Introduction

The composition and chemistry of the atmosphere is of importance because of the interactions between the atmosphere and living organisms. The composition of the Earth's atmosphere has been changed by human activity and some of these changes are harmful to human health, crops and ecosystems. Examples of problems: ACID RAINS (ACID PRECIPITATION): Deposition of acidic components in rain, snow, fog, dew, or dry particles. Occurs when SO2 and NOx are emitted into the atmosphere, undergo chemical transformations and are absorbed by water droplets in clouds. The droplets then fall to earth as rain, sn, snow or sleet. PHOTOCHEMICAL SMOG: mixture of air pollutants, usually highly reactive and oxidizing including: NOx, tropospheric ozone, VOCs, PAN, Aldehydes, etc. GLOBAL WARMING: Observed increase in the average temperature of the Earths Atmosphere and oceans in recent decades.

Air Pollutants
S. No. 1. Suspended particulate Matter, Automobile, power plants, boilers, Industries requiring crushing SPM 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. Sulphur dioxide Oxides of nitrogen NO, NO2 (NOX) Lead Carbon monoxide Hydrocarbons Chlorine Fluoride Peroxyacetyl nitrate, PAN Formaldehyde Ozone Hydrogen sulphide and grinding such as quarry, cement. Power plants, boilers, sulphuric acid manufacture, ore refining, petroleum refining. Automobiles, power plants, nitric acid manufacture, also a secondary pollutant Ore refining, battery manufacturing, automobiles. Automobiles Automobiles, petroleum refining Chlor-alkali plants. Fertilizer, aluminum refining Secondary pollutant Secondary pollutant Secondary pollutant Pulp and paper, petroleum refining. Pollutants Sources

Types of Air Pollution

Air Pollution various substances added to the atmosphere by natural events and human activities in high enough concentrations to cause harm to humans, other organisms, or materials Primary air pollutant a substance emitted directly to the atmosphere Secondary Air Pollutant a substance formed in the atmosphere as a result of reactions involving primary pollutants

NAAQS Standards for Ambient Air Pollution

Pollutant Primary/ [final rule cite] Secondary Carbon Monoxide [ primary 76 FR 54294, Aug 31, 2011 ] Lead primary [ and 73 FR 66964, Nov 12, 2008 secondary ] Nitrogen Dioxide [75 FR 6474, Feb 9, 2010 primary ] [ primary 61 FR 52852, Oct 8, 1996and ] secondary Ozone primary [ and 73 FR 16436, Mar 27, 2008 secondary ] primary PM2.5 Particle Pollution Dec 14, 2012 Averagin Level g Time 8-hour 9 ppm 1-hour 35 ppm Form Not to be exceeded more than once per year

Rolling 3 0.15 g/m3 month Not to be exceeded (1) average 1-hour Annual 100 ppb 53 ppb (2) 0.075 ppm (3) 12 g/m3 15 g/m3 98thpercentile, averaged over 3 years Annual Mean Annual fourth-highest daily maximum 8-hr concentration, averaged over 3 years annual mean, averaged over 3 years annual mean, averaged over 3 years

8-hour Annual

secondary Annual primary and 24-hour secondary

98th percentile, averaged over 3 http://www.epa.gov/air/criteria.html 35 g/m3 years

Air Quality Index (AQI)

AQI Ratings
Air Quality Index (AQI) Values 0 to 50 51 to 100 101 to 150 151 to 200 201 to 300 301 to 500 Levels of Health Concern Good Moderate Unhealthy for Sensitive Groups Unhealthy Very Unhealthy Hazardous Colors Green Yellow Orange Red Purple Maroon

AQI Calculations

If multiple pollutants are measured at a monitoring site, then the largest or "dominant" Air Quality Index value is reported for the location.

WHO AIR QUALITY GUIDELINES

Substance Lowest concentration at which adverse effects are observed 0.5 g/m3 -500 g/m3 30 mg/m3 200 g/m3 120 g/m3 Duration of exposure 1 year Doseresponse 10 minutes 1 hour 1 hour 8 hours

Lead PM SO2 CO NO2 Ozone

 Primary standards provide public health protection, including protecting the health of "sensitive" populations such as asthmatics, children, and the elderly. Secondary standards provide public welfare protection, including protection against decreased visibility and damage to animals, crops, vegetation, and buildings.

AIR POLLUTION SOURCES

Outdoor air quality is affected by:

Industrial or agricultural activities Treatment of industrial effluents and domestic residues Traffic Solid waste management Cottage industries Chemical incidents and spills

Other Industry and waste disposal Power Generation

Domestic Sources Road Transport

Agriculture

http://www.eea.europa.eu/publications/2599XXX/page010.html

Basic Pollutants Toxics

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/ Other 25% Mobile (nonroad) 20%

Point 24%

Mobile (onroad) 31%

 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

Particulate Matter Composition PM is composed of a mixture of primary and secondary compounds.

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

Particulate Matter Composition

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, 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
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, hydrogen, and oxygen Elemental Carbon (EC) composed of carbon without much hydrocarbon or oxygen. EC is black, often called soot. Liquid Water soluble nitrates, sulfates, ammonium, sodium, other inorganic ions, and some organic material absorb water vapor from the atmosphere
Chow and Watson (1997)

PM Emissions Sources
Point generally a major facility emitting pollutants from identifiable sources (pipe or smoke stack). Facilities are typically permitted.

PM Emissions Sources
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

PM Emissions Sources 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

PM Emissions Sources
Natural biogenic and geogenic emissions from wildfires, wind blown dust, plants, trees, grasses, volcanoes, geysers, seeps, soil, and lightning

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)

Soil dust Sea salt

Environmental importance: health (respiration), visibility, radiative balance, cloud formation, heterogeneous reactions, delivery of nutrients

Particulate Matter Chemistry

Coagulation: Particles collide and stick together.

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

Chemical Reaction: Gases react to form particles.

Particulate Matter Composition

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 Ammon ia NOx

Composition of PM tells us about the sources and formation processes

Gas

Particle

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 Low crown density of spruce trees

Particulate Matter Chemistry (2 of 4)

Sulfate Chemistry

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 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)

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.

Particulate Matter Chemistry

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.

Particulate Matter Chemistry

PM Formation PM Transport/Loss Sample Collection

Sources Emissions Chemical Processes

Mechanical Sea salt Dust Combustion Motor vehicles Industrial Fires Particles NaCl Crustal Particles Soot Metals OC Gases NOx SO2 VOCs NH3 Gases VOCs NH3 NOx
Winds Temperature Solar radiation Vertical mixing

gases condense onto particles cloud/fog processes transport sedimentation (dry deposition) wet deposition

Measurement Issues

condensation and coagulation photochemical production cloud/fog processes

Inlet cut points Vaporization of nitrat H2O, VOCs Adsorption of VOCs Absorption of H2O

Other gaseous Biogenic Anthropogenic

Meteorological Processes
Clouds, fog Temperature Relative humidity Solar radiation Winds Precipitation Temperature Relative humidity Winds

Particulate Matter Meteorology

How weather affects PM emissions, formation, and transport
Phenomena Aloft Pressure Pattern Emissions No direct impact. PM Formation No direct impact. PM Transport/Loss 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 PM2.5 concentrations often occur during the approach of a trough from the west. Strong surface winds tend to disperse PM2.5 regardless of season. Strong winds can create dust which can increase PM2.5 concentrations.

Winds and Transport

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. Rain can remove precursors of PM2.5. Moisture acts to increase the production of secondary PM2.5 including sulfates and nitrates. Photochemical reaction rates increase with temperature.

Temperature Inversions

No direct impact.

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

Rain Moisture

Reduces soil and fire emissions No direct impact.

Rain can remove PM2.5. No direct impact.

Temperature

Warm temperatures are associated with increased evaporative, biogenic, and 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). No direct impact.

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.

Clouds/Fog

Water droplets can enhance the formation of secondary PM2.5. Clouds can limit photochemistry, which limits photochemical production. The sun angle changes with season, which changes the amount of solar radiation available for photochemistry.

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 by season.

No direct impact.

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

AEROSOL OPTICAL DEPTH (GLOBAL MODEL) Annual mean

AEROSOL OBSERVATIONS FROM SPACE Biomass fire haze in central America yesterday (4/30/03)

Fire locations in red

Modis.gsfc.nasa.gov

BLACK CARBON EMISSIONS

DIESEL

DOMESTIC COAL BURNING

BIOMASS BURNING

Chin et al. [2000]

RADIATIVE FORCING OF CLIMATE, 1750-PRESENT

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's health . (George W. Bush, June 11 2001 Rose Garden speech)

Particles Impact Human Health and MORE

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 yellow-brown 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)

NOx EMISSIONS (Tg N yr-1) TO TROPOSPHERE

Stratosphere 0.2 Lightning 5.8 Fossil Fuel 23.1

Soils 5.1

Biomass Burning 5.2

Biofuel 2.2 Aircraft 0.5

NOx
Oxides of nitrogen formed in combustion processes are usually due to either thermal fixation of atmospheric nitrogen in combustion air or to the conversion of chemically bound nitrogen in the fuel. Thermal fixation occurs when combustion temperature is above 1600C. For natural gas and distillate oil nearly all NO results from thermal fixation. For residue oil and coal, the contribution to NO emission from fuel bound nitrogen may be significant.

The concentration of NOx formed increases with increase in excess oxygen maintained in the combustion process and with the increase in temperature of the furnace. For coal based thermal power plants in India, it ranges between 100 and 200 mg/Nm3 in the flue gas. In the case of natural gas and liquid fuels, the emission limits for flue gases prescribed in European countries is in the range of 200 - 400 mg/Nm3.

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-NONO2 cycle
NO + HO2 NO2 + OH NO + RO2 NO2 + RO

leads to net production of ozone

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 (+O2O3) O(1D) + H2O 2 OH (~10%) (~90%)

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

THE OH RADICAL: MAIN TROPOSPHERIC OXIDANT

Primary source:

O3 + hn O2 + O(1D) O(1D) + M O + M (2) O(1D) + H2O 2OH (3)

(1)

Sink: oxidation of reduced species leads to Major HO2(RO2) production OH sinks

CO + OH CO2 + H CH4 + OH CH3 + H2O HCFC + OH

Global Mean [OH] = 1.0x106 molecules cm-3

An example of gridded NOx emissions

Mapping of Tropospheric NO2

From the GOME satellite instrument (July 1996)

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

Ozone Precursor Emissions

Man-made sources
Oxides of nitrogen (NOx) through combustion VOCs through combustion and numerous other sources
Emissions

Meteorology

Chemistry

Natural sources (biogenic)

VOCs from trees/vegetation NOx from soils (Midwest fertilizer)

Concentration depends on
Source location, density, and strength Meteorology

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

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

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

Oxidation of CO - production of ozone

CO + OH CO2 + H H + O2 + M HO2 + M NO + HO2 NO2 + OH NO2 + hv NO + O O + O2 + M O3 CO + 2 O2 + hv CO2 + O3

Ozone Chemistry
Summary of ozone chemistry
NO2 + Sunlight NO + O Production O+ O2 O3 Production
Emissions Chemistry Meteorology

NO + O3 NO2 + O2 VOC + OH RO2 + H2O RO2 + NO NO2 + RO

Destruction Production of NO2 without the Destruction of O3 RO=Reactive Organic compound such as VOC

Key processes

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

Weak horizontal dispersion Weak vertical mixing

Warm air

Day and Night Chemistry

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

What breaks the cycle?

Cycle terminated by
OH + 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 upper troposphere
no dry deposition, limited wet removal

LEAD (Pb) IN AIR

SOURCES
Tetraethyl lead in petrol Mining and smelting of lead ores Industry Waste incineration Dust (e.g. homes with old lead-based paint, battery recycling, smelters)

CARCINOGENS IN AIR
Pollutant
Arsenic Benzene Chromium VI Nickel PAHs Vinyl chloride Radon

System affected
Lung Leukaemia Lung Lung Lung liver Lung, Gastrointestinal