AREP GAW

Section 7 Chemical Aspects of Air Pollution
Overview of Basic Pollutants Ozone Particulate Matter Carbon Monoxide Sulfur Dioxide Nitrogen Oxides

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Section 7 – Chemical Aspects of Air Pollution 2

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Photochemical Smog
Air pollution formed by sunlight catalyzing chemical reactions of emitted compounds Los Angeles, California • Early pollution due to London-type smog.
1905-1912, L.A. City Council adopts regulation controlling smoke

• Early 1900’s, automobile use increases.
1939-1943 visibility decreases significantly.

• Plume of pollution engulfs downtown (26 July 1943).
1943: L.A. County Board of Supervisors bans emission of dense smoke and creates office called Director of Air Pollution Control

• 1945. L.A. Health Officer suggests pollution due to locomotives, diesel trucks, backyard incinerators, lumber mills, dumps, cars. • 1946. L.A. Times hires air pollution expert to find methods to ameliorate pollution.
Section 7 – Chemical Aspects of Air Pollution 3

Section 7 – Chemical Aspects of Air Pollution 4 .AREP GAW Los Angeles. Washington. D. C. 1909) Library of Congress Prints and Photographs Division. California (December 3.

A.A. • Oil companies and business leaders argue that ozone in L. damage to materials. Postulates that ozone and precursors are main constituents of L. • 1952: Haagen-Smit finds that ozone forms when oxides of nitrogen and reactive organic gases are exposed to sunlight. biochemistry professor at Caltech. smog. originates from stratosphere. • Other researchers find that rubber cracks within minutes when exposed to high ozone. • 1950: Finds that plants sealed in a chamber and exposed to ozone exhibit similar damage as did plants in smog • Also finds that ozone caused eye irritation.AREP GAW Discovery of Ozone in Smog • 1948: Arie Haagen-Smit (1900-1977). Section 7 – Chemical Aspects of Air Pollution 5 . • Measurements of low ozone over Catalina Island disprove this. respiratory problems. begins to study plants damaged by smog.

services. and emissions from the biosphere and geosphere Section 7 – Chemical Aspects of Air Pollution 6 Pollutants originate from ● ● ● .AREP GAW Basic Pollutants (1 of 3) Categories of pollutants ● ● ● Primary – emitted directly from a source Secondary – formed in the atmosphere from a reaction of primary pollutants Precursors – primary pollutants (gases) that participate in the formation of secondary pollutants Combustion of fossil fuels and organic matter Evaporation of petroleum products or compounds used in commercial products. dust from strong winds. and manufacturing Natural production of smoke from fires.

AREP GAW Basic Pollutants (2 of 3) Pollutant Carbon Monoxide Sulfur Dioxide Ozone Nitrogen Dioxide Hydrocarbon Compounds (also called VOCs – volatile organic compounds ) Particulate Matter Abbreviation CO SO2 O3 NO2 HC PM Section 7 – Chemical Aspects of Air Pollution 7 Type Primary Primary Secondary Secondary Primary & Secondary Primary & Secondary .

AREP GAW Basic Pollutants (3 of 3) Section 7 – Chemical Aspects of Air Pollution 8 .

Dioxins. PAHs. 1998 Point 24% Mobile (onroad) 31% Section 7 – Chemical Aspects of Air Pollution 9 .AREP GAW Basic Pollutants – Toxics (1 of 2) ● ● Air toxics (hazardous air pollutants) are known or suspected to cause cancer or other serious health effects. by-product of chlorination processes) – BTEX. chemical processes) – Perchlorethylene (dry cleaning. EPA’s 188 hazardous air pollutants include – Benzene (motor fuel. oil refineries.S. Metals (Hg. degreasing) – Chloroform (solvent in adhesive and pesticides. Cr) Area/ Mobile Other 25% (nonroad) 20% National air toxics emissions sources in 1996 U. Environmental Protection Agency.

AREP GAW Basic Pollutants – Toxics (2 of 2) • Differences between toxics and criteria pollutants – Health criteria are different • No AQI-like standards for toxics • Cancer/non-cancer benchmarks (long-term exposures) • Short-term exposure limits for some – A challenge to monitor • Usually not available in real-time • Example: Dioxin requires 28 days of sampling to acquire measurable amounts in ambient air – Often localized near source Section 7 – Chemical Aspects of Air Pollution 10 .

AREP GAW Basic Pollutants – Sources (1 of 4) • Combustion • Evaporation • Natural Production Section 7 – Chemical Aspects of Air Pollution 11 .

CO2.AREP GAW Basic Pollutants – Sources (2 of 4) Combustion • Complete combustion Fuel  water and carbon dioxide (CO2) • Incomplete combustion Fuel  water. and other pollutants Pollutants are both gases and particles Section 7 – Chemical Aspects of Air Pollution 12 .

limonene (ozone. some react to produce other pollutants • Many items you can smell are evaporative pollutants – – – – Gasoline – benzene (sweet odor. greenhouse gas) Trees – pinenes.and particulate matter forming) – Baking bread. fermenting wine and beer – VOCs and ethanol (ozoneforming) Section 7 – Chemical Aspects of Air Pollution 13 .and particulate matter forming) Paint – volatile organic compounds (ozone.AREP GAW Basic Pollutants – Sources (3 of 4) Evaporation • Thousands of chemical compounds • Liquids evaporating or gases being released • Some harmful by themselves. carcinogenic) Bleach – chlorine (toxic. toxic.

ocean. microbes • Volcanoes and oil seeps produce particles and gases Section 7 – Chemical Aspects of Air Pollution 14 . sand and create particles of various sizes • Biosphere emits gases from trees. plants. animals. dirt.AREP GAW Basic Pollutants – Sources (4 of 4) Natural Production • Fires (combustion) produce gases and particles • Winds “pick up” dust. soil.

AREP GAW Ozone • Colorless gas • Composed of three oxygen atoms – Oxygen molecule (O2)—needed to sustain life – Ozone (O3) —the extra oxygen atom makes ozone very reactive • Secondary pollutant that forms from precursor gases – Nitric oxide – combustion product – Volatile organic compounds (VOCs) – evaporative and combustion products Section 7 – Chemical Aspects of Air Pollution 15 .

AREP GAW Solar radiation and chemistry • The reaction that produces ozone in the atmosphere: O + O2 + M  O3 + M • Difference between stratospheric and tropospheric ozone generation is in the source of atomic O • For solar radiation with a wavelength of less than 242 nm: O2 + hv  O + O Section 7 – Chemical Aspects of Air Pollution 16 .

AREP GAW Solar radiation and chemistry • Photochemical production of O3 in troposphere tied to NOx (NO + NO2) • For wavelengths less than 424 nm: NO2 + hv  NO + O • But NO will react with O3 NO + O3  NO2 • Cycling has no net effect on ozone Section 7 – Chemical Aspects of Air Pollution 17 .

AREP GAW Tropospheric Ozone Photolysis Troposphere ozone photolysis takes place in a narrow UV window (300-320 nm). NO2 broadly below 428 30o equinox midday Solar spectrum Section 7 – Chemical Aspects of Air Pollution 18 .

and NO2.AREP GAW Nitrogen Oxides ● ● ● ● ● Nitrogen oxides. electric utilities. Nitrogen dioxide is most visually prominent (it is the yellowbrown color in smog) The primary man-made sources of NOx are motor vehicles. commercial. which also cause respiratory problems – Contributes to the formation of acid rain (deposition) Section 7 – Chemical Aspects of Air Pollution 19 . and other industrial. is the generic term for a group of highly reactive gases. and residential sources that burn fuels Affects the respiratory system Involved in other pollutant chemistry – One of the main ingredients in the formation of ground-level ozone – Reacts to form nitrate particles. or NOx. all of which contain nitrogen and oxygen in varying amounts. acid aerosols.

AREP GAW Must make NO2 • To make significant amounts of ozone must have a way to make NO2 without consuming ozone • Presence of peroxy radicals. from the oxidation of hydrocarbons. disturbs O3-NO-NO2 cycle NO + HO2·  NO2 + OH· NO + RO2·  NO2 + RO· – leads to net production of ozone Section 7 – Chemical Aspects of Air Pollution 20 .

effectively recycled Section 7 – Chemical Aspects of Air Pollution 21 .AREP GAW The Hydroxyl Radical • produced from ozone photolysis – for radiation with wavelengths less than 320 nm: O3 + hv  O(1D) + O2 followed by O(1D) + M  O(3P) + M (+O2O3) O(1D) + H2O  2 OH· (~90%) (~10%) • OH initiates the atmospheric oxidation of a wide range of compounds in the atmosphere – referred to as ‘detergent of the atmosphere’ – typical concentrations near the surface ~106 .107cm-3 – very reactive.

AREP GAW THE OH RADICAL: MAIN TROPOSPHERIC OXIDANT • Primary source: • O3 + hn  O2 + O(1D) • O(1D) + M  O + M • O(1D) + H2O  2OH (1) (2) (3) • Sink: oxidation of reduced species –leads to HO2(RO2) production • CO + OH  CO2 + H • CH4 + OH  CH3 + H2O • HCFC + OH Major OH sinks • Global Mean [OH] = 1.0x106 molecules cm-3 Section 7 – Chemical Aspects of Air Pollution 22 .

AREP GAW Oxidation of CO .production of ozone CO + OH·  CO2 + H· H· + O2 + M  HO2· + M NO + HO2·  NO2 + OH· NO2 + hv  NO + O O + O 2 + M  O3 CO + 2 O2 + hv  CO2 + O3 Section 7 – Chemical Aspects of Air Pollution 23 .

even at low levels Section 7 – Chemical Aspects of Air Pollution 24 .AREP GAW Carbon Monoxide • • • • Odorless. colorless gas Caused by incomplete combustion of fuel Most of it comes from motor vehicles Reduces the transport of oxygen through the bloodstream • Affects mental functions and visual acuity.

AREP GAW What breaks the cycle? • Cycle terminated by OH· + NO2  HNO3 HO2· + HO2·  H2O2 • Both HNO3 and H2O2 will photolyze or react with OH to.though H2O2 less-so • washout by precipitation • dry deposition – in PBL they are effectively a loss – situation is more complicated in the upper troposphere • no dry deposition. reverse these pathways – but reactions are slow (lifetime of several days) – both are very soluble . limited wet removal Section 7 – Chemical Aspects of Air Pollution 25 . in effect.

NO. NO2) • Warm air Section 7 – Chemical Aspects of Air Pollution 26 .AREP GAW Ozone Chemistry Summary of ozone chemistry Meteorology • NO2 + Sunlight  NO + O Production • O+ O2  O3 • NO + O3  NO2 + O2 • VOC + OH  RO2 + H2O • RO2 + NO  NO2 + RO Production Emissions Chemistry Destruction Production of NO2 without the Destruction of O3 RO=Reactive Organic compound such as VOC Key processes – Weak horizontal dispersion – Weak vertical mixing • Ample sunlight (ultraviolet) • High concentrations of precursors (VOC.

AREP GAW Day and Night Chemistry Section 7 – Chemical Aspects of Air Pollution 27 .

AREP GAW Ozone Precursor Emissions (1 of 2) ● Man-made sources – Oxides of nitrogen (NOx) through combustion – VOCs through combustion and numerous other sources Meteorology Emissions Chemistry ● Natural sources (biogenic) – VOCs from trees/vegetation – NOx from soils (Midwest fertilizer) ● Concentration depends on – Source location. and strength – Meteorology Section 7 – Chemical Aspects of Air Pollution 28 . density.

5 Section 7 – Chemical Aspects of Air Pollution 29 .2 Aircraft 0.1 Biomass Burning 5.2 Lightning 5.AREP GAW NOx EMISSIONS (Tg N yr-1) TO TROPOSPHERE Stratosphere 0.2 Biofuel 2.1 Soils 5.8 Fossil Fuel 23.

AREP GAW An example of gridded NOx emissions Section 7 – Chemical Aspects of Air Pollution 30 .

AREP GAW Mapping of Tropospheric NO2 From the GOME satellite instrument (July 1996) Section 7 – Chemical Aspects of Air Pollution 31 .

AREP GAW GOME Can Provide Info on Daily Info Section 7 – Chemical Aspects of Air Pollution 32 .

AREP GAW Lightning Flashes Seen from Space DJF JJA 2000 data Section 7 – Chemical Aspects of Air Pollution 33 .

AREP GAW Global Budget of CO Section 7 – Chemical Aspects of Air Pollution 34 .

AREP GAW Satellite Observations of Biomass Fires (1997) Section 7 – Chemical Aspects of Air Pollution 35 .

3 0.8 27.5 113.5 1399 313 108 29 33 500 47 2429 904 14.3 6.2 6.AREP GAW Daily Los Angeles Emission (1987) Gas Carbon monoxide Nitric oxide Nitrogen dioxide Nitrous acid Total NOx+HONO Sulfur dioxide Sulfur trioxide Total SOx Alkanes Alkenes Aldehydes Ketones Alcohols Aromatics Hemiterpenes Total ROGs Methane Total emission Emission (tons/day) 9796 754 129 6.5 109 4.4 100 36 .132 Section 7 – Chemical Aspects of Air Pollution Percent of total 69.5 889.

2 37 .AREP GAW Percent Emission by Source-LA Source Category Stationary Mobile Total CO(g) 2 98 100 NOx(g) 24 76 100 SOx(g) 38 62 100 ROG 50 50 100 Section 7 – Chemical Aspects of Air Pollution Table 4.

Ethene 3. Propene 8.and p-Xylene 2. Methylcyclopentane Section 7 – Chemical Aspects of Air Pollution Table 4. o-Xylene 9.4 38 . Butane 10. Formaldehyde 6. Toluene 5. m. i-Pentane 7. Acetaldehyde 4.AREP GAW Most Important Gases in Smog in Terms of Ozone Reactivity and Abundance 1.

8 h 2.3 .6 d 19 h 9h 34 m HO2 O 1000 y 18 y 4y 6. ------7h 23 d ------OH 22 h 52 m 3d 6h 9.5 y 1.3 d --2.5 y ----------6y --4d NO3 29 d 4m --2d ----33 d 5m O3 650 y 17 m 200 d 3200 y ----200 d 4.6 h ROG Species n-Butane trans-2-butene Acetylene Formaldehyde Acetone Ethanol Toluene Isoprene Section 7 – Chemical Aspects of Air Pollution 39 Table 4.AREP GAW Lifetimes of ROGs Against Chemical Loss in Urban Air Phot.

AREP GAW Summary Section 7 – Chemical Aspects of Air Pollution 40 .

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Ozone Meteorology – Key Processes
• • • • • • • • Dispersion (horizontal mixing) Vertical mixing Sunlight Transport Weather pattern Geography Diurnal Season

Meteorology

Emissions

Chemistry

Section 7 – Chemical Aspects of Air Pollution 41

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Ozone Precursor Emissions (2 of 2)
Wind speed (WS) S Concentration ∝ S/WS

S

Vertical mixing (VM) Concentration ∝ S/VM

Key processes – Source location, density, and strength – Dispersion (horizontal mixing) - wind speed – Vertical mixing - inversion
Section 7 – Chemical Aspects of Air Pollution

Courtesy of New Jersey Department of Environmental Protection

42

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Daily Variation

Section 7 – Chemical Aspects of Air Pollution 43

 . .AREP GAW Volume mixing ratio (ppmv) V olum e m ixing ratio (ppm v) Source/Receptor Regions in Los Angeles .10 44 .   Urban center Volume mixing ratio (ppmv) .    NO N O O  S a n B e r n a r d in o A u g u s t  . .   Sub-urban C e n tr a l L o s A n g e le s A u g u s t  . .    NO  O NO     H our of day        H our of day  Section 7 – Chemical Aspects of Air Pollution Figure 4.

  = O (g).  Contours are ozone (ppmv) – Chemical Aspects of Air Pollution Section 7 Figure 4.9 45 .  . ppmv (g) (ppmv) NOx (ppmv) x 0.08  .24  . 0.  .   0.  .16 NO  .   .  .  .32  .     . ROG (ppmC) 0.AREP GAW Ozone Isopleth Plot  .

S. ( avg.) -h Europe (seasonal) U. ( avg.) -h  preindustrial             ppbv present background Section 7 – Chemical Aspects of Air Pollution Slide courtesy of D. AIR QUALITY STANDARDS (even more so in Europe!) Europe ( avg.) -h U.S.S.AREP GAW THIS OZONE BACKGROUND IS A SIZABLE INCREMENT TOWARDS VIOLATION OF U. Jacob 46 .

AREP GAW EU/USA SURFACE O ZO N E ENH AN CEM ENTS C AU SED BY A N T H R O P O G E N IC E M IIS S I O N S F R O M D IF F E R E N T C O N T IN E N T S S G E O SC H E M m o d e l. J u     ly N o rth A m e ric a E u ro p e A s ia L i e t a l.   ] [ Section 7 – Chemical Aspects of Air Pollution 47 .

AREP GAW Section 7 – Chemical Aspects of Air Pollution 48 .

AREP GAW Particulate Matter (1 of 3) ● ● ● ● ● ● ● Complex mixture of solid and liquid particles Composed of many different compounds Both a primary and secondary pollutant Sizes vary tremendously Forms in many ways Clean-air levels are < 5 µg/m3 * Background concentrations can be higher due to dust and smoke Concentrations range from 0 to 500+ µg/m3 * Health concerns – – – – ● ● Ultra-fine fly-ash or carbon soot Can aggravate heart diseases Associated with cardiac arrhythmias and heart attacks Can aggravate lung diseases such as asthma and bronchitis Can increase susceptibility to respiratory infection 24-hour average * Section 7 – Chemical Aspects of Air Pollution 49 .

5 μm) • Coarse particles (2.AREP GAW Particulate Matter (2 of 3) Particles come in different shapes and sizes Particle sizes • Ultra-fine particles (<0.5 to 10 μm) PM10 Crustal material Carbon chain agglomerates 50 Section 7 – Chemical Aspects of Air Pollution .1 to 2.1 μm) • Fine particles (0.

AREP GAW Particulate Matter (3 of 3) A clear (left) and dirty (right) PM filter Section 7 – Chemical Aspects of Air Pollution 51 .

● Primary PM (directly emitted) – – – – – – Suspended dust Sea salt Organic carbon Elemental carbon Metals from combustion Small amounts of sulfate and nitrate ● Secondary PM (precursor gases that form PM in the atmosphere) – Sulfur dioxide (SO2): forms sulfates – Nitrogen oxides (NOx): forms nitrates – Ammonia (NH3): forms ammonium compounds – Volatile organic compounds (VOCs): form organic carbon compounds Section 7 – Chemical Aspects of Air Pollution 52 .AREP GAW Particulate Matter Composition (1 of 3) PM is composed of a mixture of primary and secondary compounds.

sulfates. and some organic material absorb water vapor from the atmosphere Chow and Watson (1997) 53 • • • • • Section 7 – Chemical Aspects of Air Pollution . sodium. and other metal oxides Ammonium – ammonium bisulfate. Ti. often called soot. sulfate. EC is black. hydrogen. and particulate ammonium nitrate • • NaCl – salt is found in PM near sea coasts and after de-icing materials are applied Organic Carbon (OC) – consists of hundreds of separate compounds containing mainly carbon. Si. Liquid Water – soluble nitrates. nitric acid (HNO3). Fe. Ca. other inorganic ions. ammonium. and oxygen Elemental Carbon (EC) – composed of carbon without much hydrocarbon or oxygen. and nitrate are most common Sulfate – results from conversion of SO2 gas to sulfate-containing particles Nitrate – results from a reversible gas/particle equilibrium between ammonia (NH3).AREP GAW Particulate Matter Composition (3 of 3) Most PM mass in urban and nonurban areas is composed of a combination of the following chemical components • Geological Material – suspended dust consists mainly of oxides of Al.

Section 7 – Chemical Aspects of Air Pollution 54 .AREP GAW PM Emissions Sources (1 of 4) Point – generally a major facility emitting pollutants from identifiable sources (pipe or smoke stack). Facilities are typically permitted.

animal feeding operations. architectural coatings. residential wood burning. construction. swimming pools.AREP GAW PM Emissions Sources (2 of 4) Area – any low-level source of air pollution released over a diffuse area (not a point) such as consumer products. and charbroilers Section 7 – Chemical Aspects of Air Pollution 55 . open burning. waste treatment facilities.

recreational watercraft. locomotives. snow mobiles. and lawn and garden equipment Section 7 – Chemical Aspects of Air Pollution 56 . motorcycles. and buses Non-road sources include pollutants emitted by combustion engines on farm and construction equipment. agricultural equipment. airplanes. trucks. commercial marine vessels.AREP GAW Mobile • • PM Emissions Sources (3 of 4) On-road is any moving source of air pollution such as cars.

seeps. geysers. volcanoes. and lightning Section 7 – Chemical Aspects of Air Pollution 57 . trees.AREP GAW PM Emissions Sources (4 of 4) Natural – biogenic and geogenic emissions from wildfires. plants. soil. grasses. wind blown dust.

  gr bt   )  u m - g . g M ic C e o iy x t Nzha oo ( ) e aul yt t c l      u m -  g  .)   t n es . Co d Pt a ( .)   o r o l eu l a a    u m -  . u m  . d     u m - g . K n i lf Rue e W ie e g ( .) r ld f  m - u .)    - Na it t re Tr n ( .  o t oo )     .)      m - u . u m -  g Ls ne s o Agl ( e . g A of r ( bt o bs d . Wh g n C a i t D( sno . A n ( )  tat l a    u m -  g  .AREP GAW COMPOSITION OF PM2. g Section 7 – Chemical Aspects of Air Pollution M i o iy P r gl ( ) e c C . u m -  .)      u m -  g  . g Q krC O( ) u e it H a y      u m -  g  . g     A ns il P ( ) r dt le A e v      .5 IS HIGHLY VARIABLE (NARSTO PM ASSESSMENT) Sf t ua l e E hr( -  se t )   E e ( . g F so r n ( -  e   )  m - u .e ea x t d  u m -  g  . u m -  g Ami m mo u n Bc cr o lak a n b Oai cr o r n a n g c b Sl o i Oe t r h S A r w( . r l    Y kil ( )     ove  u m -  g  . 58 .

visibility.001 µm (molecular cluster) to 100 µm (small raindrop) Soil dust Sea salt Environmental importance: health (respiration).AREP GAW ORIGIN OF THE ATMOSPHERIC AEROSOL Aerosol: dispersed condensed matter suspended in a gas Size range: 0. cloud formation. heterogeneous reactions. radiative balance. delivery of nutrients… Section 7 – Chemical Aspects of Air Pollution 59 .

Section 7 – Chemical Aspects of Air Pollution 60 .AREP GAW Particulate Matter Chemistry (1 of 4) Coagulation: Particles collide and stick together. Sulfate Chemical Reaction: Gases react to form particles. Cloud/Fog Processes: Gases dissolve in a water droplet and chemically react. Condensation: Gases condense onto a small solid particle to form a liquid droplet. A particle exists when the water evaporates.

AREP GAW Particulate Matter Composition (2 of 3) PM contains many compounds Primary Particles (directly emitted) Secondary Particles (from precursor gases) VOCs Carbon (Soot) Organic Carbon SO2 Metals Ammonium Sulfate Crustal (soil.dust) Other (sea salt) Ammonium Nitrate Ammoni a NOx Composition of PM tells us about the sources and formation processes Gas Particle Section 7 – Chemical Aspects of Air Pollution 61 .

1908.AREP GAW Sulfur Dioxide • Sulfur dioxide (SO2) belongs to the family of sulfur oxide (SOx) gases. and sulfites • Contributes to acid rain Impact of low soil pH on agriculture in Victoria German sandstone statue. • Gases are formed when fuel containing sulfur (mainly coal and oil) is burned and during metal smelting and other industrial processes. 1969 Section 7 – Chemical Aspects of Air Pollution Low crown density of spruce trees 62 . sulfates. • Affects the respiratory system • Reacts in the atmosphere to form acids.

AREP GAW Particulate Matter Chemistry (2 of 4) Sulfate Chemistry ● Heterogeneous Oxidation ● ● ● ● ● Virtually all ambient sulfate (99%) is secondary. Only a small fraction of cloud droplets deposit out as rain. are scavenged by water droplets and rapidly oxidize to sulfate. NOx and hydrocarbon emissions tend to Husar (1999) enhance the photochemical oxidation rate. soluble pollutant gases. About half of SO2 oxidation to sulfate occurs in the gas phase through photochemical oxidation in the daytime. such as SO2. At least half of SO2 oxidation takes place in cloud droplets as air molecules react in clouds. Within clouds. most droplets evaporate and leave a sulfate residue or “convective debris”. formed within the atmosphere from SO2 during the summer. Typical conversion rate 1-10% per hour Section 7 – Chemical Aspects of Air Pollution 63 .

increasing their acidity Mechanisms 1. Dissolution of SO2(g) into liquid water to form H2SO3(aq) followed by aqueous chemical conversion of H2SO3(aq) and its dissociation products to H2SO4(aq) and its dissociation products. Gas-phase oxidation of SO2(g) to H2SO4(g) followed by condensation of H2SO4(g) 2. Aspects of Air Pollution Section 7 – Chemical 64 .AREP GAW Mechanisms of Converting S(IV) to S(VI) Why is converting to S(VI) important? It allows sulfuric acid to enter or form within cloud drops and aerosol particles.

AREP GAW Section 7 – Chemical Aspects of Air Pollution 65 .

Thus. HNO3 reacts with ammonia to form particulate ammonium nitrate (NH4NO3). ● ● During the nighttime. NO2 is converted into HNO3 by a series of reactions involving ozone and the nitrate radical. PM nitrate can be formed at night and during the day. – The reaction of OH with NO2 is about 10 times faster than the OH reaction with SO2. – The peak daytime conversion rate of NO2 to HNO3 in the gas phase is about 10% to 50% per hour. daytime photochemistry also forms ozone.AREP GAW Particulate Matter Chemistry (3 of 4) Nitrate Chemistry ● NO2 can be converted to nitric acid (HNO3) by reaction with hydroxyl radicals (OH) during the day. Section 7 – Chemical Aspects of Air Pollution 66 ● .

fog Temperature Relative humidity Solar radiation Winds Precipitation Temperature Relative humidity Winds Section 7 – Chemical Aspects of Air Pollution Vertical mixing 67 . H2O. VOCs • Adsorption of VOCs • Absorption of H2O condensation and coagulation photochemical production cloud/fog processes Other gaseous • Biogenic • Anthropogenic Meteorological Processes Clouds.AREP GAW Particulate Matter Chemistry (4 of 4) Emissions Particles • NaCl • Crustal Particles • Soot • Metals • OC Gases • NOx • SO2 • VOCs • NH3 Gases • VOCs • NH3 • NOx Winds Temperature Solar radiation Sources Mechanical • Sea salt • Dust Combustion • Motor vehicles • Industrial • Fires Chemical Processes PM Formation PM Transport/Loss Sample Collection gases condense onto particles cloud/fog processes transport sedimentation (dry deposition) wet deposition Measurement Issues • Inlet cut points • Vaporization of nitrate.

TheSection changes with season.5. very warm temperatures can increase vertical mixing and dispersion of pollutants. stronger winds disperse pollutants.5.5. Moisture acts to increase the production No direct impact. strong wintertime inversions and high PM2. which act to increase PM2. Clouds can limit photochemistry. A strong inversion acts to limit vertical mixing allowing for the accumulation of PM2. Rain can remove precursors of PM2. Very cold surface temperatures during the winter may produce strong surface-based inversions that confine pollutants to a shallow layer. Phenomena Aloft Pressure Pattern Winds and Transport No direct impact.5 concentrations often occur during the approach of a trough from the west. field tilling. and with temperature.5. formation of secondary PM2. Temperature Warm temperatures are associated with Photochemical reaction rates increase increased evaporative. Warm temperatures may volatize Nitrates from a solid to a gas.AREP GAW Particulate Matter Meteorology How weather affects PM emissions. Water droplets can enhance the Convective clouds are an indication of strong vertical mixing. of secondary PM2. Higher concentrations of precursors can produce faster. which disperses pollutants. Cold temperatures can also indirectly influence PM2. Although warm surface temperatures are generally associated with poor air quality conditions. biogenic.5 concentrations.5 levels may not be altered by weak troughs. formation. Inversions reduce vertical mixing and therefore increase chemical concentrations of precursors.5. road dust.5 including sulfates and nitrates.5 regardless of season. which limits photochemical production. Strong surface winds tend to disperse PM2. In general. wood burning. In mountain-valley regions. windblown dust. Troughs tend to produce conditions conducive for dispersion and removal of PM and ozone. resulting in a less ideal mixture of pollutants for chemical reactions that produce PM2. which changes the amount of solar radiation available for photochemistry. Temperature Inversions No direct impact. Strong winds can create dust which can increase PM2. more efficient chemical reactions that produce PM2. Rain Moisture Reduces soil and fire emissions No direct impact.e. and transport Emissions No direct impact.5. Clouds/Fog No direct impact. and construction vary by season. home heating on winter nights).5. PM Transport/Loss Ridges tend to produce conditions conducive for accumulation of PM2.. PM Formation No direct impact. High PM2. agriculture burning. power plant emissions. 68 .5 concentrations (i. Season Forest fires.5.Aspects of Air Pollution sun angle 7 – Chemical No direct impact. Rain can remove PM2.

1995-2000 NARSTO PM Assessment. SITES.5 µm) Red circles indicate violations of national air quality standard: 50 µg m-3 for PM10 15 µg m-3 for PM2.S.5 (particles > 2.AREP GAW ANNUAL MEAN PARTICULATE MATTER (PM) CONCENTRATIONS AT U.5 Section 7 – Chemical Aspects of Air Pollution 69 . 2003 PM10 (particles > 10 µm) PM2.

AREP GAW AEROSOL OPTICAL DEPTH (GLOBAL MODEL) Annual mean Section 7 – Chemical Aspects of Air Pollution 70 .

gov 71 .AREP GAW AEROSOL OBSERVATIONS FROM SPACE Biomass fire haze in central America yesterday (4/30/03) Fire locations in red Section 7 – Chemical Aspects of Air Pollution Modis.nasa.gsfc.

[2000] 72 .AREP GAW BLACK CARBON EMISSIONS DIESEL DOMESTIC COAL BURNING BIOMASS BURNING Section 7 – Chemical Aspects of Air Pollution Chin et al.

1750-PRESENT IPCC [2001] “Kyoto also failed to address two major pollutants that have an impact on warming: black soot and tropospheric ozone. Bush.”Aspects of Air Pollution (George W. but also dramatically improve people's7 health. Both are proven health hazards. Reducing both would not only address climate change.AREP GAW RADIATIVE FORCING OF CLIMATE. June 11 2001 Rose Section – Chemical Garden speech) 73 .

AREP GAW Particles Impact Human Health and MORE .

hazecam.net/ 75 .AREP GAW EPA REGIONAL HAZE RULE: FEDERAL CLASS I AREAS TO RETURN TO “NATURAL” VISIBILITY LEVELS BY 2064 …will require essentially total elimination of anthropogenic aerosols! • clean day moderately polluted day Acadia National Park Section 7 – Chemical Aspects of Air Pollution http://www.

April 22.S.AREP GAW ASIAN DUST INFLUENCE IN UNITED STATES Dust observations from U. IMPROVE network April 16. 2001 Asian dust in southeastern U. AZ Section 7 – Chemical Aspects of AirApril 16. 2001 Asian dust in western U. Pollution Clear day 2001: Asian dust! 76 .S.S. 0 2 4 µg m-3 6 8 Glen Canyon.

Health and Climate: Dirtier Air and a Dimmer Sun Anderson et al.. Science 2003 Smith et al.. 2002 Section 7 – Chemical Aspects of Air Pollution 77 . 2003 He et al..AREP GAW Aerosols Link Air Quality.

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