skin, and even moderate protection can substantially reduce vitamin D synthesis. However, adequate amounts of vitamin D can be produced with moderate sun exposure to the face, arms and legs, averaging 5–30 minutes twice per week without sunscreen. Vitamin D overdose is impossible from UV exposure thanks to an equilibrium the skin reaches in which vitamin D degrades as quickly as it is created.
These earlier studies were confirmed in 2019 which showed that sunscreen with a high UVA protection factor enabled significantly higher vitamin D synthesis than a low UVA protection factor sunscreen, likely because it allows more UVB transmission.

Measurements of protection

Sun protection factor and labeling

The sun protection factor is a measure of the fraction of sunburn-producing UV rays that reach the skin. For example, "SPF 15" means that of the burning radiation will reach the skin, assuming sunscreen is applied evenly at a thick dosage of 2 milligrams per square centimeter. A user can determine the effectiveness of a sunscreen by multiplying the SPF by the length of time it takes for him or her to suffer a burn without sunscreen. Thus, if a person develops a sunburn in 10 minutes when not wearing a sunscreen, the same person in the same intensity of sunlight will take 150 minutes to develop a sunburn of the same severity if wearing a sunscreen with an SPF of 15. It is important to note that sunscreens with higher SPF do not last or remain effective on the skin any longer than lower SPF and must be continually reapplied as directed, usually every two hours.
The SPF is an imperfect measure of skin damage because invisible damage and skin aging are also caused by ultraviolet type A, which does not primarily cause reddening or pain. Conventional sunscreen blocks very little UVA radiation relative to the nominal SPF; broad-spectrum sunscreens are designed to protect against both UVB and UVA. According to a 2004 study, UVA also causes DNA damage to cells deep within the skin, increasing the risk of malignant melanomas. Even some products labeled "broad-spectrum UVA/UVB protection" have not always provided good protection against UVA rays. Titanium dioxide probably gives good protection, but does not completely cover the UVA spectrum, as early 2000s research suggests that zinc oxide is superior to titanium dioxide at wavelengths 340–380 nm.
Owing to consumer confusion over the real degree and duration of protection offered, labeling restrictions are enforced in several countries. In the EU, sunscreen labels can only go up to SPF 50+. Australia's Therapeutic Goods Administration increased the upper limit to 50+ in 2012. In its 2007 and 2011 draft rules, the US Food and Drug Administration proposed a maximum SPF label of 50, to limit unrealistic claims. Others have proposed restricting the active ingredients to an SPF of no more than 50, due to lack of evidence that higher dosages provide more meaningful protection. Different sunscreen ingredients have different effectiveness against UVA and UVB.
The SPF can be measured by applying sunscreen to the skin of a volunteer and measuring how long it takes before sunburn occurs when exposed to an artificial sunlight source. In the US, such an in vivo test is required by the FDA. It can also be measured in vitro with the help of a specially designed spectrometer. In this case, the actual transmittance of the sunscreen is measured, along with the degradation of the product due to being exposed to sunlight. In this case, the transmittance of the sunscreen must be measured over all wavelengths in sunlight's UVB–UVA range, along with a table of how effective various wavelengths are in causing sunburn and the standard intensity spectrum of sunlight. Such in vitro measurements agree very well with in vivo measurements.
Numerous methods have been devised for evaluation of UVA and UVB protection. The most-reliable spectrophotochemical methods eliminate the subjective nature of grading erythema.
The ultraviolet protection factor is a similar scale developed for rating fabrics for sun protective clothing. According to recent testing by Consumer Reports, UPF ~30+ is typical for protective fabrics, while UPF ~20 is typical for standard summer fabrics.
Mathematically, the SPF is calculated from measured data as:
where is the solar irradiance spectrum, the erythemal action spectrum, and the monochromatic protection factor, all functions of the wavelength. The MPF is roughly the inverse of the transmittance at a given wavelength.
The above means that the SPF is not simply the inverse of the transmittance in the UVB region. If that were true, then applying two layers of SPF 5 sunscreen would always be equivalent to SPF 25. The actual combined SPF may be lower than the square of the single-layer SPF.

UVA protection

Persistent pigment darkening

The persistent pigment darkening method is a method of measuring UVA protection, similar to the SPF method of measuring sunburn protection. Originally developed in Japan, it is the preferred method used by manufacturers such as L'Oréal.
Instead of measuring erythema, the PPD method uses UVA radiation to cause a persistent darkening or tanning of the skin. Theoretically, a sunscreen with a PPD rating of 10 should allow a person 10 times as much UVA exposure as would be without protection. The PPD method is an in vivo test like SPF. In addition, Colipa has introduced a method that, it is claimed, can measure this in vitro and provide parity with the PPD method.

SPF equivalence

As part of revised guidelines for sunscreens in the EU, there is a requirement to provide the consumer with a minimum level of UVA protection in relation to the SPF. This should be a "UVA PF" of at least 1/3 of the SPF to carry the UVA seal.
A set of final US FDA rules effective from summer 2012 defines the phrase "broad spectrum" as providing UVA protection proportional to the UVB protection, using a standardized testing method.

Star rating system

In the UK and Ireland, the Boots star rating system is a proprietary in vitro method used to describe the ratio of UVA to UVB protection offered by sunscreen creams and sprays. Based on original work by Brian Diffey at Newcastle University, the Boots Company in Nottingham, UK, developed a method that has been widely adopted by companies marketing these products in the UK.
One-star products provide the lowest ratio of UVA protection, five-star products the highest. The method was recently revised in light of the Colipa UVA PF test and the revised EU recommendations regarding UVA PF. The method still uses a spectrophotometer to measure absorption of UVA versus UVB; the difference stems from a requirement to pre-irradiate samples to give a better indication of UVA protection and photostability when the product is used. With the current methodology, the lowest rating is three stars, the highest being five stars.
In August 2007, the FDA put out for consultation the proposal that a version of this protocol be used to inform users of American product of the protection that it gives against UVA; but this was not adopted, for fear it would be too confusing.

PA system

Asian brands, particularly Japanese ones, tend to use The Protection Grade of UVA system to measure the UVA protection that a sunscreen provides. The PA system is based on the PPD reaction and is now widely adopted on the labels of sunscreens. According to the Japan Cosmetic Industry Association, PA+ corresponds to a UVA protection factor between two and four, PA++ between four and eight, and PA+++ more than eight. This system was revised in 2013 to include PA++++ which corresponds to a PPD rating of sixteen or above.

Sunblock

Sunblock typically refers to opaque sunscreen that is effective at blocking both UVA and UVB rays and uses a heavy carrier oil to resist being washed off. Titanium dioxide and zinc oxide are two minerals that are used in sunblock.
The use of the word "sunblock" in the marketing of sunscreens is controversial. Since 2013, the FDA has banned such use because it can lead consumers to overestimate the effectiveness of products so labeled. Nonetheless, many consumers use the words sunblock and sunscreen synonymously.
For total protection against damage from the sun, the skin needs to be protected from UVA, UVB, and also IRA. Infrared radiation accounts for roughly 40% of solar energy at sea level. There is continuing debate within the dermatology community over the impact of sun-sourced IRA: Some sources indicate that early morning IRA exposure may be protective against further sun exposure by increasing cell proliferation and initiating anti-inflammatory cascades; these effects are not observed for artificial sources of intense IRA.

Active ingredients

In addition to moisturizers and other inactive ingredients, sunscreens contain one or more of the following active ingredients, which are either organic or mineral in nature:
The principal active ingredients in sunscreens are usually aromatic molecules conjugated with carbonyl groups. This general structure allows the molecule to absorb high-energy ultraviolet rays and release the energy as lower-energy rays, thereby preventing the skin-damaging ultraviolet rays from reaching the skin. So, upon exposure to UV light, most of the ingredients do not undergo significant chemical change, allowing these ingredients to retain the UV-absorbing potency without significant photodegradation. A chemical stabilizer is included in some sunscreens containing avobenzone to slow its breakdown; examples include formulations containing. The stability of avobenzone can also be improved by bemotrizinol, octocrylene and various other photostabilisers. Most organic compounds in sunscreens slowly degrade and become less effective over the course of several years even if stored properly, resulting in the expiration dates calculated for the product.
Sunscreening agents are used in some hair care products such as shampoos, conditioners and styling agents to protect against protein degradation and color loss. Currently, benzophenone-4 and ethylhexyl methoxycinnamate are the two sunscreens most commonly used in hair products. The common sunscreens used on skin are rarely used for hair products due to their texture and weight effects.
The following are the FDA allowable active ingredients in sunscreens:
UV-filterOther namesMaximum concentrationPermitted in these countriesResults of safety testingUVAUVB
p-Aminobenzoic acidPABA15% USA, AUSProtects against skin tumors in mice. Shown to increase DNA defects, however, and is now less commonly used.X
Padimate OOD-PABA, octyldimethyl-PABA, σ-PABA8% 10%
EU, USA, AUS, JPX
Phenylbenzimidazole sulfonic acidEnsulizole, Eusolex 232, PBSA, Parsol HS4% 8% 3% EU, USA, AUS, JPGenotoxic in bacteriaX
Cinoxate2-Ethoxyethyl p-methoxycinnamate3% 6% USA, AUSXX
DioxybenzoneBenzophenone-83%USA, AUSXX
OxybenzoneBenzophenone-3, Eusolex 4360, Escalol 5676% 10% 5% EU, USA, AUS, JPXX
HomosalateHomomethyl salicylate, HMS10% 15% EU, USA, AUS, JPX
Menthyl anthranilateMeradimate5%USA, AUSX
OctocryleneEusolex OCR, Parsol 340, 2-Cyano-3,3-diphenyl acrylic acid, 2-ethylhexylester10%EU, USA, AUS, JPIncreases reactive oxygen species XX
Octyl methoxycinnamateOctinoxate, EMC, OMC, Ethylhexyl methoxycinnamate, Escalol 557, 2-Ethylhexyl-paramethoxycinnamate, Parsol MCX7.5% 10% 20% EU, USA, AUS, JPBanned in Hawaii starting in 2021 - harmful to coralX
Octyl salicylateOctisalate, 2-Ethylhexyl salicylate, Escalol 587,5% 10% EU, USA, AUS, JPX
Sulisobenzone2-Hydroxy-4-Methoxybenzophenone-5-sulfonic acid, 3-Benzoyl-4-hydroxy-6-methoxybenzenesulfonic acid, Benzophenone-4, Escalol 5775% 10% EU, USA, AUS, JPXX
Trolamine salicylateTriethanolamine salicylate12%USA, AUSX
Avobenzone1--3-propane-1,3-dione, Butyl methoxy dibenzoylmethane, BMDBM, Parsol 1789, Eusolex 90203% 5% 10% EU, USA, AUS, JPX
EcamsuleMexoryl SX, Terephthalylidene Dicamphor Sulfonic Acid10%EU, AUS Protects against skin tumors in miceX
Titanium dioxideCI7789125% No limit EU, USA, AUS, JPX
Zinc oxide25% No limit EU, USA, AUS, JPProtects against skin tumors in miceXX

Zinc oxide was approved as a UV filter by the EU in 2016.
Other ingredients approved within the EU and other parts of the world, that have not been included in the current FDA Monograph:
UV-filterOther namesMaximum concentrationPermitted in
4-Methylbenzylidene camphorEnzacamene, Parsol 5000, Eusolex 6300, MBC4%*EU, AUS
Parsol Max, Tinosorb MBisoctrizole, Methylene Bis-Benzotriazolyl Tetramethylbutylphenol, MBBT10%*EU, AUS, JP
Parsol Shield, Tinosorb SBis-ethylhexyloxyphenol methoxyphenol triazine, Bemotrizinol, BEMT, anisotriazine10% 3% *EU, AUS, JP
Tinosorb A2BTris-Biphenyl Triazine10%EU
Neo Heliopan APBisdisulizole Disodium, Disodium phenyl dibenzimidazole tetrasulfonate, bisimidazylate, DPDT10%EU, AUS
Mexoryl XLDrometrizole Trisiloxane15%EU, AUS
Benzophenone-9Uvinul DS 49, CAS 3121-60-6, Sodium Dihydroxy Dimethoxy Disulfobenzophenone10%JP
Uvinul T 150Octyl triazone, ethylhexyl triazone, EHT5% 3% *EU, AUS
Uvinul A PlusDiethylamino Hydroxybenzoyl Hexyl Benzoate10% EU, JP
Uvasorb HEBIscotrizinol, Diethylhexyl butamido triazone, DBT10% 5% *EU, JP
Parsol SLXDimethico-diethylbenzalmalonate, Polysilicone-1510%EU, AUS, JP
AmiloxateIsopentyl-4-methoxycinnamate, Isoamyl p-Methoxycinnamate, IMC, Neo Heliopan E100010%*EU, AUS

* Time and Extent Application, Proposed Rule on FDA approval originally expected 2009, now expected 2015.
Many of the ingredients awaiting approval by the FDA were relatively new, and developed to absorb UVA. The 2014 Sunscreen Innovation Act was passed to accelerate the FDA approval process.

Application

The dose used in FDA sunscreen testing is 2 mg/cm2 of exposed skin. If one assumes an "average" adult build of height 5 ft 4 in and weight 150 lb with a 32-inch waist, that adult wearing a bathing suit covering the groin area should apply approximately 30 g evenly to the uncovered body area. This can be more easily thought of as a "golf ball" size amount of product per body, or at least six teaspoonfuls. Larger or smaller individuals should scale these quantities accordingly. Considering only the face, this translates to about 1/4 to 1/3 of a teaspoon for the average adult face.
Some studies have shown that people commonly apply only 1/4 to 1/2 of the amount recommended for achieving the rated sun protection factor, and in consequence the effective SPF should be downgraded to a 4th root or a square root of the advertised value, respectively. A later study found a significant exponential relation between SPF and the amount of sunscreen applied, and the results are closer to linearity than expected by theory.
Claims that substances in pill form can act as sunscreen are false and disallowed in the United States.

Regulation

; Palau
On 1 January 2020, Palau becomes the first country in the world to ban sun cream that is harmful to corals and sea life. The ban comes into effect immediately after an announcement by President Tommy Remengesau Jr.
; United States
Sunscreen labeling standards have been evolving in the United States since the FDA first adopted the SPF calculation in 1978. The FDA issued a comprehensive set of rules in June 2011, taking effect in 2012–2013, designed to help consumers identify and select suitable sunscreen products offering protection from sunburn, early skin aging, and skin cancer:
In 2019, the FDA proposed tighter regulations on sun protection and general safety, including the requirement that sunblock products with SPF greater than 15 must be broad spectrum and a prohibition on products with SPF greater than 60.

Environmental effects

Certain sunscreens in water under ultraviolet light can increase the production of hydrogen peroxide, which damages phytoplankton.
Media reports link oxybenzone in sunscreens to coral bleaching, although some environmental experts dispute the claim. A 2015 study published in the Archives of Environmental Contamination and Toxicology linked oxybenzone to affects on cell culture experiments and juvenile coral, but the study has no environmental relevance and was fraught with methodological errors and was poorly controlled. The purported link between oxybenzone and coral decline is widely disputed within the environmental community.
In 2018, the Pacific nation of Palau has become the first country to ban sun creams containing oxybenzone, octinoxate, and some other harmful elements.
A 2019 study of UV filters in oceans found far lower concentrations of oxybenzone than previously reported, and lower than known thresholds for environmental toxicity. Additionally, the National Oceanic and Atmospheric Administration has indicated that coral decline is associated with effects from climate change, overfishing, and pollution from agriculture, wastewater, and urban run-off.

History

Early civilizations used a variety of plant products to help protect the skin from sun damage. For example, ancient Greeks used olive oil for this purpose, and ancient Egyptians used extracts of rice, jasmine, and lupine plants whose products are still used in skin care today. Zinc oxide paste has also been popular for skin protection for thousands of years. Among the nomadic sea-going Sama-Bajau people of the Philippines, Malaysia, and Indonesia, a common type of sun protection was a paste called borak or burak, which was made from water weeds, rice and spices. It was used most commonly by women to protect the face and exposed skin areas from the harsh tropical sun at sea. In Myanmar, thanaka, a yellow-white cosmetic paste made of ground bark, is traditionally used for sun protection.
Early synthetic sunscreens were first used in 1928. The first major commercial product was brought to market in 1936, introduced by the founder of L'Oreal, French chemist Eugène Schueller.
Among widely used modern sunscreens, one of the earliest was produced in 1944 for the US military by Benjamin Green, an airman and later a pharmacist, as the hazards of sun overexposure became apparent to soldiers in the Pacific tropics at the height of World War II. The product, named Red Vet Pet, had limited effectiveness, working as a physical blocker of ultraviolet radiation. It was a disagreeable red, sticky substance similar to petroleum jelly. Sales boomed when Coppertone improved and commercialized the substance under the Coppertone girl and Bain de Soleil branding in the early 1950s.
In 1946, Austrian chemist Franz Greiter introduced what may have been the first effective modern sunscreen. The product, called Gletscher Crème, subsequently became the basis for the company Piz Buin, which is still today a marketer of sunscreen products, named in honor of the mountain where Greiter allegedly received the sunburn that inspired his concoction. In 1974, Greiter adapted earlier calculations from Friedrich Ellinger and Rudolf Schulze and introduced the "sun protection factor", which has become a worldwide standard for measuring the effectiveness of sunscreen. It has been estimated that Gletscher Crème had an SPF of 2.
Water-resistant sunscreens were introduced in 1977, and recent development efforts have focused on overcoming later concerns by making sunscreen protection both longer-lasting and broader-spectrum, as well as more appealing to use.

Research

New products are in development such as sunscreens based on bioadhesive nanoparticles. These function by encapsulating commercially used UV filters, while being not only adherent to the skin but also non-penetrant. This strategy inhibits primary UV-induced damage as well as secondary free radicals.
Also UV filters based on sinapate esters are under study.