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    Section 7

    Chemical Aspectsof Air Pollution

    Overview of Basic Pollutants

    OzoneParticulate Matter

    Carbon Monoxide

    Sulfur Dioxide

    Nitrogen Oxides

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    Photochemical Smog

    Air pollution formed by sunlight catalyzing chemical reactionsof emitted compounds

    Los Angeles, California

    Early pollution due to London-type smog.

    1905-1912, L.A. City Council adopts regulation controlling smoke

    Early 1900s, 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.

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    Los Angeles, California

    (December 3, 1909)

    Library of Congress Prints and Photographs Division, Washington, D. C.

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    Discovery of Ozone in Smog

    1948: Arie Haagen-Smit (1900-1977), biochemistry professor atCaltech, begins to study plants damaged by smog.

    1950: Finds that plants sealed in a chamber and exposed toozone exhibit similar damage as did plants in smog

    Also finds that ozone caused eye irritation, damage to materials,

    respiratory problems. Other researchers find that rubber cracks within minutes when

    exposed to high ozone.

    1952: Haagen-Smit finds that ozone forms when oxides ofnitrogen and reactive organic gases are exposed to sunlight.Postulates that ozone and precursors are main constituents ofL.A. smog.

    Oil companies and business leaders argue that ozone in L.A.originates from stratosphere.

    Measurements of low ozone over Catalina Island disprove this.

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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 inthe formation of secondary pollutants

    Pollutants originate from Combustion of fossil fuels and organic matter

    Evaporation of petroleum products or compounds used incommercial products, services, and manufacturing

    Natural production of smoke from fires, dust from strong

    winds, and emissions from the biosphere and geosphere

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    PrimarySO2

    Sulfur Dioxide

    Primary & SecondaryPMParticulate Matter

    Primary & SecondaryHC

    Hydrocarbon Compounds

    (also called VOCs volatile

    organic compounds )

    SecondaryNO2Nitrogen Dioxide

    SecondaryO3Ozone

    PrimaryCOCarbon Monoxide

    TypeAbbreviationPollutant

    Basic Pollutants (2 of 3)

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    Basic Pollutants (3 of 3)

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    Basic Pollutants Toxics (1 of 2)

    Air toxics (hazardous air pollutants) are known orsuspected 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)

    National air toxics emissions sources in 1996

    U.S. Environmental Protection Agency, 1998

    Area/

    Other

    25%

    Mobile

    (nonroad)

    20%

    Mobile

    (onroad)

    31%

    Point

    24%

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    Basic Pollutants Toxics (2 of 2)

    Differences between toxics and criteriapollutants

    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

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    Basic Pollutants Sources(1 of 4)

    Combustion

    Evaporation

    Natural Production

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    Basic Pollutants Sources(2 of 4)

    Combustion Complete combustion

    Fuel water and carbon dioxide (CO2)

    Incomplete combustion

    Fuel water, CO2, and other pollutants

    Pollutants are both gases and particles

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    Basic Pollutants Sources (3 of 4)

    Evaporation Thousands of chemical compounds

    Liquids evaporating or gases being released

    Some harmful by themselves, some react to produce other

    pollutants

    Many items you can smell are evaporative pollutants

    Gasoline benzene (sweet odor, toxic, carcinogenic)

    Bleach chlorine (toxic, greenhouse gas)

    Trees pinenes, limonene (ozone- and particulate matter forming)

    Paint volatile organic compounds (ozone- and particulate matterforming)

    Baking bread, fermenting wine and beer VOCs and ethanol (ozone-

    forming)

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    Basic Pollutants Sources (4 of 4)

    Natural Production Fires (combustion) produce

    gases and particles

    Winds pick up dust, dirt,

    sand and create particlesof various sizes

    Biosphere emits gases from

    trees, plants, soil, ocean,

    animals, microbes Volcanoes and oil seeps

    produce particles and gases

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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

    Secondary pollutant that forms from precursorgases

    Nitric oxide combustion product Volatile organic compounds (VOCs) evaporativeand combustion products

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    Solar radiation and chemistry

    The reaction that produces ozone in theatmosphere:

    O + O2 + M O3 + M

    Difference between stratospheric andtropospheric ozone generation is in the sourceof atomic O

    For solar radiation with a wavelength of less

    than 242 nm:O2 + hv O + O

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    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

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    Tropospheric Ozone Photolysis

    Troposphere ozone photolysis takes place in a narrow UV window(300-320 nm), NO2 broadly below 428

    30o equinoxmiddaySolar spectrum

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    Nitrogen Oxides

    Nitrogen oxides, or NOx, is the generic term for a group ofhighly reactive gases, all of which contain nitrogen andoxygen in varying amounts.

    Nitrogen dioxide is most visually prominent (it is the yellow-brown color in smog)

    The primary man-made sources of NOx are motor vehicles;electric utilities; and other industrial, commercial, andresidential 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)

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    Must make NO2

    To make significant amounts of ozone musthave a way to make NO2 without consuming

    ozone

    Presence of peroxy radicals, from the oxidation

    of hydrocarbons, disturbs O3-NO-NO2 cycleNO + HO2 NO2 + OH

    NO + RO2 NO2 + RO

    leads to net

    production of ozone

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    The Hydroxyl Radical

    produced from ozone photolysis for radiation with wavelengths less than 320

    nm:

    O3 + hv O(1D) + O2

    followed byO(1D) + M O(3P) + M (+O2O3) (~90%)

    O(1D) + H2O 2 OH (~10%)

    OH initiates the atmospheric oxidation of a wide range ofcompounds in the atmosphere

    referred to as detergent of the atmosphere

    typical concentrations near the surface ~106 - 107cm-3

    very reactive, effectively recycled

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    Section 7 Chemical Aspects of Air Pollution22

    THE OH RADICAL: MAIN

    TROPOSPHERIC OXIDANT

    Primary source: O3 + hn O2 + O(1D) (1)

    O(1D) + M O + M (2)

    O(1D) + H2O 2OH (3)

    Sink: oxidation of reduced species leadsto HO2(RO2) production

    CO + OH CO2 + H

    CH4 + OH CH3 + H2O

    HCFC + OH

    Global Mean [OH] = 1.0x106 molecules

    cm-3

    MajorOH sinks

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    Oxidation of CO - production of ozone

    CO + OH CO2 + H

    H + O2 + M HO2 + M

    NO + HO2 NO2 + OH

    NO2 + hv NO + OO + O2 + M O3

    CO + 2 O2 + hv CO2 + O3

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    Section 7 Chemical Aspects of Air Pollution24

    Carbon Monoxide

    Odorless, colorless gas

    Caused by incomplete combustion of fuel

    Most of it comes from motor vehicles

    Reduces the transport of oxygen through thebloodstream

    Affects mental functions and visual acuity,

    even at low levels

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    What breaks the cycle?

    Cycle terminated byOH + NO2 HNO3

    HO2 + HO2 H2O2

    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 uppertroposphere

    no dry deposition, limited wet removal

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    Section 7 Chemical Aspects of Air Pollution26

    Ozone ChemistrySummary of ozone chemistry

    NO2 + Sunlight NO + O Production

    O+ O2 O3 Production

    NO + O3 NO2 + O2 Destruction VOC + OH RO2 + H2O Production of NO2 without the

    RO2 + NO NO2 + RO Destruction of O3

    Emissions Chemistry

    Meteorology

    Key processes

    Ample sunlight (ultraviolet) High concentrations of precursors (VOC, NO, NO2)

    Weak horizontal dispersion

    Weak vertical mixing

    Warm air

    RO=Reactive Organic compound such as VOC

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    Section 7 Chemical Aspects of Air Pollution27

    Day and Night Chemistry

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    Section 7 Chemical Aspects of Air Pollution28

    Ozone Precursor Emissions (1 of 2)

    Man-made sources Oxides of nitrogen (NOx) through

    combustion

    VOCs through combustion and

    numerous other sources Natural sources (biogenic)

    VOCs from trees/vegetation

    NOx from soils (Midwest fertilizer)

    Concentration depends on Source location, density, andstrength

    Meteorology

    Emissions Chemistry

    Meteorology

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    Section 7 Chemical Aspects of Air Pollution29

    NOx EMISSIONS (Tg N yr-1) TO TROPOSPHERE

    Fossil Fuel23.1

    Aircraft0.5

    Biofuel2.2

    BiomassBurning

    5.2

    Soils5.1

    Lightning5.8

    Stratosphere0.2

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    An example of gridded NOx emissions

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    Mapping of Tropospheric NO2

    From the GOME satellite instrument (July 1996)

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    GOME Can Provide Info on Daily Info

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    Section 7 Chemical Aspects of Air Pollution33

    Lightning Flashes Seen from Space

    2000 data

    DJF

    JJA

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    Section 7 Chemical Aspects of Air Pollution34

    Global Budget of CO

    AREP Satellite Observations of Biomass

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    Section 7 Chemical Aspects of Air Pollution35

    Satellite Observations of Biomass

    Fires (1997)

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    Section 7 Chemical Aspects of Air Pollution36

    Daily Los Angeles Emission (1987)

    Gas Emission (tons/day) Percent of totalCarbon monoxide 9796 69.3

    Nitric oxide 754

    Nitrogen dioxide 129

    Nitrous acid 6.5

    Total NOx+HONO 889.5 6.3

    Sulfur dioxide 109

    Sulfur trioxide 4.5Total SO

    x113.5 0.8

    Alkanes 1399

    Alkenes 313

    Aldehydes 108

    Ketones 29

    Alcohols 33

    Aromatics 500

    Hemiterpenes 47

    Total ROGs 2429 27.2

    Methane 904 6.4

    Total emission 14,132 100

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    Section 7 Chemical Aspects of Air Pollution37

    Percent Emission by Source-LA

    Table 4.2

    Source Category CO(g) NOx(g) SOx(g) ROG

    Stationary 2 24 38 50

    Mobile 98 76 62 50

    Total 100 100 100 100

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    Section 7 Chemical Aspects of Air Pollution38

    Most Important Gases in Smog in Terms of

    Ozone Reactivity and Abundance

    Table 4.4

    1. m- andp-Xylene

    2. Ethene

    3. Acetaldehyde

    4. Toluene5. Formaldehyde

    6. i-Pentane

    7. Propene

    8. o-Xylene9. Butane

    10. Methylcyclopentane

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    Section 7 Chemical Aspects of Air Pollution39

    Lifetimes of ROGs Against Chemical

    Loss in Urban Air

    Table 4.3

    ROG Species Phot. OH HO2 O NO3 O3

    n-Butane --- 22 h 1000 y 18 y 29 d 650 y

    trans-2-butene --- 52 m 4 y 6.3 d 4 m 17 m

    Acetylene --- 3 d --- 2.5 y --- 200 d

    Formaldehyde 7 h 6 h 1.8 h 2.5 y 2 d 3200 y

    Acetone 23 d 9.6 d --- --- --- ---

    Ethanol --- 19 h --- --- --- ---

    Toluene --- 9 h --- 6 y 33 d 200 d

    Isoprene --- 34 m --- 4 d 5 m 4.6 h

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    Section 7 Chemical Aspects of Air Pollution40

    Summary

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    Section 7 Chemical Aspects of Air Pollution41

    Ozone Meteorology Key Processes

    Dispersion (horizontal mixing)

    Vertical mixing

    Sunlight

    Transport

    Weather pattern

    Geography

    Diurnal

    Season

    Emissions Chemistry

    Meteorology

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    Section 7 Chemical Aspects of Air Pollution42

    Ozone Precursor Emissions (2 of 2)

    Key processes

    Source location, density, and strength

    Dispersion (horizontal mixing) - wind speed

    Vertical mixing - inversion

    Concentration S/WS

    Wind speed (WS)

    S

    Courtesy of New Jersey

    Department of Environmental Protection

    Concentration S/VM

    Vertical mixing (VM)S

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    Daily Variation

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    Source/Receptor Regions in Los Angeles

    .

    .

    .

    H o u r o f d a y

    O

    N ON O

    C e n t ra l L o s A n g e le s

    A u g u s t ,

    V

    olumemixin

    gratio(ppmv)

    Figure 4.10

    .

    .

    .

    Vol

    umemixingratio(ppmv)

    H o u r o f d a y

    O

    N O

    N O

    S a n B e r n a r d in o

    A u g u s t ,

    V

    olumemixin

    gratio(ppmv

    )

    Urban center Sub-urban

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    . .

    .

    .

    .

    .

    .

    ROG (ppmC)

    NOx

    (g)(ppmv)

    ..

    .

    .

    .

    =O

    (g),ppm

    v

    Ozone Isopleth Plot

    Figure 4.9Contours are ozone (ppmv)

    NO

    x(ppmv)

    0.2

    40.0

    8 0.3

    2

    0.1

    6

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    THIS OZONE BACKGROUND IS A SIZABLE INCREMENTTHIS OZONE BACKGROUND IS A SIZABLE INCREMENT

    TOWARDS VIOLATION OF U.S. AIR QUALITY STANDARDSTOWARDS VIOLATION OF U.S. AIR QUALITY STANDARDS

    (even more so in Europe!)(even more so in Europe!)

    ppbv

    Europe(seasonal)

    U.S.(-h avg.)

    U.S.(-h avg.)

    preindustrial present

    background

    Europe(-h avg.)

    Slide courtesy of D. Jacob

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    S U R F A C E O Z O N E E N H A N C E M E N T S C A U S E D B YS U R F A C E O Z O N E E N H A N C E M E N T S C A U S E D B Y

    A N T H R O P O G E N I C E M IS S IO N S F R O M D IF F E R E N T C O N T I N E N T SA N T H R O P O G E N IC E M IS S IO N S F R O M D IF F E R E N T C O N T I N E N T SG E O S-C H E Mm o d e l , J u l y

    N o r th A m e r i c a

    E u r o p e

    A s i a

    L i e t a l . [ ]

    EU/USA

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    Particulate Matter(1 of 3)

    Ultra-fine fly-ash or

    carbon soot

    *24-hour average24-hour average

    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

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    Particulate Matter(2 of 3)Particles come in different shapes and sizes

    Particle sizes

    Ultra-fine particles (

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    Particulate Matter(3 of 3)

    A clear (left) and dirty (right) PM filter

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    Particulate Matter Composition (1 of 3)

    Primary PM (directlyemitted)

    Suspended dust Sea salt

    Organic carbon

    Elemental carbon

    Metals from combustion

    Small amounts of sulfateand 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

    PM is composed of a mixture of primary and secondarycompounds.

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    NaCl salt is found in PM near seacoasts and after de-icing materialsare applied

    Organic Carbon (OC) consists of

    hundreds of separate compoundscontaining mainly carbon, hydrogen,and oxygen

    Elemental Carbon (EC) composed of carbon without muchhydrocarbon or oxygen. EC isblack, often called soot.

    Liquid Water soluble nitrates,sulfates, ammonium, sodium, otherinorganic ions, and some organicmaterial absorb water vapor fromthe atmosphere

    Particulate Matter Composition (3 of 3)

    Chow and Watson (1997)

    Geological Material suspended

    dust consists mainly of oxides of Al,

    Si, Ca, Ti, Fe, and other metal

    oxides

    Ammonium ammonium bisulfate,

    sulfate, 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), nitric acid (HNO3),

    and particulate ammonium nitrate

    Most PM mass in urban and nonurban areas is composed of acombination of the following chemical components

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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, architecturalcoatings, waste treatment facilities, animal feeding operations, construction,

    open burning, residential wood burning, swimming pools, and charbroilers

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    PM Emissions Sources(3 of 4)Mobile

    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, andlightning

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    COMPOSITION OF PM2.5 IS HIGHLY VARIABLE (NARSTO PM

    ASSESSMENT)

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    Toronto( - )Egbert ( - )

    Abbotsford( - )

    Quaker CityOH( )

    ArendstvillePA( )

    Atlanta( )Yorkville( )MexicoCity- Pedregal ( )

    LosAngeles( - )

    Fresno( - )

    KernWildlifeRefuge( - )

    Sulfate

    Nitrate

    AmmoniumBlackcarbon

    Organiccarbon

    Soil

    Other

    . ugm -. ugm -

    . ugm -

    . ugm -

    . ugm -

    . ugm -. ugm -

    .ugm -

    . ugm -

    . ugm -

    . ugm -

    WashingtonDC( - )

    . ugm -

    ColoradoPlateau( - )

    . ugm -

    MexicoCity-Netzahualcoyotl ( )

    .ugm -

    Esther ( - )

    St. Andrews( - )

    .ugm -

    .ugm -

    ASSESSMENT)

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    GAWORIGIN OF THE ATMOSPHERIC AEROSOL

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    Soil dustSea salt

    Aerosol: dispersed condensed matter suspended in a gasSize 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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    Particulate Matter Chemistry (1 of 4)

    Coagulation: Particles collide and stick together.

    Condensation: Gases condense onto a small solid particle

    to form a liquid droplet.

    Chemical Reaction: Gases react to form particles.

    Cloud/Fog Processes: Gases dissolve in a water droplet and chemically

    react. A particle exists when the water evaporates.

    Sulfate

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    P ti l t M tt C iti

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    NOx

    Ammoni

    a

    VOCs

    Particulate Matter Composition (2 of 3)PM contains many compounds

    Primary Particles

    (directly emitted)Secondary Particles

    (from precursor gases)

    Other(sea salt)

    Crustal

    (soil,dust)

    Organic

    CarbonCarbon

    (Soot)SO2

    Ammonium

    Sulfate

    Ammonium

    Nitrate

    Metals

    Composition of PM

    tells us about

    the sources and

    formation processes

    Gas

    Particle

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    Sulfur Dioxide

    Sulfur dioxide (SO2) belongs to the family of sulfuroxide (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

    Low crown density

    of spruce trees

    German sandstone

    statue, 1908, 1969

    Impact of low soil

    pH on agriculture

    in Victoria

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    Sulfate Chemistry Virtually all ambient sulfate (99%)

    is secondary, formed within theatmosphere 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

    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

    Husar (1999)

    Heterogeneous Oxidation

    Particulate Matter Chemistry(2 of 4)

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    M h i f C ti S(IV) t

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    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, increasing their acidity

    Mechanisms

    1. Gas-phase oxidation of SO2(g) to H2SO4(g) followed by

    condensation of H2SO4(g)

    2. 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.

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    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.

    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.

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    Winds Clouds, fog Winds Temperature

    Temperature Temperature Precipitation Relative humidity

    Solar radiation Relative humidity Winds

    Vertical mixing Solar radiation

    condensation and

    coagulation

    photochemical production

    cloud/fog processes

    gases condense onto particles

    cloud/fog processes Measurement

    Issues Inlet cut points Vaporization of

    nitrate, H2O, VOCs

    Adsorption of VOCs Absorption of H2O

    transport

    sedimentation(dry deposition)

    wet deposition

    Mechanical Sea salt Dust

    Combustion Motor vehicles Industrial

    Fires

    Other gaseous

    Biogenic Anthropogenic

    Particles NaCl Crustal

    Particles Soot Metals

    OCGases

    NOx SO2 VOCs

    NH3Gases

    VOCs NH3 NOx

    SourcesSample

    CollectionPM Transport/LossPM

    FormationEmissionsChemical Processes

    Meteorological Processes

    Particulate Matter Chemistry (4 of 4)

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    Partic late Matter Meteorolog

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    Phenomena Emissions PM Formation PM Transport/Loss

    Aloft Pressure

    Pattern

    No direct impact. No direct impact. Ridges tend to produce conditions conducive for accumulation of PM2.5

    .

    Troughs tend to produce conditions conducive for dispersion and removal of PM and ozone.In mountain-valley regions, strong wintertime inversions and high PM2.5

    levels may not be

    altered by weak troughs.High PM

    2.5concentrations often occur during the approach of a trough from the west.

    Winds andTransport

    No direct impact. In general, stronger winds dispersepollutants, resulting in a less idealmixture of pollutants for chemicalreactions that produce PM

    2.5.

    Strong surface winds tend to disperse PM2.5

    regardless of season.

    Strong winds can create dust which can increase PM2.5

    concentrations.

    TemperatureInversions

    No direct impact. Inversions reduce vertical mixing andtherefore increase chemical

    concentrations of precursors. Higherconcentrations of precursors canproduce faster, more efficient chemicalreactions that produce PM

    2.5.

    A strong inversion acts to limit vertical mixing allowing for the accumulation of PM2.5

    .

    Rain Reduces soil and fire emissions Rain can remove precursors of PM2.5

    . Rain can remove PM2.5

    .

    Moisture No direct impact. Moisture acts to increase the productionof secondary PM

    2.5including sulfates and

    nitrates.

    No direct impact.

    Temperature Warm temperatures are associated withincreased evaporative, biogenic, and

    power plant emissions, which act toincrease PM

    2.5. Cold temperatures can

    also indirectly influence PM2.5

    concentrations (i.e., home heating onwinter nights).

    Photochemical reaction rates increasewith temperature.

    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-basedinversions that confine pollutants to a shallow layer.

    Clouds/Fog No direct impact. Water droplets can enhance theformation of secondary PM

    2.5. Clouds can

    limit photochemistry, which limitsphotochemical production.

    Convective clouds are an indication of strong vertical mixing, which disperses pollutants.

    Season Forest fires, wood burning, agriculture

    burning, field tilling, windblown dust,road dust, and construction vary byseason.

    The sun angle changes with season,

    which changes the amount of solarradiation available for photochemistry.

    No direct impact.

    Particulate Matter MeteorologyHow weather affects PM emissions, formation, and transport

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    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

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    GAWAEROSOL OPTICAL DEPTH (GLOBAL MODEL)

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    AEROSOL OPTICAL DEPTH (GLOBAL MODEL)

    Annual mean

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    GAWAEROSOL OBSERVATIONS FROM SPACE

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    AEROSOL OBSERVATIONS FROM SPACE

    Biomass fire haze in central America yesterday (4/30/03)

    Fire locationsin red

    Modis.gsfc.nasa.gov

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    GAW BLACK CARBON EMISSIONS

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    BLACK CARBON EMISSIONS

    Chin et al. [2000]

    DIESEL

    DOMESTICCOAL BURNING

    BIOMASSBURNING

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    GAW RADIATIVE FORCING OF CLIMATE, 1750-PRESENT

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    Kyoto also failed to address two major pollutants that have an impact onwarming:black soot and tropospheric ozone.Both are proven health

    hazards.Reducing both would not only address climate change, but also

    dramatically improve people's health. (George W. Bush, June 11 2001 Rose

    Garden speech)

    IPCC [2001]

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    p

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    GAWEPA REGIONAL HAZE RULE: FEDERAL CLASS I AREAS TO RETURN TO

    NATURAL VISIBILITY LEVELS BY 2064

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    NATURAL VISIBILITY LEVELS BY 2064

    Acadia National Park

    clean day moderately polluted day

    http://www.hazecam.net/

    will require essentially total elimination of anthropogenic aerosols!

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    GAW ASIAN DUST INFLUENCE IN UNITED STATES

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    Dust observations from U.S. IMPROVE network

    April 16, 2001Asian dust in western U.S.

    April 22, 2001Asian dust in southeastern U.S.

    GlenCanyon,AZ

    Clear day April 16, 2001: Asian dust!

    0 2 4 6 8g m-3

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    Climate:

    Dirtier Air and a Dimmer Sun

    Anderson et al., Science 2003 Smith et al., 2003 He et al., 2002