EUPHORE Chamber in Spain (204m 3` x 2) Swiss Indoor Chamber (27m 3 )

1. New Indoor and Outdoor Smog ChambersCosts, advantages/disadvantages and types of things one can study • EUPHOREChamber in Spain (204m3`x 2) • Swiss Indoor Chamber (27m3) • Caltech indoor chamber (28m3 • EPA-RTP indoor chamber indoor (14.5m3) • UNC-outdoor chamber (135m3x2) • UCR-CERT indoor (90m3x2)

2. The European PhotoreactorEUPHORE (1996) • Largest outdoor chamber (204 m3) • FEP film with a thickness of 0.127 mm (80% transmission) • Positive pressure (100-200 Pa) • State of the art instrumentation DOAS (O3, NO2, HCHO, HONO) , long-path FT-IR TDL (tunable diode laser)

3. This image shows one of the two chambers of EUPHOR

4. The European PhotoreactorEUPHORE (1996) • K.H. Becker / Project Co-cordinator becker@physchem.uni-wuppertal.de • J. Hjorthjens.hjorth@jrc.it • G. Laverdetlaverdet@cnrs-orleans.fr • M.M. Millánmillan@ceam.es • U. Plattpl@uphys.uni-heidelberg.de

5. Caltech new Indoor chambers(Cocker and Seinfeld et al, ES&T 35, 2594,2001) • Two 28m3 meters • 2 ml FEP Teflon wall • Controlled aerosol injection system • Indoor lights

8. William Carter aerosol chambers • two collapsible 90m3 FEP Teflon film reactors inside an outer enclosure. • Solar radiation is simulated with either a 200kW Argon arc lamp or multiple black lamps. • Collapsible system, positive 5 pa, Outer enclosure flushed with clean air to reduce input of dirty air from outside; temp controlled from 5-45oC • mechanism evaluation data for experiments with NOx levels as low as 2 ppb

11. New UNC outdoor aerosol dual chamber • Quonset Hut design; 270 m3 FEP Teflon film chambers. • Natural sunlight • Exchange rate with outside air 0.5 to 1.5%/hour • Particle half-live of 17 hours • Design permits chamber walls to be easily washed

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

14. New UNC aerosol smog chamber

15. Major costs for any chamber system • NOx, O3 $24,000 • 4 GC and GCMSs 200,000 • 6 nm to 900 nm particles 85,000 • 0.3 to 5 um particles 25,000 • Data system 3,500 • Light and Dew point 6,000 • Flow meters, etc 10,000 • 6 place balance 12,000 • Clean air generator 20,000 • Denuders and filter holders 10,000 • Total = ~$ 400,000 • Build a new chamber ~50,000-100,000

16. Need an analytical and an modeling group

17. Chemical mechanisms Product studies Effects of light, temperature and water vapor Generate data for modeling studies Simple compounds Complex mixtures Gases and particle interactions Research Issues that can be studied in Environmental Chambers

18. Wall effects Care is needed to extend results to the atmosphere. Problems with Environmental Chambers

19. Wall effects Aldehydes, HONO can off gas from the walls wet walls adsorb more aldehydes and NOX outer sheath of clean air purchase a “clean batch” of Teflon film have a chamber design that permits cleaning run characterization tests before and after cleaning (O3 decay)

20. Test and develop gas phase chemical mechanisms Develop product information and yields Reactivity Evaluate aerosol formation Aerosol products Aerosol kinetic mechanisms What are some historical uses for Environmental Chambers

21. The Chamber had two sides Or Darkness 300 m3 chamber Teflon Film walls

22. The Chamber had two sides Or Darkness 300 m3 chamber Teflon Film walls propylene Formaldehyde

23. The Chamber had two sides Or Darkness 300 m3 chamber Teflon Film walls propylene Formaldehyde

24. The Chamber had two sides Or Darkness NO &NO2 300 m3 chamber Teflon Film walls propylene Formaldehyde

25. Example experiment with the following chamber concentrations: • NO = 0.47 • NO2 = 0.11 ppm • Propylene = 0.99 ppmV • temp = 15 to 21oC

26. Solar Radiation Profile

27. Example Mechanism • NO2+ hn -> NO + O. k1 keyed to sunlight • O. + O2 --> O3 k2 • O3 +NO2 --> NO+ O3 k3 • H2C=O + hn --> .HC=O + H. k4 keyed to sunlight • H. +O2 --> HO2. k5 • HO2. + NO --> NO2+OH.k6 (fast) • OH.+ C=C ---> H2C=O + HO2+ H2COO. k7 • dNO2/dt = -k1[NO2]; DNO2=-k1 [NO2] Dt

28. Photochemical System

29. Photochemical System

32. Studying AEROSOLS IN Chambers • Ambient data often guides experiments • Our understanding of aerosol formation is ~20 years behind gas phase chemistry

33. PM10 Chemical Characterization in BeijingXiao-Feng, Min Hua, Ling-Yan Hea, Xiao-Yan Tang, Atmos. Environ. 39 (2005) 2819–2827

34. Characteristics of carbonaceous aerosols in Beijing, ChinaYele Suna, Guoshun Zhuang, Ying Wang, Lihui Han, Jinghua Guo, Mo Dan, Wenjie Zhang, Zifa Wang, Zhengping Hao, Atmos, Environ. 38 (2004) 5991–6004 • coal burning, traffic exhaust, and dust from the long-range transport, were the major sources of the aerosol pollution in Beijing. • Mineral aerosol from outside Beijing accounted for 79% of the total PM10 minerals and 37% of the PM2.5 in winter. It was 19% and 20% in summer

35. Characteristics of carbonaceous aerosols in Beijing, ChinaFengkui Duan, Kebin He, Yongliang Ma, Yingtao Jia,Fumo Yang, Yu Lei, S. Tanaka, T. Okuta,Chemosphere 60 (2005) 355–364 • OC/EC ratio (on a 1.5 basis showed that SOC accounted more than 50% for the total organic carbon. In winter, the SOC contribution to OC was also significant, and as high as 40%.

36. Characteristics of carbonaceous aerosols in Beijing, ChinaYele Suna, Guoshun Zhuang, Ying Wang, Lihui Han, Jinghua Guo, Mo Dan, Wenjie Zhang, Zifa Wang, Zhengping Hao, Atmos, Environ. 38 (2004) 5991–6004 • PM2.5/PM10 ratios were 0.45–0.48 in summer and 0.52–0.73 in winter • in winter. SO4 , NO3, NH4, OC,crustal matter, and EC were the six dominant species

37. Can we chemically and kinetically model Secondary Organic Aerosol Formation??? • Numerical fitting • Semi-explicit

38. From a modelingperspective Equilibrium Organic Gas-particle partitioningprovides a context for addressing SOA formation

39. Thermodynamic Equilibrium? Cgas +surf Cpart Temperature Chemical nature of gas Humidity and particle Gas/Particle Partitioning gas particle Kp will vary with 1/Po

40. Odum-Seinfeld Model SOA model Y= Mo / D HC

41. a- pinene- NOx experiments by Odum Y Mo(mg/m3) 1 0.012 1 2 0.028 8 3 0.056 22 4 0.067 34 5 0.081 38 6 0.116 83 7 0.122 94 Y= Mo / D HC

42. a-pinene a1 = 0.038, Kom1= 0.17 a2 = 0.326, Kom2 = 0.004 How is this done?

43. Overall kinetic Mechanism • links gas and particle phase rate expressions

44. -1 -1 -1 gas phase reactions min or ppm min . a 1 -pinene + O .4 Criegee1 + .6 Criegee2 à 1.492 exp-732/T 3 2. Criegee1 .3 pinacid + .15 stabcrieg1 + .8 OH à gas + .5 HO + .3 pinald + .25 oxy- pinald + .3 CO 6 1x10 2 gas gas 3. Criegee2 .35 crgprod2 + .5 oxy- pinald à gas +.35 HCHO + .15 stabcrieg2 +.8 OH + .5 HO 6 1x10 2 4. stabcrieg1 + H O pinacid -3 à 6x10 2 gas 10. oxy- prepinacid +HO oxy- pinacid à 677 exp1040/T 2 16. pinacid {walls} -7 à 4x10 exp2445/T gas partitioning reactions 22. stabcrieg1 + pinald seed1 à 29.5, gas 25. pinacid + seed1 seed1 + pinacid à 29.8, gas part 34. diacid + pinacid --> pinacid + diacid 68, gas part part part 35. diacid diacid 14 à 3.73x10 exp-10285/T part gas 44. diacid {walls} à 0.0008, part

45. Particle Phase reactions cis-pinonaldhyde Gas phase reactions C=O C=O O O polymers particle

46. Particle Phase reactions cis-pinonaldhyde C=O C=O O O Gas phase reactions particle polymers

47. Particle Phase reactions cis-pinonaldhyde C=O C=O O O Gas phase reactions polymers

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

49. Gas Phase -pinene and O3data and model Warm high concentration experiment -pinene MODEL MODEL 