1. Good Ozone and Bad Ozone MEES, March 5, 2008 Mort Sternheim, mort@umassk12.net Rob Snyder, snyder@umassk12.net STEM Education Institute Center for Hierarchical Manufacturing University of Massachusetts Amherst MEES, March 5, 2008 Mort Sternheim, mort@umassk12.net Rob Snyder, snyder@umassk12.net STEM Education Institute Center for Hierarchical Manufacturing University of Massachusetts Amherst

2. Our sponsors National Science Foundation grant to the UMass Center for Hierarchical Manufacturing, award # 0531171 NASA grant to the STEM Education Institute (ended), award # NNG05GN64G Advertisement: We are accepting teacher applications for International Polar Year and Nanotechnology Summer Institutes

3. Todays agenda 1.Ozone and ultraviolet (UV) light 2.Nanoparticles and sunscreen Hands on sunscreen activity 3.Ozone is a health problem Measuring ozone handouts Todays materials on line: www.umassk12.net/nano/MEES

4. The big ideas Ultraviolet light causes skin damage and cancer Ozone in the stratosphere blocks UV, partly Sunscreen blocks UV, partly Nanoparticles in sunscreen improve blocking Tropospheric ozone is a major part of smog, damages plants, animals, and people

5. 1. Ozone and UV Ordinary oxygen gas: O 2 (2 oxygen atoms) Ozone: O 3 (3 oxygen atoms) Polar molecule, like water Ozone is much more reactive, unstable Pale blue, poisonous gas Bad! Absorbs ultraviolet radiation! Good!

6. The Suns radiation spectrum ~ 43% is in the visible range ~ 49% is in the near infrared range ~ 7% is in the ultraviolet range < 1% is x-rays, gamma rays, radio waves. Most of the suns radiation is Ultraviolet (UV), Visible & Infrared (IR) : Source: Adapted from http://www.ucar.edu/learn/imgcat.htm

7. Some types of electromagnetic radiation The sun emits several kinds of electromagnetic radiation: Visible (Vis), Infrared (IR) and Ultra Violet (UV). Note the split into UVA, UVB, UVC Each kind is distinguished by a characteristic wavelength, frequency and energy Higher energy radiation can damage our skin Source: http://www.arpansa.gov.au/is_sunys.htm High Energy Low Energy

8. What is Radiation? Light radiation is often thought of as a wave with a wavelength ( ), speed (c), and frequency (f) related by Source: http://www.pueblo.gsa.gov/cic_text/health/sun_uv/sun-uv-you.htm Since c (the speed of light) is constant, the wavelength and frequency are inversely related This means that light with a short wavelength will have a high frequency and visa versa.

9. Radiation energy comes in packets or photons The size of an energy packet or photon (E) is determined by the frequency of the radiation (f) E f E f Radiation with a higher frequency has more energy in each packet The amount of energy in a packet determines how it interacts with our skin

10. Very high energy radiation (UVC) is currently blocked by the ozone layer High energy radiation (UVB) does the most immediate damage (sunburns) But lower energy radiation (UVA) can penetrate deeper into the skin, leading to long term damage Source: N.A. Shaath. The Chemistry of Sunscreens. In: Lowe NJ, Shaath NA, Pathak MA, editors. Sunscreens, development, evaluation, and regulatory aspects. New York: Marcel Dekker; 1997. p. 263-283. Skin Damage

11. Good ozone In the stratosphere, absorbs 97+ % of solar UV, protecting life from harm Produced by solar UV light from O 2 : – O 2 + UV (radiation < 240 nm) 2 O – O + O 2 O 3 Ozone – oxygen cycle: – O 3 + UV (< 320 nm) O 2 + O This cycle heats the atmosphere slightly, so ozone is a greenhouse gas

12. 12 Ozone (parts per million) 0 20 40 60 80 100 Altitude (km) Troposphere Mesosphere Thermosphere Ozone In the Atmosphere Altitude (miles) 10 0 20 30 40 50 60 90% of ozone is in the stratosphere 02468 10% of ozone is in the troposphere

13. 13 UVc - 100% Absorption UVb - 90% Absorption UVa - 50% Absorption & Scattering Ozone is the Earths natural sunscreen Ozone (parts per million) 0 20 40 60 80 100 Altitude (km) Troposphere Mesosphere Thermosphere Altitude (miles) 10 0 20 30 40 50 60 02468

14. Ozone layer Ozone in stratosphere, 10 to 50 km above surface Ozone Can be depleted by free radical catalysts – NO, OH, Cl, Br – from natural sources Also from chlorofluorocarbons (CFCs) (freons) and bromofluorocarbons (halons) – UV light produces free Cl, Br radicals – Cl, Br catalyze chain reactions destroying ~100,000 ozone molecules Used in aerosols, refrigerators, air conditioners, fire extinguishers

15. Chemicals that Destroy Stratospheric Ozone Cl is much more abundant than Br Br is about 50 times more effective at O 3 destruction From Ozone FAQ - see http://www.unep.org/ozone/faq.shtml

16. Ozone depletion Ozone levels decreasing ~4% per year since 70s More skin cancer? Larger seasonal decrease in lower altitudes (troposphere) in polar regions: the ozone hole CFCs phased out globally by 1996 (Montreal Protocol, 1987) – will take decades to leave atmosphere Ozone levels have stabilized Recovery will take decades

17. Low level (tropospheric) ozone Formed by interaction of UV with hydrocarbons, nitrogen oxides from natural sources plus car exhausts, etc. Major air pollution (smog) component Can cause serious damage to lungs Fatal in very high concentrations for people, animals Damage to plants – UNH Forest Watch looks at white pine needles which store data for 3 years – www.forestwatch.sr.unh.edu – Excellent school project Measure with ozone sensitive paper, new meters

18. Ozone levels 3 – 10 ppb: Threshold of perception. Typical indoor level when outdoor levels are low 50 ppb: Maximum allowed indoor levels 100 ppb: Maximum allowed in industrial work area 150 - 500 ppb: Typical outdoor peak urban levels 300 ppb: Threshold for nasal, throat irritation 500 ppb: Smog alert #1 in Los Angeles. Can cause nausea, headaches; lead to lung edema.

19. Higher ozone levels 1000 – 1500 ppb: Smog alerts #2, 3 in LA. Headaches, chest pains after 2 hours 12,000 ppb: Lethal for guinea pigs after 3 hrs 50,000 ppb: Lethal for humans after 60 minutes

20. 2. Nanoparticles and sunscreen 1 nanometer = 10 -9 meter ~ 10 atomic diameters Nanoparticles: 1 to 100 nm in diameter, or about 10 to 1000 atomic diameters Sunscreen PowerPoint and activities based on NanoSense web site – http://nanosense.org/activities/clearsunscreen

21. Nano Products Number of products using nanomaterials is growing very rapidly – Doubling every year? Clothing, food and beverages, sporting goods, coatings, cosmetics, personal care Sunscreens: many use nanomaterials – Some labeled as containing nanoparticles – Some not labeled

22. http://www.masspolicy.org/p df/workshop/rejeski.pdf

23. Why Use Sunscreen? Too much unprotected sun exposure leads to: Premature skin aging (e.g. wrinkles) Sunburns Skin cancer Sources: http://www.oasishospital.org/previousnews.html; http://wohba.com/archive/2005_03_01_archive.html

24. Skin Cancer Rates are Rising Fast Skin cancer: Is ~50% of all cancer cases Has > 1 million cases diagnosed each year Causes 1 person to die every hour Probability of getting skin cancer: 1930 : 1 in 5,000 2004 : 1 in 65 2050 : 1 in 10… http://www.skincarephysicians.com/skincancernet/whatis.html; http://www.msu.edu/~aslocum/sun/skincancer.htm Causes of the increase: Decrease ozone protection Increased time in the sun Increased use of tanning beds Sources: http://www.msnbc.msn.com/id/8379291/site/newsweek/ ;

25. Radiation Type Characteristic Wavelength ( Energy per Photon % of Total Radiation Reaching Earth Effects on Human Skin Visible to Human Eye? UVC~200-290 nm (Short-wave UV) High Energy ~0% (<1% of all UV) DNA DamageNo UVB~290-320 nm (Mid-range UV)Medium Energy ~.35% (5% of all UV) Sunburn DNA Damage Skin Cancer No UVA~320-400 nm (Long-wave UV) Low Energy ~6.5% (95 % of all UV) Tanning Skin Aging DNA Damage Skin Cancer No Vis~400-700 nm Lower Energy ~43 %None Currently Known Yes IR~700-120,000 nm Lowest Energy ~49%Heat Sensation (high IR) No Sun Radiation Summary Increasing Energy Increasing Wavelength

26. Which Sunscreen Should You Use??? New and Improved Now with Nano-Z SPF 50 Goes on Clear Safe for Children Broadband Protection

27. Sources: http://www.bbc.co.uk/wiltshire/content/articles/2005/05/05/peoples_war_feature.shtml http://www.arpansa.gov.au/is_sunys.htm A Brief History of Sunscreens: The Beginning First developed for soldiers in WWII (1940s) to block sunburn causing rays Shorter wavelengths (more energy) called UVC Longer wavelengths (less energy) called UVA These were called UVB rays WWII soldier in the sun

28. Sources: http://www.shop.beautysurg.com/ProductImages/skincare/14521.jpg and http://www.shop.beautysurg.com/ProductImages/skincare/14520.jpg A Brief History of Sunscreens: The SPF Rating SPF (Sunscreen Protection Factor) Number – Measures the strength of UVB protection only – Higher SPF # = more protection from UVB – Doesnt tell you anything about protection from UVA Sunscreens first developed to prevent sunburn – Ingredients were good UVB blockers

29. A Brief History of Sunscreens: The UVA Problem UVA rays have no immediate visible effects but cause serious long term damage – Cancer – Skin aging Sunscreen makers working to find UVA blockers – No official rating of UVA protection yet Source: http://www.cs.wright.edu/~agoshtas/fig8.jpg Twenty different skin cancer lesions

30. How do you know if your sunscreen is a good UVA blocker?

31. Know Your Sunscreen: Look at the Ingredients Lotion has inactive ingredients – Dont block UV light UV blocking agents are active ingredients – Usually have more than one kind present Source: Original Image UV blocking agents suspended in a lotion – Colloidal suspension Two kinds of active ingredients – Organic ingredients and inorganic ingredients

32. Organic Ingredients: The Basics Organic = Carbon Atoms – Hydrogen, oxygen & nitrogen atoms are also often involved Structure – Covalent bonds – Exist as individual molecules Size – Molecular formula determines size – Typical a few to several dozen Å (<10 nm) Sources: http://www.3dchem.com/molecules.asp?ID=135# and original image Octyl methoxycinnamate (C 18 H 26 O 3 ) an organic sunscreen ingredient

33. Organic Ingredients: UV Absorption 1.Electrons capture the energy from UV rays 2.They jump to higher energy levels 3.The energy is released as infrared rays which are harmless (each ray is low in energy) Source: Adapted from http://www.3dchem.com/molecules.asp?ID=135#and http://members.aol.com/WSRNet/tut/absorbu.htm hf=2.48 eV3hf=2.48 eV

34. Organic Ingredients: Absorption Range Organic molecules only absorb UV rays whose energy matches difference between electron energy levels – Different kinds of molecules have different peaks and ranges of absorption – Using more than one kind of ingredient (molecule) gives broader protection One Ingredient Two Ingredients Three Ingredients Source: Graphs adapted from http://www.aims.gov.au/pages/research/projects/sunscreens/pages/sunscreens02.html

35. Organic Ingredients: Absorption Range cont. Most organic ingredients that are currently used were selected because they are good UVB absorbers – The FDA has approved 15 organic ingredients Sunscreen makers are trying to develop organic ingredients that are good UVA blockers – Avobenzone (also known as Parasol 1789) is a new FDA approved UVA blocker Source: http://jchemed.chem.wisc.edu/JCEWWW/Features/MonthlyMolecules/2004/Oct/JCE2004p1491fig4.gif

36. How are inorganic sunscreen ingredients different from organic ones? How might this affect the way they absorb UV light?

37. Inorganic Ingredients: The Basics Atoms Involved – Zinc or Titanium – Oxygen Structure – Ionic attraction – Cluster of ions – Formula unit doesnt dictate size Size – Varies with # of ions in cluster – ~10 nm – 300 nm Source: http://www.microspheres-nanospheres.com/Images/Titania/TIO2%20P7.jpg and image adapted from http://www.cse.clrc.ac.uk/msi/projects/ropa.shtml Group of TiO 2 particles Detail of the ions in one cluster

38. Inorganic Ingredients: Cluster Size Inorganic ingredients come in different cluster sizes (sometimes called particles) – Different number of ions can cluster together – Must be a multiple of the formula unit ZnO always has equal numbers of Zn and O atoms TiO 2 always has twice as many O as Ti atoms ~100 nm TiO2 particle ~200 nm TiO 2 particle Source: Images adapted from http://www.cse.clrc.ac.uk/msi/projects/ropa.shtml

39. Inorganic Ingredients: UV Absorption Inorganics have a different absorption mechanism than organics Absorb consistently through whole UV range up to ~380nm Source: Graph adapted from http://www.aims.gov.au/pages/research/projects/sunscreens/pages/sunscreens02.html

40. Why not use inorganics? Appearance Matters Traditional inorganic sunscreens have appear white on our skin Many people dont like how this looks, so they dont use sunscreen with inorganic ingredients Of the people who do use them, most apply too little to get full protection Source: http://www.4girls.gov/body/sunscreen.jpg

41. Why Do They Appear White? Traditional ZnO and TiO 2 clusters are large – (> 200nm) Large clusters scatter visible light – (400-700 nm) – Maximum scattering occurs for wavelengths twice as large as the clusters The scattered light is reflected to our eyes, appearing white Source: Original image

42. Organic Sunscreen Molecules are Too Small to Scatter Light ~200 nm TiO 2 particle Methoxycinnamate (Inorganic)(Organic) (Note that these images are not drawn to scale) Source: Images adapted from http://www.cse.clrc.ac.uk/msi/projects/ropa.shtml and http://www.3dchem.com/molecules.asp?ID=135#

43. Waves and obstacles Waves go around small obstacles Waves scatter all around from obstacles of sizes comparable to a wavelength Water wave (ripple tank) simulation: http://www.falstad.com/ripple/ http://www.falstad.com/ripple/

44. What could we do to inorganic clusters to prevent them from scattering visible light? Source: Adapted from http://www.loc.gov/rr/scitech/mysteries/images/sunscreen2.jpg

45. Nanosized Inorganic Clusters Source: Graph adapted from http://www.aims.gov.au/pages/research/projects/sunscreens/pages/sunscreens02.html Maximum scattering occurs for wavelengths twice as large as the clusters – Make the clusters smaller (100 nm or less) and they wont scatter visible light

46. Nano-Sunscreen Appears Clear Source: http://www.science.org.au/sats2003/images/barber-slide3.jpg Nanosized ZnO particles Large ZnO particles

47. In Summary… Nanoparticle sunscreen ingredients are small inorganic clusters that: – Provide good UV protection by absorbing both UVB and UVA light – Appear clear on our skin because they are too small to scatter visible light Source: http://www.smalltimes.com/images/st_advancednanotech_inside_.jpg

48. Essential Questions: Time for Answers 1.What are the most important factors to consider in choosing a sunscreen? 2.How do you know if a sunscreen has nano ingredients? 3.How do nano sunscreen ingredients differ from other ingredients currently used in sunscreens?

49. Testing sunscreen activity Use UV sensitive beads Compare opacity/transparency of samples for visible light and UV light

50. How can we measure ground level ozone? Ozone paper – Moderate cost – Adequate for relative measurements – Used for NASA Globe project But: – Inconsistent sensitivity one batch to the next – Insensitive to low ozone levels

51. Sources for ozone sensitive papers Vistanomics – www.ecobadge.com – Eco badge kit (30 test cards), $38.95 – Eco badge lesson books middle school, 150 cards, 119.95 Ozone Services – www.ozonelab.com/products/OLM/o3ts.htm – Ozone test strips, 105 ppb, 12 strips, $13.50 – 30 strips, $33.50

52. Miniature Ozone Sensor for K-12 Outreach Joyce Cheung, Paul Voss, Smith College David Greenberg, Greenfield Community College

53. Miniature ozone sensor Under development at Smith College Measures ozone, pressure, pressure Uses a semiconductor to detect ozone Works at low and high ozone levels Measure at 10 minute intervals and store 2 weeks of data Accurate data at parts per billion level Moderate cost

54. Instrument Intercomparison Red: AIRNow-Tech, Chicopee Station Blue: Smith College, McConnell Building Black: Smith College, Whately AirMap Station