1. Chem. 253 – 2/18 Lecture

2. Announcements I Return HW 1.2 + Group assignment HW 1.2 – some needed to show work (e.g. conversions from molec cm -3 s -1 to g cm -3 yr -1 ) Last Week’s Group Assignment –scores were lower than expected –some blame from clarity of instructions –some problems were like non-collected review questions New HW assignment (1.4 – posted on website)

3. Announcements II Exam 2 Coming Up – Wed after next This Week’s Group Assignment –On Photochemical Smog production Today’s Lecture Topics – Tropospheric Chemistry –Review of last week’s topics/Additional Photochemistry –The other unhealthy part to smog – particulate matter –Gas phase sulfur chemistry –Aerosol chemistry –Clouds and cloud chemistry

4. Tropospheric Photochemistry Review of Main Concepts I Initiation of Oxidation –mostly by OH (O 3 and NO 3 are less significant oxidants) Hydrocarbon + CO Oxidation –OH initiates oxidation (to CO 2 in the case of CO and to carbonyls in the case of alkanes/alkenes) –Reactions also result in RO 2 radicals (R = H, CH 3, other alkyl group) –Reaction rates vary vastly (very slow for CH 4, slow for CO and small alkanes, faster for alkenes and aldehydes)

5. Tropospheric Photochemistry Review of Main Concepts II NO x and Ozone Formation –NO is primarily formed from combustion in air (e.g. cars and power plants) –NO + RO 2 → NO 2 + [RO] (RO = OH or radical capable of forming HO 2 ) –Above reaction recycles HO 2 to OH and is needed for O 3 production –Tropospheric O 3 production: NO 2 + h → NO + O O + O 2 + M → O 3 + M Radical Ending Reactions – Limit Cycles (OH + NO 2 → HNO 3, 2HO 2 → H 2 O 2 + O 2 )

6. Tropospheric Photochemistry Review of Main Concepts III Situations can be NO x or VOC Limited –NO x limited means reduction of NO x will be best for decreasing ozone –VOC limited means reduction in VOCs will best for decreasing ozone –NO x limited generally occurs under relatively low NO x conditions and VOC limited under relatively low VOC conditions –Urban areas tend to be VOC limited (high NO x ), while rural areas tend to be NO x limited (low NO x )

7. Tropospheric Photochemistry Beyond Ozone Ozone is Usually of Interest Because of: –health issues –role in generating OH –significant initiator (reacts with alkenes) Other Hazardous Compounds –radicals (OH, HO 2 ), NO 2, reservoir species (e.g. peracetyl nitrate, nitric acid, hydrogen peroxide) Other Health Issue is Aerosols: –one source is secondary aerosol (produced through OH initiated or related reactions) –aerosol generated from anthropogenic VOCs and natural VOCs (enhanced by higher OH/ozone)

8. Tropospheric Chemistry Particulate Matter/Aerosols Definitions –Aerosol = suspension of particles in a gas –Particles can be liquid or solid –Particulate Matter = the particle phase of an aerosol –Particulate Matter is also subdivided based on particle size TSP = total suspended particulate matter (typical units are  g m -3 ) PM 2.5 = particulate matter under 2.5  m in diameter –PM is traditionally collected using inlet (e.g. removes particles larger than 2.5  m for PM 2.5 ) and filters

9. Particulate Matter/Aerosols Rationale for Studying 1. Important in biogeochemical cycles (e.g. S cycle) 2. Direct Effects on Visibility and Climate (covered with Greenhouse gases later) 3. Effects on Clouds and Precipitation Physics and Chemistry 4. Effects on Human Health

10. Aerosols – Effects on Visibility View from my window on typical day Aerosol particles reduce visibility by scattering light Picture on unusually clear day from CSUS internet site View of mountains blocked by particle scattering

11. Aerosols – Effects on Climate www.osei.noaa.gov/Events/Fires/ Direct Effect of aerosols - aerosols scatter more light back to space, leading to cooling at the earth’s surface. Example: Star Fire, Aug., 2001 smoke region looks lighter due to light scattered back to space

12. Example of clouds modified by ship exhaust http://www-das.uwyo.edu/~geerts/cwx/notes/chap08/contrail.html Aerosols Effects on Clouds/Climate

13. Aerosols – Effects on Health High aerosol concentrations correlate with hospital visits Brauer and Hisham- Hashim, ES&T, 32, 1998

14. Aerosols – Size Matters Many Properties of Aerosol Particles Depend on Their Size Most Aerosols have Log-Normal Size Distributions Common Types of Size Distributions –Number (number of particles of given size) –Mass (or Volume) –Surface Area

15. Aerosols – Normal Distribution Normal Distribution (not very common) Mean diameter = 34 nm; Standard deviation (σ) = 5 nm

16. Aerosols – Log Normal Distributions Log normal distribution – appears as a normal distribution when x-axis is plotted on log scale Geometric Mean Diameter = 23 nm; Geometric Standard Deviation (σ) = 1.8

17. Aerosols – Calculation Example How many 10 nm particles (d = 10 nm) would have the same volume as 1 100 nm particles? –N*[  (10 nm) 3 /6] = 1*[  (100 nm) 3 /6] –N = (100/10) 3 = 1000 How many 10 nm particles would have the same surface area as 1 100 nm particle? –N*[  (10 nm) 2 ] = 1*[  (100 nm) 2 ] –N = 100

18. Aerosols – N and Mass Distributions Same aerosol, number distribution is dominated by smaller particles, mass distribution is dominated by larger particles For Number: Geometric Mean Diameter = 23 nm; Geometric Standard Deviation (σ) = 1.8 For Mass: Geometric mean = 65 nm

19. Break for Group Activity

20. Aerosols – Sources of Aerosols Major Classes (Based on Composition) –Soil Dust (coarse particles) –Sea Salt (coarse particles) –Sulfate (fine particles) –Carbonaceous or Organic (fine particles) Classes (Based on Sources) –Primary Sources –Secondary Sources (typically from oxidation of gaseous precursors) Note: particle “aging” and physical processes make distinction of particle classes more difficult

21. Aerosols – Sizes of Various Aerosols Surface Area Distribution (3 modes) (Whitby, 1978) ultrafine mode (dominates #) source accumulation mode sink sources: coagulation + vapor deposition growth (both from ultrafine) sink: washout coarse mode (dominates mass in boundary layer)

22. Sulfur Chemistry Forms –reduced sulfur (H 2 S, OCS, CH 3 SCH 3 ) -2 oxidation state –partially oxidized (CH 3 SOCH 3, SO 2 ) –fully oxidized (H 2 SO 4, NH 4 HSO 4 (s)) (+6 oxidation state) Chemical Fate in Atmosphere –Oxidation –Rates depend on stability (slow for OCS, fast for H 2 S, CH 3 SCH 3 )

23. Sulfur Chemistry Sources Natural Sources –Volcanoes (large SO 2 source) continuous out-gassing large eruptions (significant source of stratospheric SO 2 ) –Biota (largest sources is CH 3 SCH 3 in oceans) –Sea-salt (direct in oxidized form) Anthropogenic (mostly in form SO 2 ) –coal burning (from coal S – which varies depending on source) –smelting of metal oxides to metals (e.g. Cu production) –other fuel combustion/production (H 2 S with natural gas, heavier liquid fuels containing S)

24. Sulfur Chemistry Sources Note on Text – Anthropogenic sources are ~ 70% of total Anthropogenic – control strategies –oxidize S, remove as H 2 SO 4 or through particle traps –scrubbers (typically basic solutions to trap SO 2 gases) –remove before combustion (done with high S coal and also for diesel fuel)

25. Sulfur Chemistry Reactions Reduced Sulfur Compounds (H 2 S, CH 3 SCH 3 ) –mostly oxidized to SO 2 through OH initiated reactions –CH 3 SCH 3 also produces CH 3 SO 3 H (a tracer of natural S) Sulfur Dioxide –Gas Phase Reaction: 1)SO 2 + OH + O 2 → SO 3 + HO 2 (2 steps) 2)and SO 3 + H 2 O(g) → H 2 SO 4 (g) 3)H 2 SO 4 (g) → H 2 SO 4 (s) Step 3 can occur through a) addition to existing particles (growth of particles) or b) formation of new particles (one of very few ways to form new particles via atmospheric reactions)

26. Sulfur Chemistry Reactions Sulfur Dioxide –Aqueous Phase Reactions First step is dissolution (SO 2 (g) + H 2 O (l) → H 2 SO 3 (aq)) Then reaction with dissolved oxidants (O 3 and H 2 O 2 ) –Will Cover In Detail Later –Note that gas phase oxidation and aqueous phase oxidation results in H 2 SO 4 produced in aerosol particles – but in different sized particles

27. Atmospheric Aerosols – Carbonaceous Primary Sources –Biomass combustion (forest fire smoke) –Inefficient Fossil Fuel Combustion –Mechanically Produced (e.g. from tires) Secondary Sources (generally richer in O) –Photooxidation of gaseous precursors (e.g.  -pinene to pinonic acid) –Other (cloud, aerosol reactions)

28. Atmospheric Aerosols – Carbonaceous - Composition Rogge et al., ES&T, 1993; Los Angeles Samples

29. Atmospheric Aerosols – “ Aging” of Aerosols 1.Sea-salt and soil dust particles -Acids affect particle composition -Examples: -CaCO 3 (s) + 2HNO 3 (g) → Ca(NO 3 ) 2 (s) + CO 2 (g) + H 2 O(g) -2NaCl(s) + H 2 SO 4 (aq) → Na 2 SO 2 + 2HCl(g) 2.Fine particles -Neutralization of sulfuric acid -H 2 SO 4 (aq) + 2NH 3 (g) → (NH 4 ) 2 SO 4 (s) -Oxidation/Nitration of Organic Compounds -Aggregation/Growth of particles

30. Atmospheric Aerosols – Presence of Water At relative humidity (RH) less than 100%, many aerosol particles exist at concentrated solutions Concentration of solute is related to RH through Raoult’s law (provided particles are large enough): Where: P H2O = the vapor pressure of water, P H2O = the saturated vapor pressure of water; P H2O / P H2O = RH X H2O = the mole fraction of water in the solution i = number of species following dissociation (e.g. for NaCl, i = 2)

31. Atmospheric Aerosols – Removal of Aerosols Dry deposition particles –Most important for coarse particles (D>1 μm) –Settling rate larger for larger particles –Very small particles (<30 nm) can be removed efficiently to surfaces because they have faster diffusion rates

32. Atmospheric Aerosols – Removal of Aerosols Wet Deposition –Removal in precipitation processes –Major pathway for fine particles but inefficient for particles with D <50 nm –In-cloud scavenging (1) nucleation of cloud droplets on aerosol particles and 2) formation of precipitation from cloud droplets) –Below-cloud scavenging

33. Cloud Chemistry Rationale for Studying - Cloud reactions can be important (e.g. formation of H 2 SO 4 ) - Precipitation composition depends on cloud composition - Provide introduction to aqueous chemistry

34. Cloud Chemistry - Incorporation of Pollutants

35. Main mechanisms - Nucleation of cloud droplets on aerosol particles - Scavenging of gases - Reactions within the droplet

36. Cloud Chemistry Nucleation of Cloud Droplets (some review?) Cloud droplets can not form in the absence of aerosol particles unless RH ~ 300%. Cloud droplets nucleate on aerosol particles at RH of ~100.1 to ~101%. Cloud droplets should nucleate when RH = 100% except that the vapor pressure over a curved surface is less than that over a flat surface (due to water surface tension) Smaller particles (d < 50 nm) have more curved surfaces and are harder to nucleate

37. Cloud Chemistry - Nucleation of Cloud Droplets Nucleation more readily occurs with: - Larger particles - Particles with more water soluble compounds (due to growth according to Raoult’s law) - Compounds that reduce surface tension - Smaller aerosol number concentrations (less competition for water so higher RH values)

38. Cloud Chemistry - Nucleation of Cloud Droplets The concentration of constituents incorporated from nucleation depends on the efficiency of nucleation and on the liquid water content (or LWC). LWC = g liquid H 2 O/m 3 of air The higher the LWC, the lower the concentration (dilution effect) Cloud nucleation leads to heterogeneous cloud droplet composition – Ignored here for calculations

39. Cloud Chemistry - Scavenging of Gases Also Important for covering water chemistry (e.g. uptake of CO 2 by oceans) For “unreactive” gases, the transfer of gases to cloud droplets depends on: the Henry’s law constant (always) In special cases, transfer can depend on LWC (if high), or can be limited by diffusion Henry’s Law: where K H = constant (at given T) and X = molecule of interest

40. Cloud Chemistry - Scavenging of Gases: “unreactive” gases When LWC and K H are relatively low, we can assume that P X is constant Then [X] = K H ∙P X When K H is high (>1000 M/atm), conservation of mass must be considered (P X decreases as molecules are transferred from gas to liquid) We will only consider 2 cases (low K H case and 100% gas to water case)

41. Cloud Chemistry - Scavenging of Gases “unreactive” gases For compounds with high Henry’s law constants, a significant fraction of compound will dissolve in solution f A = 10 -6 K H RT(LWC) where f A = aqueous fraction (not used in assigned problems) When f A ~ 1, can use same method as for cloud nucleation From Seinfeld and Pandis (1998)

42. Cloud Chemistry - Scavenging of Gases: “reactive” gases Many of the gases considered are acidic and react further Example: Dissolution of SO 2 gas Reaction:Equation: SO 2 (g) + H 2 O(l) ↔ H 2 SO 3 (aq)K H = [H 2 SO 3 ]/P SO2 H 2 SO 3 (aq) ↔ H + + HSO 3 - K a1 = [H + ][HSO 3 - ]/[H 2 SO 3 (aq)] HSO 3 - ↔ H + + SO 3 2- K a2 = [H + ][SO 3 2- ]/[HSO 3 - ] Note: concentration of dissolved SO 2 = [S(IV)] = [H 2 SO 3 ] + [HSO 3 - ] + [SO 3 2- ] = [H 2 SO 3 ](1 + K a1 /[H + ] + K a1 K a2 /[H + ] 2 ) “Effective” Henry’s law constant = K H * = K H (1 + K a1 /[H + ] + K a1 K a2 /[H + ] 2 ) = function of pH

43. Cloud Chemistry Some Example Problems Why is a RH over 100% required for cloud droplet nucleation? Why is nucleation efficiency higher in less polluted regions? An ammonium bisulfate aerosol that has a concentration of 5.0 μg m -3 is nucleated with 50% efficiency (by mass) in a cloud that has a LWC of 0.40 g m -3. What is the molar concentration? What is the cloud pH? Example Problem (low K H case): What is the concentration of CH 3 OH in cloud water if the gas phase mixing ratio is 10 ppbv and a LWC of 0.2 g/m 3 ? The Henry’s law constant is 290 M/atm (at given temp.). Assume an atmospheric pressure of 0.9 atm and 20°C.