VII. Tropospheric Ozone Catalytic Cycles Terminating the Cycles Initiating Organic Chemistry Meteorology.

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VII. Tropospheric Ozone Catalytic Cycles Terminating the Cycles Initiating Organic Chemistry Meteorology

Ozone Damages lung – hard on kids, the aged, and anyone with bad lungs Concentrations ppbv (continental background) 80 ppbv (EPA 8 hour limit) 120 ppbv (old EPA 1 hour limit)

EPA Map of Peak Ozone Concentration 0-60 ppb ppb ppb ppb ppb 125+ ppb No Data

Source of Ground-Level O 3 NO 2 + h → NO + O O + O 2 → O 3 NO + O 3 → NO 2 + O 2 NO x = NO + NO 2 NO x + sunlight yields O 3 These 3 reactions  steady state w/limited [O 3 ]

Add CO and HO x Chemistry OH + CO → H + CO 2 H + O 2 → HO 2 HO 2 + NO → OH + NO 2 NO 2 + h → NO + O O + O 2 → O 3 CO + 2 O 2 → CO 2 + O 3 CO CO 2 OH HO 2 NO NO 2 h O O3O3 O2O2

Add Organic Compounds… OH + CH 4 → CH 3 + HOH CH 3 + O 2 → CH 3 OO CH 3 OO + NO → CH 3 O + NO 2 CH 3 O + O 2 → CH 2 =O + HO 2 HO 2 + NO → OH + NO 2 2{NO 2 + h → NO + O} 2{O + O 2 → O 3 } CH O 2 → CH 2 =O + 2 O 3 + H 2 O

NO x Concentrations Urban 5-20 ppbv Rural 0.1 – 5 ppbv Remote ppbv [HOO] ≈ Sum over [ROO] << [NO x ] except for Remote k(ROO + NO) ≈ k(HOO + NO) ≈ k(ROO + HOO) So HOO and ROO mostly react with NO

Termination of Cycles RO  RH + OH, O 2 → ROO  NO NO 2 h RONO 2 Limits NO x Cycling and organic radical chem.

Termination of Cycles at High [NO 2 ] NO 2 RCH 3 RCH=O OH HO 2 NO NO 2 h HONO 2 Stops HO x Cycling

Termination of Cycles at low [NO x ] RO  ROO  NO NO 2 h HOO  ROOH 2 HOO  → HOOH + O 2 organic radical chem. HOx cycling

Contour of Maximum [O 3 ] VOC (ppmC) NO x (ppb) [O 3 ] max 160 ppb 120 ppb 80 ppb NO x : VOC ≈ 1:7 downtown downwind

Fate of Organic Compounds- OH vacuum cleaner of the atmosphere OH + RH → R  + HOH OH + RCH=CH 2 → RCHCH 2 OH or RCH(OH)CH 2  OH Production photochemical (daylight) O( 1 D) + HOH → 2 OH HONO + h → OH + NO HOO + NO → OH + NO 2 HOO from CH 2 =O + h and organic radicals 

NO 3 + RCH=CH 2 → RCHCH 2 ONO 2 or RCH(ONO 2 )CH 2  NO 3 Production NO + O 3 → NO 2 + O 2 NO 2 + O 3 → NO 3 + O 2 (slower than NO 2 + h ) NO 2 + NO 3 → N 2 O 5 NO 3 + h → NO 2 + O or NO + O 2 (  = seconds) [NO 3 ] only significant in the dark !! Fate of Organic Compounds- NO 3 

Fate of Organic Compounds- O 3

Activity

Meteorology and Air Pollution “Dilution is the Solution to Pollution” Dispersing vs. Trapping pollutants Planetary Boundary Layer - region influenced by surface (convection) - vertical mixing time scale of 1 hour - 1st 100 m – 2 km - diurnal (daily) cycle

Planetary Boundary Layer

Ozone and Topography

Topography and Meteorology Pacific Ocean(km)San Bernadino Mtns

Topography and Meteorology Pacific Ocean(km)San Bernadino Mtns

Topography and Meteorology

Inversion Layer Warmer above than below, so air is trapped time limited, specific geography

Key Points Sunlight, NO x, and Organics Cycles in HO x and NO x NO x is globally limiting reagent OH removes organics (O 3, NO 3 ) Kinetics calculations - steady state concentrations - fate of species Topography (meteorology)