David Wollensak Ms. Borowski Scientific & Technical Writing Literature Review Importance of Coral Reefs Coral reefs provide for more organisms per unit area than any other form of marine ecosystems. Of these organisms, 800 species are corals, 4,000 species are fish, and much more species are yet to be identified. The biodiversity of these super-ecosystems contributes to the possibilities of cures for bacterial infections in humans, arthritis, viruses, and cancer. In addition to advancements in health, another benefit provided by coral reefs is that these marine environments produce trade goods and supplies that amount to $375 billion each year. Also, coral reefs protect coasts from tidal damage and avert erosion. The reefs protect valuable wetlands along the coast, and they also provide shelter to harbors and ports from storm waves. Across the globe, approximately 500,000,000 people live within 100 kilometers from a coral reef and are beneficiaries of the services provided by the reef (Importance of Coral Reefs, 2008). Basics of Coral Most corals maintain a symbiotic relationship with dinoflagellates, which are unicellular protozoan, zooxanthellae. The coral provides shelter for the zooxanthellae and also the required chemicals used by the dinoflagellates during photosynthesis. For the coral, the zooxanthellae produces oxygen which assists the coral rid itself of waste. The zooxanthellae also provides the coral with compounds produced through photosynthesis that contribute to the coral in structuring its calcium carbonate skeleton. The symbiotic relationship between the zooxanthellae and the coral is essential to the life of coral and sustainability of coral reefs (Symbiotic Algae, 2011). Coral Bleaching Coral bleaching is when the coral host excommunicates the zooxanthellae algae living in its tissues. When this occurs, the coral will transform into a white ghost of its previous self (the zooxanthellae algae provide the coral with its color). When this event occurs, the coral is not dead. However, the coral is placed under extreme stress and becomes prone to mortality. In the past, mass bleaching events have dotted the timeline, wiping out frightening amounts of coral from the ocean. For example, the Caribbean lost 50% of its coral reefs due to a mass bleaching phenomenon. Events similar to this one occur globally (What is Coral Bleaching, 2015). Figure 1. Image of bleached coral next to a healthy coral in the Great Barrier Reef (Hoegh-Goldburg, 2015). Basics of UV Light Light’s frequency is provided by the amount of energy the light contains; light with high energy has a high frequency and light with low energy has low frequency. Wavelengths of high energy light fluctuate at high speeds and wavelengths of low energy light fluctuate at low speeds. At the moment of contact between light and a material, the material does three things to the light: scattering the light (bouncing the light off in various directions), allowing the light to pass through, or absorbing the light (either completely or only in specific wavelengths). Scattering Transmission Absorption Figure 2. Depicted above are the reactions of light when it comes in contact with an object. The electromagnetic spectrum is the array of types of light given off by the sun. In the spectrum, ultraviolet light falls between visible light (while some ultraviolet light still being visible) and xray. The measurements of the wavelengths of ultraviolet light range from 100 to 10,000 angstroms. An angstrom is a measurement of length, which is equal to one tenth of one nanometer (The Nature of Light, 2010). Table 1. Ranges of angstroms associated with each type of light in the spectrum of light. Gamma 0.01 – 10 angstroms X-Ray 10 – 100 angstroms Ultraviolet 100 – 10000 angstroms Visible 3800 – 7500 angstroms Infrared Microwave Radiowave 10000 – 10000000 100000000 100000000 angstroms angstroms angstroms The variety of wavelengths within the ultraviolet light spectrum can be categorized as either UVA, UVB, or UVC. UVA light has the longest wavelength (3200-4000 angstroms). UVA can be further divided into two categories: UVA I (3400-4000 angstroms) and UVA II (3200-3400 angstroms). Ninety-five percent of the ultraviolet light that the earth experiences on the surface is UVA. UVB light has shorter wavelengths (2900-3200 angstroms) than UVA. Because UVA light and UVB light both harm organisms, protection from both wavelengths is necessary. UVC has the shortest wavelengths but most of the UVC radiation from the sun is absorbed by the ozone (Epstien, Wang 2015). The light that reaches the surface of the earth is comprised of 4% ultraviolet light, 52% infrared or weaker light, and 44% visible light (The Nature of Light, 2010). Table 2. Ranges of angstroms associated with different forms of ultraviolet light. Ultraviolet Light UVA UVB UVC 4000-3200 angstroms 3200-2800 angstroms 2800-100 angstroms UVAI UVAII 4000-3400 angstroms 3400-3200 angstroms Photosynthetic organisms only use visible light for the process of synthesizing food. Infrared light is not used for photosynthesis because the energy levels are too low. In addition, ultraviolet light is not used because the energy levels are too high, and UV light impacts plants negatively, it causes the creation of free radicals which are known to break essential chemical bonds. In summary, visible light has perfect energy levels used for photosynthesis (July, 2010 The Nature of Light). Ultraviolet Light in the Ocean The ocean is divided into three different zones which are categorized by their relation to light. The epipelagic zone of the ocean spans from the surface down to two-hundred meters deep. This zone is defined by the amount of light available that is sufficient enough for the process of photosynthesis. The next layer down, the mesopelagic zone, contains only enough light for vision, not photosynthesis. The next region down is known as the aphotic zone, where no sunlight is present (Sosik, 2004). Figure 3. A map of the different zones of the ocean along with their depths in meters and feet (Layers of the Ocean, 2015). The water in the ocean absorbs light much more efficiently than air in the atmosphere. Visible light is comprised of an array of different wavelengths; and each wavelength is seen as a different color of the rainbow. Ocean water absorbs the colors yellow, red, and orange; and this leaves blue wavelengths penetrating deep into the ocean, which gives the sea its blue appearance. Because the ocean does not absorb lights with shorter wavelengths, along with the blue light, ultraviolet light also penetrates deep into the ocean. If a scuba diver were to wear glasses that could view ultraviolet wavelengths, about 50% of the light he would see looking vertically and sideways would be ultraviolet light (Sosik, 2004). The small fraction of the ocean where sufficient amounts of sunlight penetrate is the only area where marine photosynthesis can occur. This part of the ocean is only the upper two hundred meters. Ultraviolet radiation is capable of causing harm to both terrestrial and marine life. The presence of high energy ultraviolet light in this location of the ocean may cause disastrous effects. Scientists have recently found out that UV radiation harms life deeper down in the ocean than previously thought. The death of phytoplankton, the retardation of the growth of phytoplankton, and the disruption of the relations between marine organisms are all caused by growing amounts of UV light penetrating the ocean (Sosik, 2004). Ocean species have adapted to the increased amounts of ultraviolet light present in their environment by developing pigments that absorb UV wavelengths, containing the skill the heal DNA harmed by UV, and formulating the behavior of escaping UV light by retreating deeper into the ocean. Unfortunately, fluctuations in the ozone are occurring too quickly in order for the evolution of marine species to keep up with. The entirety of the spectrum of life may be affected by this change due to the identity of phytoplankton as a base for many of Earth’s ecosystems and chemical processes (Sosik, 2004). Impacts of Ultraviolet Light on Coral The limpid qualities of open ocean water allow ultraviolet radiation to penetrate down to twenty meters in depth. Alarming amounts of UV-B have been measured as deep as ten meters, and furthermore, the effects of UV-B on life in the marine environment extend down to thirty meters in depth. High photon flux densities, which are the numbers of photons in specific areas for set amounts of time (cm-2 s-1), occur frequently during the advent of blooms of dinoflagellates in shallow waters. These high photon flux densities could cause photochemical damage that is induced by ultraviolet radiation. At the cause of these new environmental conditions, the dinoflagellates could adapt in order to survive, but these adaptations could result in a dearth of biological diversity (Banaszak, 2015). Processes that determine biological impact, that approximate the impact of specific wavelengths on biological functions, such as photosynthesis, suggest that UV-A suppresses photosynthesis while the impacts of UV-B on photosynthesis are more drastic. Where there are high levels of ozone disintegration, the repair functions of organisms that are meant to counteract the damage done by exposure to harmful ultraviolet wavelengths are not fast enough to keep up with the rates of damage induced. If the UV penetration in the ozone increases, then the UV penetration in the ocean also increases proportionally at all depths. Hence, ultraviolet radiation will be a growing significant factor affecting surface level blooming dinoflagellates. This will specifically target the dinoflagellates in symbiotic relationships with coral (Banaszak, 2015). Ultraviolet radiation (UVR) is capable of causing numerous harmful effects on marine organisms, specifically dinoflagellates. UVR is capable of deactivating RNA, DNA, proteins, and the synthesis of these biological structures inside of the dinoflagellates. These damages can lead to the prevention of cell division and growth, which can lead to the death of the cells. Increased exposure to UV-B has significant impacts on organism growth and awareness of freeliving dinoflagellates as well as dinoflagellates involved in symbiotic relationships with coral. Finally, exposure to ultraviolet radiation induces the demolition of photosynthetic pigments in dinoflagellates (Banaszak, 2015). Impacts of Sunblock on the Ocean The residue from cosmetic and personal-care products such as sunscreen or makeup create environmental issues as they leak into ecosystems. UV filters (as those used in sunscreen) are considered particularly harmful to marine environments. While ultraviolet filters do take away from the UV light that directly harms marine organisms, they are also known to degenerate the symbiotic relationship between coral and its photosynthesis partner zooxanthellae. The harm to coral is detrimental to the entirety of the ecosystem (Blitz, 2008). Once the main components of sunscreen arrive in marine ecosystems, different ingredients of the sunscreen settle in varying parts of the environment. The components may be bioconcentrated (the process of accumulation of water-borne chemicals by fish and other aquatic animals through non-dietary routes) and/or bioaccumulated (the accumulation of chemicals or pesticides in an organism) into the food web. The varying inorganic and organic components can be photo-excited by sunlight creating higher concentrations of reactive oxygen compounds that have detrimental effects on phytoplankton or be photodegraded by-products. Additional ingredients of sunscreen dissolve in water and induce algal growth (Sanchez-Quiles, Tovar-Sanchez, 2015). Figure 4. Depicted above is a graphic that shows the different things that sunscreen can do once exposed to a marine environment (Sosik, H. M., 2004). Basics of Sunscreen The essential factors of sunblock are the UV filters, which are materials that are capable of absorbing light in the UVA and the UVB ranges (4000-3200 angstroms and 3200-2800 angstroms respectively) and close to no absorption of visible light (Sanchez-Quiles, TovarSanchez, 2015). The UV filters can be categorized into two sections: inorganic and organic filters. Organic filters include substances such as cinnamates, camphor products, p-aminobenzoic acid and its products, salicylates, and benzophenone products. Inorganic filters are limited to only two compounds: titanium-dioxide and zinc-oxide. The inorganic components of sunscreen are nanoparticles (TiO2) and nanorods (ZnO) in order to continue their protection from UV wavelengths as well as not whiten the skin. Different benefits are provided by the two UV filters. Organic filters are capable of absorbing definite wavelengths while the inorganic filters provide a wide variety of protection because they reflect, absorb, and scatter UV-light. Sunblock is typically made up of one or more or a mixture of these components; and combinations of inorganic and organic filters provide favorable UV protection (Sanchez-Quiles, Tovar-Sanchez 2015). In order to prevent the introduction of alien chemicals into marine environments, divers are cautioned not to wear sunblock in the vicinity of coral reefs. A recent experiment supports this idea that sunblock is harmful to sea life (Brown, 2008). This issue was first recognized by Mexican resort managers when small pools of water (also known as cenotes) along the Yucatan coast became frequently used as swimming holes for tourists by Mexican resort managers. Roberto Danovaro from the Polytechnic University of Marche in Ancona, Italy states that the death count of organisms living in the cenotes spiked during this time. Sunblock was looked to as the suspect, so many resorts prohibited the beachgoers/divers from applying sunblock while swimming in areas near coral reefs or in cenotes (Brown, 2008). Benzophenone-3 Benzophenone-3 is becoming more and more of a threat to the stability of marine environments. Benzophenone-3 can be found in various everyday products used worldwide. Oxybenzone is an ingredient in shampoos and conditioners, lip balms and other cosmetics, a variety of facial products, dish soaps, and sunscreens. This chemical is introduced to marine ecosystems via waders and boats. Oxybenzone is a photo-toxicant, which means that in order for the toxic effects of oxybenzone to be activated, light is required. The toxic effects of benzophenone-3 are worsened with more light exposure. Oxybenzone is hazardous to coral reefs because it debilitates the corals durability to climate change (Downs, 2015). Coral reef areas worldwide are exposed to between 6,000 and 14,000 tons of benzophenone-3 based sunscreens each year. About 10% of the globe’s reefs are at risk of being exposed to this detrimental chemical, and about 40% of the coastal reef areas experience this same risk. At Okinawa Island, Japan, the reefs that range from 300-600 meters away from the shore experience approximately 0.4 to 3.8 parts per trillion of oxybenzone. In South America, coastal reefs experience levels of an average of 54 to 578 parts per trillion of oxybenzone. Benzophenone-3 is especially alarming because despite its half-life in seawater being only many months, there is a constant income of oxybenzone into the oceans. This creates a seemingly constant exposure to oxybenzone by the corals (Downs, 2015). Interestingly, in an experiment testing the effects of benzophenone-3 on coral planulae, this chemical still deformed the planulae into a debilitated, immobile state in both darkened and lightened conditions. Also, the coral planulae exhibited alarming rates of coral bleaching in both conditions. When the coral planulae was exposed to higher concentrations of benzophenone-3, the rate of coral bleaching increased. Oxybenzone is identified as a genotoxicant to corals, meaning that this chemical destructively impacts the DNA of coral. As the concentrations of benzophenone-3 were increased during the experiment, higher rates of DNA-AP lesions were observed. In addition to that, oxybenzone is a skeletal endocrine disruptor, which means that it induces the process that changes the cartilage of the planulae into bone. When exposed to benzophenone-3, the coral planulae become enveloped inside of their own skeleton (Downs, 2015). UV Absorption and Potential of Chicken Eggshell Cuticle It was demonstrated that the absence of the external coats of bird eggshells with cuticles increases UV reflectance. This proposes that the cuticle regulates the reflectance of UV light in white eggshells. It is assumed that this regulation of UV light is attained by the absorption of UV-wavelengths by substances in the organic portion of the eggshell (cuticle). The chicken eggshell is intriguing due to the fact that the absorption of UV light significantly decreased after the removal of the cuticle. This proposes that a trait of the chicken eggshell raises the intrinsic reflectance of UV light of calcite potentially via nanostructuring (no known pigment is capable of absorbing light across the entirety of the spectrum of wavelengths), but it is not accurately discerned what this function is. The data of the experiment offer the idea that cuticle absorbs UV-light. The eggshells of birds are exceptional candidates for biomimetic projects (clothing, paints, sunscreen, etc.) because it decreases the harmful impacts of exposure to the sun. Chicken eggshells in particular are favorable candidates for biomimetic research because the UVreflectance traits exceed being of solely calcite (Fecheyr-Lippens, 2015). Figure 5. This diagram shows the effects of the EDTA treatment on the UV-Chroma of the avian eggshells over time (Fecheyr-Lippens, 2015). Composition of Chicken Eggshell The results of the study suggest that the cuticles of avian eggshells absorb UV-light because of their high concentrations of organic compounds (calcium phosphates in the cuticle in opposition to the mainly calcite eggshell). Two known components of the eggshell that specifically absorb UV-light are the tetrapyrrole pigments- biliverdin and protoporphyrin IX, yet it is assumed that other components of the eggshell also absorb UV-light and advance the efficiency of absorption of the tetrapyrrole pigments. The cuticle is composed of lipids, polysaccharides, calcium carbonate, proteins, and calcium phosphates. The components of the proteins (amino acids) and the calcium phosphates have a noticeably larger pool of light waves that they are capable of absorbing than biliverdin and protoporphyrin IX. Both families of compounds capitalize their UV-light absorption potential and are main ingredients of the avian eggshell. Specifically, the cuticle of the chicken eggshell is composed of 85-90% proteins, 2.53.5% lipids, and 4-5% polysaccharides. These carbon based factors absorb UV-light. It is also possible for the inorganic factors also absorb UV-light (Fecheyr-Lippens, 2015). Figure 6. These graphs show the dispersed reflectance of UV-light over a time duration of EDTA treatment. The gray area represents the UV wavelength range (Fecheyr-Lippens, 2015). Eggshells as a Waste Product The disposal of eggshells is a daunting topic for the waste management industry. Organizations are paying up to $100,000 annually to manage the waste of eggshells in landfills. In addition to that, the quantity of eggshells being disposed of each year is huge and requires ample amounts of space in landfills. Also, the protein-based membrane on the inside of the eggshell rots in the landfills and attracts rodents, which contaminate the disposal systems (Sonenklar, 1999). Literature Cited Sosik, H. M., Johnsen, S. (2004, October, 15). Shedding Light on Light in the Ocean. Oceanus Magazine, 43. “Layers of the Ocean.” – Deep Sea Creatures on Sea and Sky. N.p., n.d. Web. 22 Nov. 2015 Downs, C., Kramarsky-Winter, E., Segal, R., Fauth, J., Knutson, S., Bronstein, O., . . . Loya, Y. (2015). Toxicological Effects of the Sunscreen UV Filter, Oxybenzone (Benzophenone3), on Coral Planulae and Cultured Primary Cells and Its Environmental Contamination in Hawaii and the U.S. Virgin Islands. Springer Science. doi:10.1007/s00244-015-0227-7 Importance of Coral Reefs. (2008, March 25). Retrieved November 24, 2015. Symbiotic Algae. (2011, May 13). Retrieved November 24, 2015. What is Coral Bleaching? (2015, October 8). Retrieved November 26, 2015. Hoegh-Goldburg, O. (n.d.). Coral Bleaching. Retrieved Novomber 26, 2015. Brown, S. (2008). Sunscreen wipes out corals. Nature: International weekly journal of science. doi: 10.1038/news.2008.537 Fecheyr-Lippens, D. C. and Igic. B. and D’Alba L. and Hanley. D. and Verdes. A. and Holford. M. and Waterhouse. G. I. and Grim. T. and Hauber. M. E. and Shawkey. M. D. (2015). The cuticle modulates ultraviolet reflectance of avian eggshells. In Biology Open. The Company of Biologists. doi: 10.1242/bio.012211 Sanchez-Quiles, D. Tovar-Sanchez, A. (2015). Are sunscreens a new environmental risk associated with tourism?. Environmental International. Trench, R, K. Banaszak, A, T. (2001). Ultraviolet Sunscreens in Dinoflagellates. Protist, Volume 152, pp. 93-101.
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