Sunscreen and Make- up and Pants, Oh My!

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1 Sunscreen and Make- up and Pants, Oh My! Nanomaterials What Are They, Where Are They, Why Are They There and How Might They Emerge in Litigation? Knight S. Anderson Tucker Ellis, LLP 2016 Environmental, Mass Torts & Products Liability Litigation Joint CLE Seminar 1

2 In 1991, Sumio Iijima, a researcher with NEC, published a paper on the synthesis of "needle- like tubes" of carbon. Though there is debate as to whether Sumio was actually the first to discover these particles, as they had apparently been previously observed 40 years before by Russian scientists, his article is marked as the beginning of the nanotechnology revolution. What revolution you say? Never heard of it you say? Well, get on board. People are predicting that the nanotechnology revolution will make the computer revolution look like a blip on the radar - - seriously. Though nanotechnology has been around for more than two decades, we are just now starting to see the impact that various parts of it can have in and on everyday life, as well as the implications of its application in the future. Nanotechnology is and will continue to affect a variety of products we buy, including sunscreen, cosmetics, sporting equipment, clothing, computers and other electronics, and car parts, to batteries that we use for much longer, to the shirts and pants we wear. Nanomaterials will even change the way we treat cancer and other diseases. Though hard to track, it appears that there are currently more than 500 products that incorporate nanomaterials which are used for a variety of applications. It has been reported that the number of the nanotech products has increased more than 100% year over year recently. Industry experts have been forecasting that nanotechnology will provide game- changing advances in the areas of renewable energy, computers, communications, pollution cleanup, agriculture, medicine, and beyond. So, joint the revolution! (Or, at least be aware of it.) I. What Exactly Are Nanomaterials and Nanotubes? Nano in Greek is a prefix that means dwarf and is shorthand for nanometer. Nanomaterials are typically defined as materials that have at least one dimension that is between 1 and 100 nanometers. (A nanometer is 1/1 Billionth of a meter). How small is that? Well, this comma, for example, is about 500,000 nanometers. Yup, 500,000! 2

A nanometer is the distance that a hair in the average beard grows in the time it takes a man to lift a razor to his face to shave.

3 So, how small is a nanometer? A human hair is approximately 100,000 nm in diameter. A piece of paper is around 100,000 nm thick. A single molecule of water (H2O) is about 0.22 nm across. How small is a nanometer? A nanometer is the distance that a hair in the average beard grows in the time it takes a man to lift a razor to his face to shave. They are small, VERY VERY SMALL. Molecules of Carbon A fullerene is a molecule of carbon in the form of a hollow sphere, ellipsoid, tube, and many other shapes. A spherical fullerene is called Buckminsterfullerene (which are also known as a buckyballs ). 3

The first fullerene molecule to be discovered, and the family's namesake, Buckminsterfullerene (C60), was prepared in 1985 by researchers at Rice University.

Fullerenes have also been found to occur in nature and, remarkably, even in outer space. What is a Nanotube?

4 The first fullerene molecule to be discovered, and the family's namesake, Buckminsterfullerene (C60), was prepared in 1985 by researchers at Rice University. The name paid homage to Buckminster Fuller, the creator of the geodesic dome, which these molecules resemble. Fullerenes are used for anti- oxidant and smoothing properties in moisturizers. Fullerenes have also been found to occur in nature and, remarkably, even in outer space. What is a Nanotube? Nanotubes are members of the fullerene structural family but are nanometer- scale tubular structures with a sub- micrometer diameter and a length much longer than their diameter. Their name is derived from their long, hollow structure with walls formed by graphene, which are one- atom- thick sheets. These sheets are rolled at specific angles, and the combination of the rolling angle and radius determines the properties of the nanotube, for example, whether the individual nanotube is a metal or semiconductor. Engineered nanomaterials or ENM can be made from a wide variety of substances. Presently, ENMs are being made from carbon- based materials, but also from metals or metal oxides, including zinc, iron, cerium, zirconium, gold, silver, copper, lead, cadmium, geranium, and selenium. Key nanomaterials currently in production include metal oxides, fullerenes, carbon nanotubes, and quantum dots. 4

(MWNTs). Nanotubes are categorized as single- walled nanotubes (SWNTs) and multi- walled nanotubes "Multi- walled Carbon Nanotube" by Eric Wieser - Own work. Licensed under CC BY- SA 3.

5 (MWNTs). Nanotubes are categorized as single- walled nanotubes (SWNTs) and multi- walled nanotubes "Multi- walled Carbon Nanotube" by Eric Wieser - Own work. Licensed under CC BY- SA 3.0 via Commons The term nanotube may refer to any of a variety of tubular structures, including: BCN nanotubes (Boron Carbon Nitrogen), which were first manufactured in Carbon nanotubes (CNT) Carbon Nanotubes have unusual properties, which are valuable for nanotechnology, electronics, optics and other fields of materials science and technology. CNTs, per unit weight, range from 10 to 100 times stronger than steel, have a thermal conductivity higher than diamond, and better electrical conductivity than copper. CNTs have a huge surface area which is utilized when they are used as the electrodes in capacitors to provide more current and they provide better electrical and mechanical stability than many other materials. In particular, owing to their extraordinary thermal conductivity and mechanical and electrical properties, carbon nanotubes find applications as additives to various structural materials. To date carbon nanotubes have been constructed with length- to- diameter ratio of up to 132,000,000:1, 5

6 which is significantly larger than for any other material. There are now more than 40 CNT suppliers globally. DNA nanotubes include the manufacture of artificial nucleic acid structures for technological uses. "DNA tetrahedron white" by Antony Own work. Licensed under CC BY- SA 3.0 via Commons Inorganic nanotubes Inorganic nanotubes have been observed to occur naturally in some mineral deposits. However, the first synthetic inorganic nanotubes did not appear until the synthesis of nanotubes composed of tungsten disulfide (WS2) in Silicon nanotubes Silicon nanotubes are nanoparticles which create a tube- like structure from silicon atoms. They are technologically important because bulk silicon is the key material in the semiconductor industry. 6

7 Silver nanotubes Silver, in a variety of forms, is currently the most commonly used nano- material. Titania nanotubes Titanium dioxide, also known as titanium (IV) oxide or titania, is the naturally occurring oxide of titanium, chemical formula TiO. Nanotubes from titanium oxide are being examined for use in various products, such as sunscreens and UV blocking pigments, photocatalysts and as a drug delivery device. Tungsten (IV) sulfide nanotubes Tungsten disulfide is the first material which was found to form inorganic nanotubes in Nanotubes have or can be created to exhibit properties that make them useful for a variety of applications, such as high durability, high conductivity, strength or reactivity. II. Why Nanomaterials? Nanotechnology changes things because familiar materials begin to develop odd properties when they are nanosize. Substances behave differently, even magically, at the nanoscale level because that s where many of the essential properties of matter are determined. For example, if you arrange calcium carbonate molecules in a saw- toothed pattern, you get chalk, but if you stack those same calcium carbonate molecules properly, they form the tough, iridescent shell of an abalone. Titanium Dioxide and Zinc Oxide are opaque white, but when shrunk to nanosize, transform from white to clear. Also, you can tear a piece of aluminum foil into tiny pieces and it will still behave like aluminum, even if the pieces are microscopic. But, if these pieces become small enough, 20 to 30 nanometers the pieces can explode. Researchers are studying them for use in rocket propulsion. Understanding these nanoscale properties, scientists can engineer exotic new materials, such as plastic that conducts electricity and coatings that prevent iron from rusting. One analogy is: it s like if 7

8 you keep shrinking it, and then at some point, all at once, it turns into a dog. I know, crazy, right. Additionally, as these materials are engineered, they can be designed and made almost perfectly for very specific purposes and in particular sizes and shapes. Nanomaterials are used in a wide range of products and industrial processes that take advantage of their novel properties (physical, thermal, optical, and biological). These properties are in part determined by the chemical composition, size or shape, crystal structure, solubility, adhesion, or surface chemistry, charge, or area of the engineered nanomaterial. III. What Products Are Nanomaterials Used In? In 2005, the Project on Emerging Nanotechnologies (PEN) at the Woodrow Wilson International Center for Scholars established an inventory of consumer products sold around the world that advertise having engineered nanomaterials. That inventory contained more than 1,000 entries. And, as of 2009, the National Science Foundation estimated that up to $92 billion worth of nanotechnology- enabled products were sold in the United States annually, and that number had grown dramatically year over year and was predicted to continue to do so. Nanotechnology is used to make a wide variety of products you have probably encountered: 1. Sunscreen 2. Make- up 3. Stain- resistant fabrics using nano- coatings that bond with the material, so that little nano- sized molecular hooks attach to the fabric and repel water, but because these are nano- sized they don t make the fabric stiff. 4. Anti- Bacterial Fabrics that have silver nanoparticles added to stop bacteria and smells they are being used in socks, shirts and pillows, bedding and fabrics of other products to kill bacteria. 8

9 5. Computer Screens and solar arrays that are thinner and even flexible and that have improved color, contrast and definition. 6. Food storage containers designed to keep leftovers fresh longer. 7. Batteries that might recharge in 5 minutes and have an extended usable life. 8. Water and oil purifiers for filtering toxic chemicals, dissolved salts and biological contaminants from water. 9. Dietary and Nutritional Supplements which include nanomaterials that help deliver vitamins on a molecular level. 10. Personal care products such as hair- stimulating shampoo with gold, toothpastes with antibacterial silver nanoparticles and skin cream with energizing, detoxifying nanoparticles. 11. Plastics and polymers 12. Inks 13. Paper 14. Cosmetics 15. Pharmaceuticals and medical treatments which use nanomaterials to deliver therapeutic drugs or agents directly to particular cells. 16. Creams and Lotions that contain liposomes or now nanosomes that help to improve the solubility of ingredients and add shimmer or nanoemulsions where one liquid disperses in nano- scale size droplets throughout the another, creating a liquid so well- mixed and fine that it may be sprayed. 17. Coatings that might be anti- graffiti, anti- static, anti- mist or anti- glare or that can block UV light while letting visible light through or coat medical devices to help counteract the rejection in the body. 9

10 18. Paints that contain carbon nanotubes to prevent barnacles or algae from adhering to the hull of a vessel or that have improved qualities such as hardness, scratch, mold and bacteria resistance, easy clean and that last much longer in between applications. 19. Composites such as tennis rackets, baseball bats and body armor. 20. Glass that uses nanomaterials to become opaque, colored, reflective or an insulator. Presently, manufacturers are not required to report the use of engineered nanomaterials in the United States, except for single and multi- walled carbon nanotubes, for which the U.S. Environmental Protection Agency (EPA) finalized new rules in September IV. How Might Nanotubes Emerge in Litigation? There is some concern that nanotechnology or nanomaterials, when inhaled or ingested or if they are otherwise able to enter the body, might cause disease or injury and that they may be difficult to identify and to scientifically associate or link with exposure to nanomaterials. At this point in time, it is the fear of the possibility of nano- disease resulting from inhalation, ingestion and/or other exposures to nanomaterials. Though some have suggested the possibility of nanomaterials causing disease or even cancer has been supported by analogy (for example to asbestos, silica and PCBs) or based upon anecdotal evidence, researchers have actually studied the possibility of exposure and disease from nanomaterials. To date, while there have been some limited research studies, including both in vivo and in vitro studies, that have yielded some toxicity data on nanomaterials, especially carbon nanotubes, no link between nanomaterials and disease in humans has been established and no cases of human illness or death have been definitively attributed to engineered nanomaterials. To even have the possibility to cause disease, these nanomaterials must be released into the breathing zone and inhaled and retained in the body. Different products lead to different potential 10

11 exposures and, therefore, pose different potential hazards. For consumers, experts say, the greatest exposure probably comes from products that are inhaled or ingested or otherwise come into intimate contact with the body. Food and drinking water naturally comprise particles in the nanometer scale, and humans have always been exposed to nanometer- scale particles from things like smoke, dust, ash, and fine clays through air, food and water. Unlike the nanomaterials in food or water or personal care products, which might come into direct contact with consumers bodies, nanomaterials incorporated into composite products are much more securely embedded in a matrix and should present little or no chance even for exposure. Also, what is the effect of nanomaterials discharged into water on plants, animals, the food chain and drinking water? And, even if certain nanomaterials are found to be hazardous in the research lab, further research would need to be done to determine which ones, made out of what material, what size and shape and aspect ratio, at what dose over what period of time is a hazard presented and what are those specific hazards? The novel biological and physical properties of some engineered nanomaterials pose unique challenges to scientific research, and anyone investigating if they might be harmful to people, wildlife, and the environment. One problem is that it is exceedingly difficult to image materials smaller than 50 nm inside the human body, and quantifying carbon nanotubes is all but impossible, which poses a major challenge to assessing whether nanoparticles reach specific organs when evaluating data from toxicity studies. Additionally, compared with larger particles, nanoparticles tiny size means tissues may take them up more readily and allow them the unusual ability to travel throughout the body, including into cells and cell nuclei, and across the placenta and the blood brain barrier. It is estimated that people inhale around 10 million nanometer scale particles in every breath. However, so great is the diversity and variation of engineered nanomaterials that one report estimated conducting traditional in vivo toxicology studies on the nanomaterials currently in commerce 11

12 could take more than 50 years and cost upwards of $1 billion. Recently, the EPA announced it had awarded $5.5 million to three consortia to support innovative health and safety research on nanomaterials. According to an EPA press release, the grants will help researchers determine whether certain nanomaterials can leach out of products such as paints, plastics, and fabrics when they are used or disposed of and whether they could become toxic to people and the environment. Conclusion So, now you know at least something about nanotechnology and nanomaterials and why and how they are important, as well as some of the types of products in which they are being used. You can be aware of the possibility of nanomaterials emerging as a topic or even a hot topic in future litigation, whether it s pollution or property damage or regulatory issues or if they might be suggested or implicated as a possible cause or the cause of disease and injury in the future. While we are only at the beginning of the nanotechnology revolution, we are at the very beginning of the litigation cycle related thereto, if there should be one. Right now, awareness is the key. While nanomaterials are very small, their future is huge. Will nanomaterials emerge in future litigation and, if so, will it be on a nanoscale, a small scale or something much larger, say, perhaps, as a mass tort? Each of those possibilities is real, but only the future knows for sure. 12

13 Bibliography of Select Background Articles 1. A Research Strategy for Environmental, Health, and Safety Aspects of Engineered Nanomaterials. Committee to Develop a Research Strategy for Environmental, Health, and Safety Aspects of Engineered Nanomaterials; National Research Council. (2012). ISBN Project on Emerging Nanotechnologies http :// [Accessed on 18 May 2007]. 3. Institute of Occupational Medicine Nanoparticles: An occupational hygiene review. 4. Institute of Occupational Medicine A scoping study to identify hazard data needs for addressing the risks presented by nanoparticles and nanotubes. 5. ISO Concept Database. Nanotechnologies Terminology and Definitions for Nano- objects- - Nanoparticle, Nanofibre, and Nanoplate. Nanoscale. Geneva, Switzerland: International Organization for Standardization. 6. Analysis of Consumer Products Inventory [website]. Washington, DC: The Project on Emerging Nanotechnologies, Woodrow Wilson International Center for Scholars. 7. Kuzma J, verhage P. Nanotechnology in Agriculture and Food Production: Anticipated Applications. Washington, DC: The Project on Emerging Nanotechnologies, Woodrow Wilson International Center for Scholars (2006). 8. Oberdorster, G., E. Oberdorster, J. Oberdorster Nanotoxicology: An emerging discipline evolving from studies of ultrafine particles. Environ. Health Perspect. 113(7) : Hansen SF, et al. Categorization framework to aid hazard identification of nanomaterials. Nanotoxicology 1(3): (2007); doi: / A significant new use rule, or SNUR, requires that manufacturers, importers, and processors of certain substances notify the EPA at least 90 days before beginning any activity designated by the agency as a significant new use of an existing chemical substance in this case, the use of a nanoscale form of carbon. 11. Choi J- Y, et al. The impact of toxicity testing costs on nanomaterial regulation. Environ Sci Technol 43(9): (2009); doi: /es802388s. 12. Nanotoxicology A Pathologist s Perspective. Madhusudan et al., Toxicol Pathol : 301 originally published online 14 December EPA. EPA Awards $5.5 Million to Support Nanotechnology Research: Research to Help Determine Whether Health Risks Exist [press release]. 17 Feb Washington, DC:U.S. EPA. 14. Paracelsus in nanotoxicology. Lison et al. Particle and Fibre Toxicology 2014, 11:35. 13

nanomaterials? Worry About? Should we worry about Should we Did you know? What are nanomaterials?

nanomaterials? Worry About? Should we worry about Should we Did you know? What are nanomaterials? worry about nanomaterials? Nanomaterials contain particles which are smaller than 100 nanometres (0.0000001 metres) across. Their size means they often possess very different properties from the same materials