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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
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
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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, services, and manufacturing Natural production of smoke from fires, dust from strong winds, and emissions from the biosphere and geosphere
Section 7 Chemical Aspects of Air Pollution 6
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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
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Basic Pollutants (3 of 3)
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Air toxics (hazardous air pollutants) are known or suspected to cause cancer or other serious health effects. EPAs 188 hazardous air pollutants include
Benzene (motor fuel, oil refineries, chemical processes) Perchlorethylene (dry cleaning, degreasing) Chloroform (solvent in adhesive and pesticides, by-product of chlorination processes) BTEX, Dioxins, PAHs, Metals (Hg, Cr) Area/ Mobile
Other 25% (nonroad) 20%
National air toxics emissions sources in 1996 U.S. Environmental Protection Agency, 1998
Point 24%
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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
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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
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Nitrogen Oxides
Nitrogen oxides, or NOx, is the generic term for a group of highly reactive gases, all of which contain nitrogen and oxygen in varying amounts. Nitrogen dioxide is most visually prominent (it is the yellowbrown color in smog) The primary man-made sources of NOx are motor vehicles; electric utilities; and other industrial, commercial, 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, acid aerosols, and NO2, which also cause respiratory problems Contributes to the formation of acid rain (deposition)
Section 7 Chemical Aspects of Air Pollution 19
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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, effectively recycled
Section 7 Chemical Aspects of Air Pollution 21
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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, even at low levels
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Both HNO3 and H2O2 will photolyze or react with OH to, in effect, reverse these pathways but reactions are slow (lifetime of several days) both are very soluble - 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, limited wet removal
Section 7 Chemical Aspects of Air Pollution 25
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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
Key processes
Weak horizontal dispersion Weak vertical mixing
Warm air
Section 7 Chemical Aspects of Air Pollution 26
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Man-made sources
Oxides of nitrogen (NOx) through combustion VOCs through combustion and numerous other sources
Meteorology
Emissions
Chemistry
Concentration depends on
Source location, density, and strength Meteorology
Section 7 Chemical Aspects of Air Pollution 28
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Soils 5.1
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JJA
2000 data
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Global Budget of CO
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Emission (tons/day)
9796 754 129 6.5 889.5 109 4.5 113.5 1399 313 108 29 33 500 47 2429 904 14,132
Section 7 Chemical Aspects of Air Pollution
Percent of total
69.3
6.3
0.8
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Table 4.2
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Table 4.4
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ROG Species n-Butane trans-2-butene Acetylene Formaldehyde Acetone Ethanol Toluene Isoprene
Table 4.3
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Summary
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Meteorology
Emissions
Chemistry
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Key processes Source location, density, and strength Dispersion (horizontal mixing) - wind speed Vertical mixing - inversion
Section 7 Chemical Aspects of Air Pollution
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Daily Variation
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. . .
Sub-urban
C e n tr a l L o s A n g e le s A u g u s t , NO N O O
S a n B e r n a r d in o A u g u s t , NO
NO H our of day
H our of day
Figure 4.10
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(g) (ppmv)
NOx (ppmv) x
0.08
. .
0.16
NO
0.24
. ROG (ppmC)
0.32
Figure 4.9
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THIS OZONE BACKGROUND IS A SIZABLE INCREMENT TOWARDS VIOLATION OF U.S. AIR QUALITY STANDARDS (even more so in Europe!)
Europe ( avg.) -h Europe (seasonal) U.S. ( avg.) -h U.S. ( avg.) -h
preindustrial
ppbv
present background
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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
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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 g/m3 * Background concentrations can be higher due to dust and smoke Concentrations range from 0 to 500+ g/m3 * Health concerns
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
*
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Particulate Matter (2 of 3)
Particles come in different shapes and sizes Particle sizes Ultra-fine particles (<0.1 m) Fine particles (0.1 to 2.5 m) Coarse particles (2.5 to 10 m)
PM10
Crustal material
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Particulate Matter (3 of 3)
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PM Emissions Sources (1 of 4)
Point generally a major facility emitting pollutants from identifiable sources (pipe or smoke stack). Facilities are typically permitted.
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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, architectural coatings, waste treatment facilities, animal feeding operations, construction, open burning, residential wood burning, swimming pools, and charbroilers
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Mobile
PM Emissions Sources (3 of 4)
On-road is any moving source of air pollution such as cars, trucks, motorcycles, and buses Non-road sources include pollutants emitted by combustion engines on farm and construction equipment, locomotives, commercial marine vessels, recreational watercraft, airplanes, snow mobiles, agricultural equipment, and lawn and garden equipment
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PM Emissions Sources (4 of 4)
Natural biogenic and geogenic emissions from wildfires, wind blown dust, plants, trees, grasses, volcanoes, geysers, seeps, soil, and lightning
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u m . g
F so r n ( - e ) m - u . g
Q krC O( ) u e it H a y u m - g .
K n i lf Rue e W ie e g ( - ) r ld f m - u . g
A ns il P ( ) r dt le A e v . u m - g
Ls ne s o Agl ( e
- ) m - u . g
M ic C e o iy x t Nzha oo ( ) e aul yt t c l u m - g .
Wh g n C a i t D( sno
- ) u m - g .
Co d Pt a ( - ) o r o l eu l a a u m - . g
M i o iy P r gl ( ) e c C - e ea x t d u m - g .
r l Y kil ( ) ove u m - g .
A n ( ) tat l a u m - g .
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ORIGIN OF THE ATMOSPHERIC AEROSOL Aerosol: dispersed condensed matter suspended in a gas Size range: 0.001 m (molecular cluster) to 100 m (small raindrop)
Environmental importance: health (respiration), visibility, radiative balance, cloud formation, heterogeneous reactions, delivery of nutrients
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Condensation: Gases condense onto a small solid particle to form a liquid droplet.
Cloud/Fog Processes: Gases dissolve in a water droplet and chemically react. A particle exists when the water evaporates.
Sulfate
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Metals
Ammonium Sulfate Crustal (soil,dust) Other (sea salt) Ammonium Nitrate Ammoni a NOx
Gas
Particle
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Sulfur Dioxide
Sulfur dioxide (SO2) belongs to the family of sulfur oxide (SOx) gases. Gases are formed when fuel containing sulfur (mainly coal and oil) is burned and during metal smelting and other industrial processes. Affects the respiratory system Reacts in the atmosphere to form acids, sulfates, and sulfites Contributes to acid rain
Impact of low soil pH on agriculture in Victoria German sandstone statue, 1908, 1969
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Heterogeneous Oxidation
Virtually all ambient sulfate (99%) is secondary, formed within the atmosphere from SO2 during the summer. About half of SO2 oxidation to sulfate occurs in the gas phase through photochemical oxidation in the daytime. NOx and hydrocarbon emissions tend to Husar (1999) enhance the photochemical oxidation rate. At least half of SO2 oxidation takes place in cloud droplets as air molecules react in clouds. Within clouds, soluble pollutant gases, such as SO2, are scavenged by water droplets and rapidly oxidize to sulfate. Only a small fraction of cloud droplets deposit out as rain; most droplets evaporate and leave a sulfate residue or convective debris. Typical conversion rate 1-10% per hour
Section 7 Chemical Aspects of Air Pollution 63
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NO2 can be converted to nitric acid (HNO3) by reaction with hydroxyl radicals (OH) 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.
During the nighttime, NO2 is converted into HNO3 by a series of reactions involving ozone and the nitrate radical. HNO3 reacts with ammonia to form particulate ammonium nitrate (NH4NO3). Thus, PM nitrate can be formed at night and during the day; daytime photochemistry also forms ozone.
Section 7 Chemical Aspects of Air Pollution 66
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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, H2O, VOCs Adsorption of VOCs Absorption of H2O
Meteorological Processes
Winds Precipitation
Vertical mixing
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No direct impact.
In general, stronger winds disperse pollutants, resulting in a less ideal mixture of pollutants for chemical reactions that produce PM2.5. Inversions reduce vertical mixing and therefore increase chemical concentrations of precursors. Higher concentrations of precursors can produce faster, more efficient chemical reactions that produce PM2.5.
Strong surface winds tend to disperse PM2.5 regardless of season. Strong winds can create dust which can increase PM2.5 concentrations.
Temperature Inversions
No direct impact.
A strong inversion acts to limit vertical mixing allowing for the accumulation of PM2.5.
Rain Moisture
Moisture acts to increase the production No direct impact. of secondary PM2.5 including sulfates and nitrates. Although warm surface temperatures are generally associated with poor air quality conditions, very warm temperatures can increase vertical mixing and dispersion of pollutants. Warm temperatures may volatize Nitrates from a solid to a gas. Very cold surface temperatures during the winter may produce strong surface-based inversions that confine pollutants to a shallow layer.
Temperature
Warm temperatures are associated with Photochemical reaction rates increase increased evaporative, biogenic, and with temperature. power plant emissions, which act to increase PM2.5. Cold temperatures can also indirectly influence PM2.5 concentrations (i.e., home heating on winter nights).
Clouds/Fog
No direct impact.
Water droplets can enhance the Convective clouds are an indication of strong vertical mixing, which disperses pollutants. formation of secondary PM2.5. Clouds can limit photochemistry, which limits photochemical production. TheSection changes with season,Aspects of Air Pollution sun angle 7 Chemical No direct impact. which changes the amount of solar radiation available for photochemistry.
Season
Forest fires, wood burning, agriculture burning, field tilling, windblown dust, road dust, and construction vary by season.
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ANNUAL MEAN PARTICULATE MATTER (PM) CONCENTRATIONS AT U.S. SITES, 1995-2000 NARSTO PM Assessment, 2003 PM10 (particles > 10 m) PM2.5 (particles > 2.5 m)
Red circles indicate violations of national air quality standard: 50 g m-3 for PM10 15 g m-3 for PM2.5
Section 7 Chemical Aspects of Air Pollution 69
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AEROSOL OBSERVATIONS FROM SPACE Biomass fire haze in central America yesterday (4/30/03)
Modis.gsfc.nasa.gov
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BIOMASS BURNING
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IPCC [2001]
Kyoto also failed to address two major pollutants that have an impact on warming: black soot and tropospheric ozone. Both are proven health hazards. Reducing both would not only address climate change, but also dramatically improve people's7 health.Aspects of Air Pollution (George W. Bush, June 11 2001 Rose Section Chemical Garden speech)
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EPA REGIONAL HAZE RULE: FEDERAL CLASS I AREAS TO RETURN TO NATURAL VISIBILITY LEVELS BY 2064
clean day
http://www.hazecam.net/
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ASIAN DUST INFLUENCE IN UNITED STATES Dust observations from U.S. IMPROVE network
April 16, 2001 Asian dust in western U.S. April 22, 2001 Asian dust in southeastern U.S.
4 g m-3
Glen Canyon, AZ
Section 7 Chemical Aspects of AirApril 16, Pollution
Clear day
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Aerosols Link Air Quality, Health and Climate: Dirtier Air and a Dimmer Sun
He et al., 2002