Envir Chem at KMUTT-JGSEE – Jun. –Sept., 09

1. Envir Chem at KMUTT-JGSEE – Jun. –Sept., 09 • Time: • Location: • http://www.unc.edu/courses/2009fall/enst/430/001/ • Rich Kamens; • kamens@unc.edu • http://www.unc.edu/~kamens/

2. Textbook • Environmental Chemistry by Colin Beard and Michael Cann, ISBN > ISBN-13 978-1-4292-0146-0 , publishers W.H. Freeman and Company, New York, 773 pages, 2008

3. Who is Richard Kamens • Professor of Atmospheric chemistry and teach graduate classes in Environmental chemistry • Direct a smog chamber research group • Focus on aerosol formation in the atmosphere • Direct a student exchange program between UNC and Thai Universities

4. UNC outdoor chamber

5. Gas/Particle partitioning of toxics organics on different aerosols

6. New UNC Aerosol Smog Chamber

7. Dual 270m3 chamber fine particle t 1/2 >17 h

8. We generate models to predict organic aerosol formation in the atmosphere from smog chamber experiments • Numerical fitting • Semi-explicit

9. cis-pinonaldhyde Gas phase reactions C=O C=O O O particle Link gas and particle phases

10. kon koff particle C=O O kon koff • [ igas] + [part] [ipart] Kp = kon/koff

11. + CO, HO OH 2, CHO O norpinonaldehyde COOH O O O O norpinonic O acid Criegee1 3 COOH O O O pinonic acid O a -pinene CH CHO O 3 + other O COOH products Criegee2 COOH pinic acid Mechanism

12. pinonaldehyde

13. Overall kinetic Mechanism • linked gas and particle phase rate expressions

15. Chemical System + NOx+ sunlight + ozone----> aerosols a-pinene

16. data NO model O3 NO2 ppmV NO2 Time in hours EST 0.95 ppm a-pinene + 0. 44ppm NOx

17. O O 3 mg/m Gas phase pinonaldehdye Time in hours EST

18. 3 mg/m Measured particle mass vs. model Particle phase Particle phase data 3 mg/m model TSP model TSP Time in hours EST

19. UNC outdoor chamber group

20. The Thai-CEP Undergraduate/Graduate Exchange Program The UNC-Thailand Field site • Pollution does not understand boarders. • We must begin to address these problems from both inside and outside ones culture.

21. General Approach • Since 2001, UNC-CEP undergraduates participated in a 6+ month experience in Thailand that begins at the end of May 2001 • Small groups of UNC students come together with Thai students to study and work on a research project at various Thai universities. • Thai students will go back with UNC students for a semester at UNC.

22. Classes UNC students take 3 direct contact/web-based environmental classes • Atmospheric and ecotoxicology • LCA • Energy and the Environment • Climate Change and Eco • Biomass and Energy • Energy and the Environ

23. Feasibility of Ethanol Use and an Energy Analysis and Environmental Impact of Ethanol in Thailand:KMUTT 2001- 2002

24. The Feasibility of Bio-diesel Production as Petroleum Substitute in Thailand: KMUTT 2004 Energy balance Used vegetable oil Production from Jatropha

25. Water Quality Report:Mae Kha Canal & Ping River: CMU, Chiang Mai, 2004

26. Air Pollution in NorthernThailand

33. Long standing relationship with Peking Universityand CRAESSince 1983 there were 13 visiting Chinese scholars in our research group at UNC

34. Introduction to Environmental Physical Organic Chemistry • Environmental chemistry may be defined as "the study of sources, reactions, transport, effects, and fates of chemical species in water, soil, and air environments, and the effects of technology thereon.” Manahan, 1994

35. Class objectives: • Highlight some important areas in environmental chemistry • present some of the common techniques that environmental chemists use to quantify process that occur in the environment • It is assumed that everyone has courses in organic and physical chemistry.

36. Class objectives: • We will cover general topics: Global warming, Strat. O3, aerosols, photochemical smog, acid rain, etc. • Develop relationships will be used to help quantify equilibrium and kinetic processes

37. Thermodynamics • ui = uo1 +RT ln pi/p*iL • fi = i Xipi*pure liquid • RT lnfi hx /fiopure liq = RT lnfi H2O/fiopure liqfihx = fi H2O • ln Kp = a 1/T+b

38. Vapor pressure How to calculate boiling points

39. Vapor pressure and Henry’s law sat P sat sat *    i K P V iL iw sat iaw iw C iw Solubility and activity coefficients Octanol-water partitioning coefficients

40. Homework, quizzes, exams • There will be example homework exercises; These types of questions will appear on exams.

41. Why the interest? There are more than 100,000 synthetic chemicals that are in daily use: solvents components of detergents dyes and varnishes additives in plastics and textiles chemicals used for construction antifouling agents herbicides, insecticides,fungicides

42. Some examples of environmental chemicals Polynuclear Aromatic HC (PAHs) Dioxins Ketones PCBs CFCs DDT O3, NO2, aerosols, SO2

43. PAHs Formed from small ethylene radicals “building blocks” produced when carbon based fuels are burned Sources are all types of burning in ChiangMai, Thailand:a) 2-stroke motorcycle engines b) cars- light diesels c) open burning d) barbecued meat??

44. Combustion Formation of PAH Badger and Spotswood 1960

45. PAHs Metabolized to epoxides which are carcinogenic; O PAH are indirect acting mutagens in bacterial mutagenicity tests (Ames-TA98+s9) methyl PAHs are often more biologically active than PAHs

46. Carcinogenic tests with PAHs Professor Gernot Grimmer extracted different types of smoke particles He then took the extract and applied it to mouse skin and implanted it into rat lungs How did he obtain extracts? How did he fractionate his extracts??

47. Extraction by soxhlet extraction starts with solvent (MeCl2) in a flask

48. Extraction by soxhlet extraction starts with solvent (MeCl2) in a flask MeCl2

49. The solvent is heated and starts to evaporate Heat

50. Evaporated solvent goes into a water cooled condenser where hot solvent drips out Heat