Enst 110: May 15 – June 17, 2006

1. Enst 110: May 15 – June 17, 2006 • Mon-Fri, room 9:45AM-11:15AM • Location: Murphey room 204 Call number 33409, Section 001 • http://www.unc.edu/courses/2006ss1/enst/110/001/ • Rich Kamens; 966 5452 • kamens@unc.edu • http://airsite.unc.edu/~kamens/

2. Textbook • "Environmental Chemistry by Colin Beard and Michael Cann, ISBN 0-7167-4877-0, publishers W.H. Freeman and Company, New York, 652 pages, 2005

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

4. UNC outdoor chamber

5. New UNC Aerosol Smog Chamber

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

7. 3 mg/m Measured particle mass vs. model Particle phase Particle phase data 3 mg/m model TSP model TSP Time in hours EST

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

9. 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.

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

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

14. Introduction to Environmental 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

15. 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 calculus and general chemistry.

16. 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

17. 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

18. Vapor pressure How to calculate boiling points

19. 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

20. Additional Principles • Organic Acid-bases and LFERs • diffusion • chemical spills and mass transfer • Organic reactions in the environment • Solid- liquid interactions • photochemistry

21. Homework, quizzes, exams • To insure that most of us stay reasonably current with the lectures and readings, an option is to have 8-10 unannounced quizzes throughout the semester. • They will take ~10 minutes. Quizzes will count 10% of your grade.

22. Another option is a set of short questions to be answered and handed in before most lectures (20% of your grade)—your choice!

23. There will be a homework problem set associated with each assigned chapter of the book. • These problem sets should take between 1 and 3 hrs.

24. Some of these could appear on exams • There will be two exams

25. Important Environmental Issues • Global warming and stratospheric ozone depletion • Concentration of environmental pollutants at the poles; pesticides in foods, etc. • Buildup of environmental chemicals in the oceans; contamination of soil and ground water • Particle exposure, photochemical oxidant exposure, acid deposition • Energy shortages

26. Why the interest? There are more than 70,000 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

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

28. 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??

29. Combustion Formation of PAH Badger and Spotswood 1960

30. Some PAH structures fluoranthene naphthalene anthracene benz(a)anthracene phenanthrene benzo(a)pyrene [BaP]

31. PAHs Naphthalene, phenanthrene and anthracene are found in the gas phase pyrene and fluoranthene are in both the gas and particle phase BaA and BaP are mostly on the particles, Why???

32. 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

33. 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??

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

35. Hot solvent fills this chamber and bathes the filter Heat

36. The solvent in the filter chamber then drains back into the heated flask withchemicalsfrom the particleson the filter Heat

37. The organic liquid in the soxhlet flask can be concentrated by evaporation by a dry nitrogen stream or rotary evaporation • the extract can then be fractionated into different polarity compound groups

38. Professor Grimmer fractionated the exhaust extracts HPLC uv orfluorescencedetector Total Total PAH 2&3 rings PAHs>3 rings Total-PAHs

39. What did Grimmer see when exposed rats and mice to the different fractions? • skin painted mice • implanted rat lungs

41. Analysis of reaction products • soxhlet extraction for 3 hours • blow up with dry gentle flow of nitrogen to about 0.5 to 1 ml • evaporation to about 0.5 to 1 ml • 1 to 2 ul injected directly to GC-MS (EI and CI) • The remainder solution: derivatization

42. In environmental samples why don’t we see some large highly oxygenated compounds that form in the atmophere?? Reverse reactions to the original aldehyde parent structures can occur during sample work up/solvent extraction procedures;

43. PFBHA O-(2,3,4,5,6-pentafluorobenzyl) -hydroxylamine for carbonyl groups

44. Pentafluorobenzyl bromide (PFBBr)derivatization for carboxylic and hydroxyl groups P F B B r F F H C C H 3 3 O O H C H C O H C O F C H B r 2 2 F F F F H C C H O 3 3 O C H C O C H F H O C H B r 2 2 F F F F F F C H C H O O 3 3 C H C O C H F O C 2 H B r F C H 2 2 2 F F F F

45. BSTFA for carbonyl, hydroxyl, and/or carboxylic

46. GC-EIMS for Oxygenated Terpenoids

47. Thermal desorption particle beam mass spectrometry (Paul Ziemann) Particle generator or smog chamber

48. Chlorinated dibenzo dioxins and Furans These are some of the most toxic organics in the environment - LD50 Created by burning organics which have chlorine; incineration is a big source of atmospheric dioxins and furans bleaching in making paper is another source

49. Combustion Formation of Dioxins from Polychlorinated phenol O H Clx . OH Clx Flame . O O H + Polychlorinated Phenol C l y O + OH O Cly Cly Clx O Clx O H Chlorinated dibenzo dioxin Shaub & Tsang, ES&T 1983.

50. They have the following general structures O Cl x O Cl y chlorinated dioxin