purdue/ANE

1. www.purdue.edu/ANE Agriculture, Engineering, Science Center for the Environment Birck Nanotechnology Center

2. Manufactured Nanomaterials in the Environment Ron Turco, Loring Nies, Chad Jafvert, Bruce Applegate, Natalie Carroll, Tim Filley, Robert Blanchette1, Leila Nyberg, Zhonghua Tong, Pradnya Kulkarni, Marianne Bischoff and Benjamin Held1 Purdue University and University of Minnesota1

3. RD-83172001-0 Acknowledgements The authors acknowledge support from the National Science Foundation (NSF) under Award EEC-0404006 & United States EPA under Award RD-83172001-0

4. Nanotechnology Defined • Working at length scales of ~1–100 nanometers [nm] • Results in new properties and functions • Allows an ability to control (to see, measure, and manipulate) matter on the atomic & molecular scale • Allows us to manipulate systems spanning from nano- to macroscopic scales

5. 1 cm 1 mm 100 mm 1 mm 100 nm 1 nm How small is a Nanometer? Start with a centimeter Divide it into 10 equal parts (millimeter long)Divide that into 10 equal parts (100 micrometers) Divide that into 100 equal parts (micrometer)Divide that into 10 equal parts (100 nanometers) Divide that into 100 equal parts (Nanometer) bean flea human hair bacterium virus Nano- material 1 cm = 10,000,000 nm

6. “There’s plenty of room at the bottom” (1959) • The inspiration for nanotechnology came from Richard P. Feynman, 1959: • ”The problems in chemistry and biology can be greatly helped if our ability to see what we are doing, and do thing on an atomic level, is ultimately developed – a development which I think cannot be avoided.”

7. Science (1985) • Fullerenes are discovered by Robert Curl, Harold Kroto and Richard Smalley (Noble Prize) • Spherical fullerenes -- buckyballs, • Cylindrical nanotubes -- buckytubes

8. Nano-technology ~ 30 years later • Eric Drexler (1986) Student in Feynman’s lab Engines of Creation The Coming Era of Nanotechnology (concept of “molecular manufacturing”) Creation of the National Nanotechnology Initiative (NNI-Funding) (~25% DOD)

9. National Nanotechnology Initiative (NNI) Budget History

10. The manufacturing technology of the 21st century • Fabrication of devices with atomic or molecular scale precision • Devices with some minimum feature sizes of less than 100 nanometers (nm) are considered to be products of nanotechnology • The products can have quantum level features

11. From the Bottom • NT allows a bottom-up manufacturing approach • Nanotechnology processes can add: • material until the product has been created • makes the process similar to biological systems • theoretically possible to start with one atom • Production at 120 to 180 nm

12. Materials • Lighter, stronger and programmable materials • Lower failure rates and reduced life-cycle costs • Better electrical efficiencies • Bio-inspired /Bio-reactive materials • Multifunctional, adaptive materials • Self-healing materials • Self-cleaning surfaces (e.g., windows)

13. Nano-based Products • Computing, Data Storage, Electronics • Organic light-emitting diodes (OLEDs) • Nanoscale transistors • LCDs, LEDs, MP3s, electronic ink displays, thin film batteries, and flexible electronics • Integrated nanosensors: • Collecting, processing and communicating data with minimal size, weight, and power consumption

14. Clothing/Film Products • Color-changing fabrics • Breathable waterproof ski jacket • Wrinkle-resistant, stain-repellent threads • Nanofilms are used now on eyeglasses, computer displays, and cameras to protect or treat the surfaces.

15. Health and Medicine Products • Bandages embedded with silver nanoparticles – kill bacteria • Drug delivery via a patch • Thin films on implantations into the human body (for example screws, joints, and stents) allowing devices to last longer • Respiration monitors that are many times more sensitive • Nano-skin for skin graft applications

16. Health • Nanocrystalline Sunscreen • Zinc oxide provides broad-spectrum protection against UVA and UVB rays • Main ingredient is Z-COTE • Made with nanotechnology . . . Nano-dispersed zinc oxide. . . . Goes from a white color to clear

17. Energy • Energy Production: Clean, less expensive sources • Solar energy: Photovoltaic cells • Better Energy Utilization • Materials of construction sensing changing conditions and in response, altering their inner structure

18. Environmental • Environmental cleanup • Filters built out of carbon nanotubes, • Antifouling filters • Sieves that can filter bacteria and poliovirus particles out of drinking water

19. Sports Products • Tennis rackets • Nanotube Power and VS Nanotube Drive lightweight • Tennis balls • Wilson Double Core tennis balls • NanoDynamics golf ball • This ball is engineered with nanoparticles to spin less to reduce the slice/hook problems • Stronger golf clubs • More accurate bowling balls

20. Potential Military NT(DARPA) • Rugged/Embedded/Interlinked low-energy nanosensors to create pervasive networks • Monitor for chemical & biological agents • Implanted sensors for identification and health

21. Potential Military NT(DARPA) • Nanofiber composites • Heat resistant, lighter and stronger • Cloaking devices • Fuel Cells (H2 –storage) electric vehicles • Strengthening of light armor • Better autonomous vehicles • (combination of small electronics and nanofiber composites)

22. Potential Military NT(DARPA) • Propellants and explosives with higher energy density • Miniaturized guidance systems

23. Everything is great? • Fears of Gray Goo • Fears from “Prey” • Comparisons of nano to biotech • Generally no knowledge of environmental fate • No data to back claims on either side of the argument

24. Exposure Routes • Nanomaterials in clothing (uniforms) and equipment break off and enter the body and environment • Nanoparticles as surface coverings erode and enter environment • Nano-based fuels/explosives/ cloaking agents create residuals

25. A Nanomaterials Fate? Drift Uptake Introduction Volatilization Sorption Degradation Runoff Drainage -- Tile Flow Leaching

26. Question: Is C60 is impacting the microbiology in the soil food web? http://www.blm.gov/nstc/soil/bacteria/index.html

27. The talk presents the findings from a number of ongoing projects Soils Work Biosolids Work Fungal Work

28. Typical Midwest Soils and chemical C60 preparations methods are established. • Formation: Deguchi, et al., 2001 • Concentration: Fortner et al., 2005 • Size: DLS system

29. Our chosen soil microbiology methods are well established and documented Evaluate Microbial Systems Microbial Form (PLFA/PCR-DGGE) Three domains model Functions (CO2 CH4) Size (Biomass) Glucose Assimilation (14C-CO2) Fungal Abilities (13C)

30. C60 and nC60 had little impact on soil functions Soil Respiration Biomass Size 6-months nC60 1 ppm / C60 1000 ppm – Drummer Soil

31. No impact from longer incubations – Glucose assimilation testing method established Test procedure Response Soil Challenged Soil Incubated Soil Tested NanoMaterial Soil 14C-CO2 Time 14C-Glucose

32. Microbial profiling showed no difference after six months DGEE – 6 months PLFA 3 or 6 Months

33. Combinations of fullerenes with soil water stress show no effects Five water potentials Two nano materials (nC60, C60, C12) Two Soils Respiratory response

34. Soil diversity showed effects from C60 combined with water potential Fatty Acids patterns from soils with nanomatrials and under water stresses (each symbol has an associated water potential)

35. Preliminary data suggests nC60 crystal size had no effect on soil response nC60 formed in different size classes (mixing speed) added to soil Respiratory response after 30 day exposure

36. Assessing the Impact of Nanomaterials on Anaerobic Microbial Communities

37. Environmental Receptor: The Wastewater Treatment Plant http://www.waterencyclopedia.com/images/wsci_04_img0570.jpg

38. Objectives and Hypotheses • Objective I. • Examine the effect of C60 on an anaerobic community. • Hypothesis I. • C60 will remain inert and exert no detectable toxic effects on anaerobic communities. Methanogenesis (community function) will be unaffected by treatment with C60.

39. Objectives and Hypotheses • Objective II. • Develop Three-Domain Community Analysis • Hypothesis II. • Three-Domain Community Analysis will detect shifts in anaerobic communities more completely than the more widely used analysis of community structure in a single domain.

40. Community Function Measured by Anaerobic Toxicity Assay +/- Substrate: C6H12O6 CH3OH CH3CH2OH (G/M/E)

41. Concentration – Dependent Antibiotic Toxicity • - G/M/E reference.  - 2 mg/L metronidazole + G/M/E.  - 200 mg/L metronidazole + G/M/E.

42. C60 Did Not Inhibit Gas Formation • - G/M/E Substrate Reference • - C60 dissolved in MeOH/EtOH + G/M/E ▬ - aqeuous suspension C60 + G/M/E ▲- C60 dissolved in toluene, plated on dried sludge + G/M/E

43. Archaea Eukarya Bacteria Antibiotic treatment induced community chagnes shifts in all three domains R1 m M1 M1 M2 M2* R1 M1 R2 M2 R1 R2 R2*

44. C60 did not affect Archaeal Community Profile Increasing % G+C A B C H1 D F G H2 Denaturing gradient gel electrophoresis with Archaea primers, showing similar community profiles at the end of each experiment for treated samples and reference samples.

45. No Bacterial Community Shifts with C60 treatment Increasing % G+C A B C H1 D F G H2 DGGE with Bacteria primers, showing similar community profiles at the end of each experiment for treated samples and reference samples.

46. Conclusions and Significance • No evidence of C60 toxicity to any subset of the microbial community, No evidence of major community shifts • No methods for measurement of nanomaterials or products in the environment, nano risk assessment not yet standardized • Important role for analysis of microbial community structure and function • Long-term studies of C60 in the environment will be necessary to determine biodegradation potential

47. Outreach • Mission (objectives) of the outreach program are helping the general public, especially high school students, understand the science behind the manufactured nanoparticles. • www.purdue.edu/ANE

48. Outreach

49. www.purdue.edu/ANE