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1.AIR POLLUTION
Principles of air pollution This module includes a brief overview of the basic elements of air pollution that are relevant to emissions inventories, including: Definition of air pollution Effects of air pollution (human health, environmental) Classification of pollutants CO, Lead, NOx, PM, SO2, VOC Air toxics Ozone depleting substances (ODSs) Greenhouse gases Visibility degrading pollutants Photochemical smog - ozone Air Quality Management Model 1.1. Importance of the Atmosphere Troposphere > Provides oxygen for humans and animals > Provides carbon dioxide for plants > Transports water (precipitation) > Serves as medium for sound Stratosphere > Provides heat near earths surface > Shields earth from harmful radiation Thermosphere > Makes long distance communication possible 1.2. What is Clean Air? Composition of Natural Air in Troposphere: > Argon (0.9%) > Other (0.1%) Carbon dioxide 330 ppm Neon 18 ppm

Helium 5 ppm Methane 1.5 ppm Other Gases 1 ppm

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Properties: > Exhibits properties of a fluid occupies space > Has mass weighs more than 4.5 x 1018 kg > Is a mixture Gases Tiny solid particles Water Droplets 1 Clean air is found in few, if any, places on earth. Air carries water droplets, ice crystals, and dust, but these are not considered part of the composition of air. The amount of water in air and the form it is in are related to air temperature. Air can contain a lot of moisture or very little moisture (relative humidity). This is not the case for components of air whose relative amounts remain constant. The pie chart refers to composition of dry air at ground level. In air quality, we are primarily concerned with ambient air the air around us in the troposphere. Ambient air is the air we feel when the wind blows, the air we see when it is filled with mist or smoke, and the air we breathe. Air exhibits properties of a fluid flowing to fill corners, holes, rocks and crannies. Air occupies space. Air has mass Air mixture is made up of gases, particles, and water droplets. Each of which has mass and weight. 5,000,000,000,000,000 tons. 1 1.3. Air Pollution Definition Presence of substances in the air in concentrations that create health and environmental problems Sources > Naturally occurring > Man-Made Is a mixture > Gases > Water Droplets > Particles

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Air pollution is a visible or invisible particle or gas found in the air that is not part of the natural composition of air. -Health impact in humans: asthma condition, cancer & noncancer effects, coughing, irritated breathing, etc. -Environmental Impacts on plants and animals: diversity, endangered species, death, etc. Impaired visibility: haze Property impact: pollutants form acid precipitation which damages property and materials Ambient air contains most of the pollutants that affect humans and their environment. Air contains both natural gases, water droplets, and particles and chemicals added by humans. These substances react with each other to form different compounds. For example, O reacts readily with S to form SO2 or with N to form NOx. CO2 and H2O react to form carbonic acid, resulting in acid rain. SO2 and NOx react with water vapor to form sulfuric and nitric acids. NOx, VOC and other components react in sunlight to form ozone. Many other substances are found mixed with gases in the air. Tiny water droplets, and fine particles of smoke, dust, and salts contribute to haze, fog and smog. Every location on the earth experiences some type of mist, fog, or haze resulting form interactions of different air components (natural or man-made). Natural air pollution has been around since the formation of the earth. During the 1800s, pollution created by humans started to become a major concern. Most of the gaseous components of air are part of natural complex biochemical cycles of elements, such as C, N, and S. Although there have been changes in cycling patterns over geologic time, changes are usually slow and natural ecosystems keep the system in balance. The air pollution problem comes when human activities introduce large quantities of additional compounds into the atmosphere which disrupts the normal biochemical cycle. 1.4. Air Pollution Effect on Humans This shows the whole cycle for air pollution for humans. Sources: Stationary (factories, residences, etc.) and Mobile (Onroad and Nonroad) Dispersion: Pollutants carried short or long distances by wind. Air quality is highly dependent on weather conditions. The movement of air affects general air quality. Winds help to dissipate air pollutants, whereas stagnant air can promote the buildup of pollutants to unhealthy conditions. Transformation: Natural substances and air pollutants react with each other to form different compounds. Examples: SO2 reacts with water vapor to form sulfuric acids, resulting in acid rain. NOx, VOC and other components react in sunlight to form ozone. Formaldehyde is secondarily formed in the atmosphere.

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Deposition: Pollutants are deposited either by dry deposition (without precipitation) or wet deposition (precipitation). Most of the water droplets carried by air eventually fall to the earth as precipitation. Air pollutants are washed from the atmosphere in precipitation to the earth. Deposition of air pollutants then becomes land and water pollution. Evaporation and Reentrainment: Pollutants from land and water are also taken up back into the air. Exposure to humans: occurs after deposition. - Inhalation (breathing) - Dermal (skin) - Ingestion (diet) discuss bioaccumulation/ bio-magnification. As pollutant moves up food chain, some air pollutants become more concentrated as they are transferred along the food chain. Ex. Mercury. Health effects on humans; target organs - Cancer endpoint Noncancer endpoints respiratory effects (asthma, coughing, reduced lung capacity, etc.), birth defects, reproductive (reduced sperm counts), neurological (methyl mercury affects muscle control), etc. 1.5. Emission Types Anthropogenic (man-made) > Stationary sources Indoors Outdoors > Mobile sources Onroad Nonroad Natural > Plants and soils > Lightning and volcanoes Wildfires In describing a given air mass and the chemical reactions occurring therein, both anthropogenic and natural sources of primary emissions must be considered and their relative importance evaluated. The importance of emission source types can vary by geographic area, by pollutant, and by season.

Natural air pollutants have always been part of earths history. Particulate matter and variety of gases from volcanoes, forest fires and decaying organic matter in oceans and swamps enter the atmosphere at irregular intervals. Naturally produced greenhouse gases have contributed to periods of global warming. Plants and soils In the open seas and in marshes and swamps, decay processes produce levels of methane gas. Plants also release pollutants directly to the air that contribute to ozone formation. Volcanoes contribute particulate matter, ash and gases into the atmosphere. Their emission can affect visibility and the temperature of the earth. Forest fires contribute variety of pollutants, ash and smoke. 3 1.6. Adverse Impacts of Air Pollutants Health and environmental effects can be acute or chronic Impact of substance is related to: > Atmospheric lifetime of pollutant > Concentration of pollutant > Exposure of organism to pollutant > Dose response of pollutant Emission inventories are an important component of risk assessment studies Slide introduces the negatives effects caused by air pollution, i.e., health impacts and environmental impacts. These effects can be acute (short term), or chronic (long term). Factors defining and influencing these impacts are described in subsequent slides. 6

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1.7.

Environmental Effects

1.7.1. Haze Caused by scattering and absorption of light by particles and gases > Primary PM > Soot (elemental carbon) > PM precursors: SOx, NOx, VOC, NH3 Effects: > Acid Rain formation > Reduced visual range It is most simply described as the haze which obscures the clarity, color, texture, and form of what

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we see. Every location on the earth experiences some type of mist, fog, or haze resulting form interactions of different air components (natural or man-made). Visibility impairment occurs as a result of the scattering and absorption of light by particles and gases in the atmosphere. Haze is caused when sunlight encounters tiny pollution particles in the air. Some light is absorbed by particles. Other light is scattered away before it reaches an observer. More pollutants mean more absorption and scattering of light, which reduce the clarity and color of what we see. Some types of particles such as sulfates, scatter more light, particularly during humid conditions. Visibility is degraded when a veil of white or brown haze hangs in the air blurring the view. Most of this haze is not natural. It is air pollution, carried by the wind often many hundreds of miles from where it originated. The visual range of many US parks has been substantially reduced by air pollution. In eastern US parks, average visual range has decreased from 90 miles to 15-25 miles. In the Western US, visual range has decreased from 140 miles to 35-90 miles. Tiny water droplets, and fine particles of smoke, dust, and salts contribute to haze, fog and smog. Particles can be from directly-emitting sources (primary PM and soot), or formed from PM precursors (such as nitrate and sulfate aerosols). Air pollutants come from a variety of natural and manmade sources. Natural sources can include windblown dust, and soot from wildfires. Manmade sources can include motor vehicles, electric utility and industrial fuel burning, and manufacturing operations. Particulate matter pollution is the major cause of reduced visibility (haze). Some haze-causing particles are directly emitted to the air. Others are formed when gases emitted to the air form particles as they are carried many miles from the source of the pollutants. Effects: The same particles which are linked to serious health effects [sulfates, nitrates, organic carbon, soot (elemental carbon), and soil dust] can significantly affect our ability to see. Some of the pollutants which form haze have also been linked to serious health problems and environmental damage. - Increased respiratory illness, Decreased lung function, and Premature death. - Particles such as nitrates and sulfates contribute to acid rain formation which makes lakes, rivers, and streams unsuitable for many fish, and erodes buildings, historical monuments, and paint on cars. 4 1.7.2. Acid Rain Acid Rain is primarily a result of > SO2 and NOx emissions interacting with sunlight and water vapor to form sulfuric

and nitric acids Effects: > Damage to vegetation > Damage to crops > Damage to animals > Damage to monuments Damage to drinking water Acid Rain: The process of acid deposition begins with emission of SO2 and NOx. These pollutants interact with sunlight and water vapor in the upper atmosphere to form acidic compounds (sulfuric acid, nitric acid, sulfates, and nitrates). CO2 and H2O also react to form carbonic acid. These compounds fall to Earth in form of wet acid deposition as acid rain or snow. During dry periods, the gases might combine with dust or other airborne particles and fall as dry acid precipitation. Acid rain may fall out hundreds of miles away from the area where SO2 or NOx were emitted into the air. 8

Bi Thanh Hi

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Acid rain damage affects crops, vegetation, animals, buildings, monuments, drinking water, etc. The extent of damage cause by acid deposition depends on the total acidity deposited in a particular area the acid sensitivity of the area. An area with acid-neutralizing compounds in soil could possibly withstand years of acid deposition without problems. In areas where soil is extremely thin or has little acid-buffering capacity in streams and lakes results in areas that are so acidic they cannot support animal or plant life. Human health is also affected by acid rain drinking water increases in toxic metals that are carried by acidic water and lung disease caused by breathing acid-laden air 1.7.3. Photochemical Smog Ozone is primary component of smog > Formed when NOx and VOC and other pollutants are in presence of sunlight Effects: > Damage to vegetation Haze Ozone is a major component in smog. Ozone is an odorless, colorless gas composed of three atoms of oxygen. Ozone occurs both in the Earth's upper atmosphere and at ground level. Ozone can be

good or bad, depending on where it is found. In the Earth's lower atmosphere, near ground level, ozone is formed when NOx and VOC and other pollutants emitted by cars, power plants, industrial boilers, refineries, chemical plants, and other sources react chemically in the presence of sunlight. As ground-level ozone concentrations increase, more and more people experience health effects, the effects become more serious, and more people are admitted to the hospital for respiratory problems. When ozone levels are very high, everyone should be concerned about ozone exposure. Ozone can cause several types of short-term health effects in the lungs: Ozone can irritate the respiratory system - coughing, feel an irritation in your throat, and/or experience an uncomfortable sensation in your chest. These symptoms can last for a few hours after ozone exposure and may even become painful. 9

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Ozone can reduce lung function - When this happens, you may notice that breathing starts to feel uncomfortable. If you are exercising or working outdoors, you may notice that you are taking more rapid and shallow breaths than normal. Reduced lung function can be a particular problem for outdoor workers, competitive athletes, and other people who exercise outdoors. Ozone can aggravate asthma - When ozone levels are high, more asthmatics have asthma attacks that require a doctor's attention or the use of additional medication. Ozone can inflame and damage the lining of the lung - Ozone damages the cells that line the air spaces in the lung. Within a few days, the damaged cells are replaced and the old cells are shed-much in the way that skin peels after a sunburn. If this kind of damage occurs repeatedly, the lung may change permanently in a way that could cause long-term health effects and a lower quality of life. Ozone may have other effects on people's health. Ozone may aggravate chronic lung diseases, such as emphysema and bronchitis. Also, studies in animals suggest that ozone may reduce the immune system's ability to fight off bacterial infections in the respiratory system. Ozone causes environmental effects: Damages vegetation 5 Smog - haze 1.7.4. Global Warming Primary pollutants:

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> Carbon dioxide > Methane > Nitrous oxide Affects: > Forests > Crop yields > Water supplies > Animals Ecosystems Global Warming - According to the National Academy of Sciences, the Earth's surface temperature has risen by about 1 degree Fahrenheit in the past century, with accelerated warming during the past two decades. There is new and stronger evidence that most of the warming over the last 50 years is attributable to human activities. Human activities have altered the chemical composition of the atmosphere through the buildup of greenhouse gases primarily carbon dioxide, methane, and nitrous oxide. These gases trap heat and create the greenhouse effect. Energy from the sun drives the earths weather and climate, and heats the earths surface; in turn, the earth radiates energy back into space. Atmospheric greenhouse gases (water vapor, carbon dioxide, and other gases) trap some of the outgoing energy, retaining heat somewhat like the glass panels of a greenhouse. Without this natural greenhouse effect, temperatures would be much lower than they are now, and life as known today would not be possible. Instead, thanks to greenhouse gases, the earths average temperature is a more hospitable 60F. However, problems may arise when the atmospheric concentration of greenhouse gases increase. Since the beginning of the industrial revolution, atmospheric concentrations of carbon dioxide have increased nearly 30%, methane concentrations have more than doubled, and nitrous oxide concentrations have risen by about 15%. These increases have enhanced the heat-trapping capability of the earths atmosphere. Sulfate aerosols, a common air pollutant, cool the atmosphere by reflecting light back into space; however, sulfates are short-lived in the atmosphere and vary regionally. Scientists generally believe that the combustion of fossil fuels and other human activities are the primary reason for the increased concentration of carbon dioxide. Plant respiration and the decomposition of organic matter release more than 10 times the CO2 released by human activities; but these releases have generally been in balance during the centuries leading up to the industrial revolution with carbon dioxide absorbed by terrestrial vegetation and the

oceans. 11

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Global mean surface temperatures have increased 0.5-1.0F since the late 19th century. The 20th century's 10 warmest years all occurred in the last 15 years of the century. The snow cover in the Northern Hemisphere and floating ice in the Arctic Ocean have decreased. Globally, sea level has risen 4-8 inches over the past century. Worldwide precipitation over land has increased by about one percent. Increasing concentrations of greenhouse gases are likely to accelerate the rate of climate change. Scientists expect that the average global surface temperature could rise 1-4.5F (0.6-2.5C) in the next fifty years, and 2.2-10F (1.45.8C) in the next century, with significant regional variation. Evaporation will increase as the climate warms, which will increase average global precipitation. Soil moisture is likely to decline in many regions. Intense rainstorms are likely to become more frequent. Sea level is likely to rise. Effects- Changing regional climate could alter: Forests Crop yields Water supplies Human health Many types of ecosystems e.g., deserts may expand into existing rangelands 1.8. Example Classification of Air Pollutants CO, Lead, NOx, Particulate Matter, SO2, Ozone (these 6 pollutants are known in U.S. as criteria air pollutants) Air Toxics Ozone Depleting Substances Greenhouse Gases Photochemical Smog Visibility Degrading Pollutants US classifies first bullet as criteria pollutants because US has produced extensive criteria documents summarizing all relevant information for setting of US ambient standards for regulatory purposes. Classification of Air Pollutants in your Country What pollutants are of interest in your country? What pollutants are regulated in your country? Engage countries in discussion and have them answer these questions in their manual. Then

compile answers on flip chart. Pollutant Regulation 12

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1.8.1.

U. S. Criteria Air Pollutants

Air pollutants for which air quality criteria have been issued in the U.S. > Particulate matter (PM) > Carbon monoxide (CO) > Nitrogen oxides (NOx) > Sulfur dioxide (SO2) > Lead (Pb) > Ammonia (NH3) > Ozone (O3) PM primary sources are diesel engines, power plants, industries, wind blown dust, combustion sources, mines, unpaved roads. CO primary sources are vehicles burning gasoline, indoor sources such as stoves, combustion sources NOx vehicles, combustion sources, coal burning stoves, combustion sources SO2 combustion sources, refineries, coal combustion Pb leaded gasoline, metal refineries Ammonia feedlots, fires, fertilizer plants Ozone vehicles, formed from other pollutants in presence of sunlight VOC solvent usage, mobile sources, industrial facilities 1.8.2. Air Toxics Pollutants capable of causing serious illnesses (e.g., cancer, birth defects) or even death Health effects are typically irreversible Health effects generally associated with years of exposure rather than hours or days Some persist in the environment, either remaining in the air or depositing on soil and in waterways Some bioaccumulate in the environment Toxic in small amounts Persistent bioaccumulative toxics: Alkyl-lead, Dioxins, Furans, Mercury and compounds,

Octachlorostyrene, Polychlorinated biphenyls (PCBs), Aldrin/Dieldrin, Chlordane, DDT- DDDDDE, Hexachlorobenzene, Mirex, Toxaphene Includes: > Volatile Organic compounds > Metals > Semivolatiles > Other We often incorrectly think of air toxics and PM and VOCs as being separate > Air toxics comprise a significant percentage of volatiles and metals > Most urban toxic hot spots are in same areas as where VOC and PM are emitted 13

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Air toxics affect the same populations as VOC and PM Thousands of new chemicals being introduced into our environment each year Air toxics can be emitted as both gases and particulate matter. As such there can be significant overlap with criteria emissions. For example, a refinerys benzene emissions stream is both an air toxics emissions source and a VOC emissions source. 99 NEI for HAPs 5.1 M tpy HAP VOC/PM 4.3 M tpy (84% of emissions) HAP nonVOC/PM 0.8 M tpy (16% of emissions) Toxics can be important from the standpoint of both direct emissions and inhalation, and from secondary exposure through deposition and subsequent uptake through the food chain. Exposure can be increased from ingestion since many toxics tend to become more concentrated as they pass through the chain. Air toxics can present more challenging control issues. Some species, e.g., arsenic, can become enriched in the fine particle component of an emissions stream, and therefore, be more difficult to control. Some toxics (e.g., dioxin) also have physio-chemical characteristics such that they are emitted in a vapor form (and can pass through traditional PM controls), but condense when cooled outside the stack and are deposited in the air and on the ground (open to possible reentrainment). 1.8.3. Air Toxics: Persistent Pollutants

POPs (persistent organic pollutants) and Heavy Metals > What are Persistent Pollutants? From natural or man-made sources Persist in the environment Bioaccumulate in the food chain Toxic to humans and wildlife Capable of traveling long distances in the air and water Toxicity Persistence Bioaccumulation

> Why are POPs subjects of global interest?

-Long-Range Transport 14

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These 4 criteria are the reason these chemicals needed to be addressed with a global treaty First, Already a regional agreement, negotiated under the auspices of the Economic Commission for Europe (LRTAP) Europe, US, Canada, and former Soviet Union states mostly developed countries and economies in transition Another reason is what makes a POP a POP. For a global agreement, the last is probably the most important, because as LRTAP suggests were talking about transboundary. If my upwind or down food chain neighbors dont join me in taking action, I may not be able to solve the problem on my own. This has come to be known as the Global Commons issue. Other examples of this include the Montreal Protocol on stratospheric ozone and the Kyoto Protocol on global climate. POPs are a little different in that there is also very much a local component they can also be quite nasty in the immediate vicinity in which theyre released.

TRANSITION: So who are these guys?

Often with a halogen such as chlorine, making them very stable and resistant to breaking down. This is in fact why POPs pesticides are so effective, they hang around for many years (Chlordane as a termite control). Capability to travel long distances in sufficient quantities to cause harm in another country is what justifies regional or global action to address these pollutants. POPs (persistent organic pollutants) and Heavy Metals > Potential Impacts Linked to reproductive, behavioral, developmental, endocrine disruption, & other health effects Exposure through: 15 production and use consuming foods contaminated with persistent pollutants

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Potential higher risk populations: those exposed during use those who subsist on fish & wildlife

> List of POPs and Heavy Metals Mercury and compounds Octachlorostyrene Polychlorinated biphenyls (PCBs) DDT, DDD, DDE Alkylated lead Dioxins & Furans Aldrin Dieldrin Endrin Toxaphene Heptachlor Mirex 8 Chlordane Hexachlorobenzene 1.8.4. Ozone Depleting Substances (ODS) Chlorofluorocarbons (CFCs) and other ODS accumulate in stratosphere due to long atmospheric lifetimes

Hydrochlorofluorocarbons are suggested replacements due to shorter atmospheric lifetime but have higher toxicity May be inventoried using mass balance approach What are your countrys commitments to phase out ODSs?

Examples of ODSs include chlorofluorocarbons (CFCs) (refrigerants, propellants), hydrochlorofluorocarbons (HCFCs), methyl bromide (ag chemical), carbon tetrachloride (dry cleaning), trichloroethane (degreaser, adhesives, solvents), and halons (firefighting chemical). The Montreal Protocol requires all ODSs are supposed to be phased out by 2030. Halons 1.8.5. CFCs Carbon tetrachloride Trichloroethane Methyl bromide HCFCs Greenhouse Gas Pollutants Accumulate in the troposphere due to long atmospheric lifetimes > Carbon dioxide (CO2) > Methane (CH4) > Nitrous oxide (N2O) Emissions Source: 2000 data from World Resources Institute CO2 Emissions Million metric tons World Asia (excluding 23,842 7,337 CH4 Emissions Million metric tons of CO2 equivalent 5.948 2,150 N2O Emissions Thousand metric tons of CO2 equivalent 3,402,881 1,395,861

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Middle East) China 3,176 803 644,725 India 1,028 445 398,980 Thailand 154 76 13,083 Primary GHG sources are: CO2 fuel combustion fossil fuel, solid waste, wood and wood products 1.8.6. CH4 livestock management; production and transport of coal, natural gas, and oil; and decomposition of organic wastes in municipal solid waste landfills N2O mainly agricultural soils; agricultural and industrial activities; combustion of solid waste and fossil fuels. 9 Visibility Degrading Pollutants Caused by scattering and absorption of light by particles and gases > Primary PM > Soot (elemental carbon) > PM precursors: SOx, NOx, VOC, NH3 Visibility impairment occurs as a result of the scattering and absorption of light by particles and gases in the atmosphere. It is most simply described as the haze which obscures the clarity, color, texture, and form of what we see. Particles can be from directly-emitting sources (primary PM and soot), or formed from PM precursors (such as nitrate and sulfate aerosols). Air Quality Management Model

1.9.

We have discussed air pollution what it is , sources of air pollution, effects of air pollution, and types of pollutants. The goal of an air quality management program is to improve air quality in a geographic area in order to improve the quality of life for a population. The air quality management model depicts how air quality is typically managed by agencies. It is a loop that is continuously applied over time to address new problems as they arise and revise older strategies if needed. The basic steps include:

Establish health and environmental goals your air quality program wants to achieve Determine what reductions in emissions and risks are needed to achieve established goals Determine how to achieve the reductions (voluntary, regulatory, economic incentives, partnerships, etc.) Implement reductions and enforce regulations if established Evaluate results after implementation of reductions Revise program if results do not meet established goals or if new problems not addressed by goals arise

In the model, emissions inventories are used to determine what reductions are needed and to evaluate results (pink boxes).

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Summary: Principles of Air Pollution

Air pollutants can be directly emitted by anthropogenic and natural sources to the atmosphere or formed

in the atmosphere by chemical reactions Air pollutants can have impacts on a local, regional, or global scale Air pollutants have human health and environmental effects Humans may be exposed to air pollutants indoors or outdoors Focus of training is on pollutants for which air quality standards have been established by various agencies > PM, CO, NO2, SO2, Pb, NH3, O3 Other important pollutants with health and environmental impacts > Air toxics, ODSs, GHGs, haze pollutants The air quality management model is an approach for describing how air pollution 10

2. Emission Inventory Fundamentals

This module covers the basic information needed in order to develop an emission inventory: What is an air emission inventory? Uses of emissions inventories Characteristics; Base year Pollutants Source Types Modeling Inventory needs Temporal and Spatial resolution Speciation Emissions inventory development Top-down vs. bottom-up Emission Inventory techniques (mass balance, source testing, extrapolation) 2.1. What is an Air Pollutant Emissions Inventory? Inventory - a comprehensive listing by sources of air pollutant emissions in a geographic area during a specific time period Sources:

 Stationary Point and Nonpoint Mobile Onroad and Nonroad Geographic area Global National Regional Local (city or neighborhood) Facility Specific Time Period Hour Day Month Season Year 2.2. Why Do We Need Air Emission Inventories? Public interest in clean air Fundamental Component of Air Quality Management Plan > To identify sources and problem areas > To establish a baseline for future planning > To develop air quality control plans and mitigation strategies > To establish regulations and permit conditions for industrial facilities and basis for emissions trading programs Fundamental Component of Air Quality Management Plan > To measure progress/changes over time to achieve cleaner air (track trends or progress toward air quality goals) > To determine compliance with environmental regulations To use in Modeling > Air quality modeling predict ambient concentration > Exposure modeling and risk assessments predict human health and ecological risks To help site ambient monitors Global Assessments

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To understand the impact of air pollution from your country on other nations To determine compliance with international treaties, for example, United Nations Framework Convention on Climate Change (UNFCCC) One primary reason for EIs is public interest in clean air. Are citizens getting sick from air pollution (increased visits to hospitals; complaints about coughs, runny eyes, etc.; increase in cancer incidences)? Are environmental effects occurring (decreased crop yields, odors, destruction of property)? Causes (pollutants and sources of health and environmental effects) What purpose do inventories serve in environmental protection and air quality management programs? Inventories are the fundamental building block of an air program. It is difficult to plan and implement a meaningful and successful air quality program without benefit of a good inventory. They indicate what is the baseline or starting point for assessing the status of a source's or an area's air quality problems. Inventories also give perspective on the nature of air quality problems, i.e., are the problems the result of emissions from point, nonpoint, or mobile sources, and what specific sources may need to be targeted. What are the pollutants and their emissions? What sources emit pollutants? Where and when are pollutants emitted from the sources? After identifying the problem, air quality control plans can be established using data from the baseline inventory. A high quality emission inventory provides the information needed to determine the type and extent of controls that may be required. The inventory assists in the formulation of control and maintenance strategies. These strategies may include regulations, permit program or an emissions trading program. Emission Inventories are important part of these strategies. - Industrial facilities need to know their emissions to determine specifications for control equipment - Regulators use inventories to calculate permit fees for normal operations and penalties for excess emissions - Regulators may create emission trading program to reduce emissions by setting up a banking and/or trading program. Industries may be able to bank emissions by removing polluting equipment and then using credits when applying for permits to build or modify new facilities that generate new emissions. Goal is keep net emissions below previous emission level. Emission inventories are used to calculate emission credits generated from pollution reduction activities. A high quality emission inventory provides the information needed to determine the type and extent of controls that may be required. The inventory assists in the formulation of control and

maintenance strategies. Inventories are also indirect indicators of overall air quality changes. Emission trends help to determine if air quality control programs are successful. Uncertainty analyses can be used to identify areas for improvement in emission inventories. Regulations are often established for facilities. Emission Inventories are needed to determine: 1. If regulations apply to a facility. The facility can use the emission inventory to evaluate the expected impact of future actions (what if emission controls are added, what if operating hours were reduced, what a different fuel source is substituted, etc.) Actual best estimate of emissions over a time period; based on actual rates of production; assumes control equipment properly operating Potential maximum rate of release over a time period; based on maximum throughput equipment capacity 12 1. If affected facilities comply with the regulations. Environmental treaties such as the United Nations Framework Convention on Climate Change (UNFCC) have emission inventory reporting requirements. One primary use of air emission inventories is modeling: Ambient air quality modeling and risk assessments. The use of inventory data as inputs of air quality modeling is crucial. If the quality and completeness of the inventory data used in the modeling is poor, the modeling results will be ineffective in determining the impact of pollution. Modeling requires different data elements in an inventory than in inventories used to track trends. Costs increase substantially when modeling is involved due to the level of detail in the inventory that is needed for modeling. Inventory results can be used to help in deciding where to site ambient monitors. The cost to operate ambient monitors to assess air pollution problems is much greater than preparing emission inventories. One approach used in air quality management is to first compile an emission inventory to determine sources and locations with air pollution problems. Then using the emission inventory information, you can decide where to site ambient monitors to further investigate air pollution problems.

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Inventories are also indirect indicators of overall air quality changes. Emission trends help to determine if air quality control programs are successful. Uncertainty analyses can be used to identify areas for improvement in emission inventories.

Environmental treaties such as the United Nations Framework Convention on Climate Change (UNFCC) have emission inventory reporting requirements. Growing evidence of intercontinental transport of O3, PM, Hg & POPs based on observational and modeling studies (Jacob/GRL/1999, Fiore/JGR/2002, Jaffe/AE/2002, Jacob/RPO/2003). Intercontinental Transport of Air Pollutants (POPS, PM, O3, and Hg) can significantly impact air quality over the USA and other regions Importance of impacts will increase in the future due to rapid growth in Asian emissions (Streets/AE/2001&2003 Impact of trans-Pacific transport is persistent thru the year; maximum impact of Asian emissions to the USA occurred in the Spring (~1.3 ug/m3 of PM2.5 and ~2.3 ppb of O3 in the West; ~0.9 ug/m3 and ~1 ppb in the East, monthly average) Future year simulations (2030) showed that sustainable development scenarios will significantly improve air quality in both Asia and North America 13 2.3. Air Pollution Control in the 21st Century

1920 2.4.

1950

1970

1980

1990

2000

What Do You Use Air Emission Inventories for in Your Country? Describe your countrys air quality management program > Goals > Problems: Pollutants and sources > Reduction strategies (regulations, voluntary reductions, trading, etc.) > Implementation and Enforcement activities > Evaluation of results > Describe how emission inventories are used in your air quality management program. Describe potential uses for emission inventories in your air quality management program. Each country should spend a few minutes describing their program and the uses of EIs in their air quality management programs. First write down description working as a group per country. Then discuss results with class. Emission Inventory Characteristics

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2.5.

Base year Geographic area Pollutants Source Categories Modeling parameters Spatial resolution Temporal resolution Speciation Every inventory is characterized by certain common parameters. Details related to these characteristics are discussed next. 2.5.1. Base Year

Base Year > Identifies the year for which emissions are estimated > Provides a benchmark for comparison with previous and future inventories compiled for different years > Provides a common basis for all the emission estimates

Year is selected based on purpose of the inventory, regulatory requirements, and data availability The base year defines the time period for which source activity data, such as fuel consumption, gasoline or chemical production, or number of employees, are determined for use in emissions calculations. It is important to note that comparisons of emissions between different base years may be more difficult to do if the estimation methods between the base years are different (e.g., one year based on emission factors and the other based on source testing). 2.5.2. Geographic Area Establishes geographic domain for the inventory Determines the sources to be included in the inventory based on their location Can be based on political boundaries (i.e., city, province, or country borders), air shed boundaries, or other (possibly arbitrary) considerations Is determined based on the purpose of the inventory > City-, district-, province-level, national analyses of air quality impacts (e.g., 100 to 500 km2) using modeling Discuss that inventory geographic coverage areas are sometimes defined by the domains of modeling grids. For the purpose of air quality dispersion modeling, modeling grid cell sizes (e.g., 4 km grids) may be established for the inventory. Especially for nonpoint and mobile sources, these grid cell sizes define how categories will be inventoried and spatially allocated. 14

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2.5.3.

Pollutants

Pollutants selected based on the purpose of the inventory Particulate matter analysis: PM10 and PM2.5, secondary aerosols Ozone analysis: NOx, VOC primarily (can include other carbon compounds) Visibility analysis > NOx, SOx, VOC, CO, PM10, PM2.5, NH3 Elemental and organic carbon (EC/OC) Greenhouse gases assessment > CH4, N2O, CO2 > HFCs, PCFs, and SF6 > Ozone depleting substances (ODS) > CFCs, HCFCs, halons, CCl4, methyl chloroform (C2H3Cl3), methyl bromide (CH3Br) Air toxics analysis > Important to use CAS #s > Keep in mind that toxicity varies by chemical Carcinogens Non-carcinogens > Compound groups Report individual compounds by CAS # for risk assessments Air toxics analysis: Compounds Groups Polycyclic Organic Matter: Includes organic compounds emitted from combustion sources with more than one benzene ring, and which have a boiling point greater than or equal to 1000 C . Examples include polycyclic aromatic hydrocarbons (PAHs), chrysene, benzo(a)pyrene, and naphthalene. Dioxins and Furans: Compounds can be grouped by 2,3,7,8 TCDD Toxic Equivalents (TEQs).TEQs are multipliers for some dioxin and furan congeners to get to a common basis of toxicity. Diesel PM - Mixture of particles that is a component of diesel exhaust. Diesel PM has Cancer and noncancer health effects Glycol ethers

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Xylenes and Cresols (ortho-, meta-, and para-) Metals: > Antimony, Beryllium, Cadmium, Cobalt, Manganese, Selenium > Chromium: report as hexavalent and trivalent > Lead: report as Organic and inorganic > Mercury: report as Particulate, gaseous elemental, and gaseous divalent > Nickel : report as Nickel subsulfide and other nickel compounds A visibility inventory would include sulfur oxides (sulfur aerosols); nitrogen oxides, PM2.5, elemental carbon (EC), organic carbon (OC), and ammonia. (NH3 in high doses can be toxic, although it is not normally inventoried as a toxic pollutant.) Methane, nitrous oxide, carbon dioxide hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), and sulfur hexafluoride (SF6) are the chief GHG species usually inventoried. There are several other gases that do not have a direct global warming effect, but which, because of their indirect effects on the formation or destruction of other GHGs, are often included in GHG inventories. These gases include CO, NOx, NMVOCs, and aerosols . Ozone depelting substances: CFCs being phased out due to Montreal Protocol; HCFCs, PCFs, SF6 make up small portion (~2%) of total GHGs. An air toxics inventory would contain volatile and particulate matter and non-VOC and non-PM air toxics. VOC ex. Benzene, xylene, toluene Heavy Metals ex. Arsenic, cadmium, mercury, lead, etc. Non VOC and non PM chlorine, hydrogen chloride, hydrogen fluoride Toxicity varies among the different metal compounds. Some compounds are carcinogens, some arent. Examples: Cr+3 is not a carcinogen, but Cr+6 IS. In EPAs NATA work, they speciate the % of Cr compounds that are Cr+6 based on the source category (see handout). For example, electroplating emission are assumed to be 98% CR+6. Having to make these types of assumptions introduces uncertainty. Nickel carbonyl and nickel oxide not carcinogens, but nickel subsulfide and nickel refinery dust ARE. 15 2.5.4. Source Categories Anthropogenic (man-made) and Natural sources may be included in an inventory. Anthropogenic Sources include:

> Stationary Point and Nonpoint sources > Mobile Onroad and Nonroad sources Natural sources include: > Biogenic emissions from vegetation > Geogenic emissions from soil, volcanoes, and geothermal activities Wildfires and wind erosion are classified as either anthropogenic or natural by different countries Indoor and Other source categories Point source locations are identified using either latitude/longitude or Universal Transverse Mercator (UTM) coordinates. These sources can be located by overall facility coordinates or stackspecific coordinates. Nonpoint, mobile, and natural emissions typically allocated to some geographic area such as a province or municipality. 2.5.4.1. Point Sources Emissions may be released from large or small point sources. Examples include electrical generating facilities, chemical manufacturing plants, secondary metal smelters, etc. Emissions may be released from: > Equipment leaks, > Transfer of materials from one location to another, or > Emissions stacks or vents

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Point Source Considerations May be defined based on: > Point source cutoffs / thresholds (e.g., 12 metric tons per year NOx) > Regulations or laws (e.g., all petroleum refineries are point sources) > Location or regulatory jurisdiction (e.g., regulated by city, state, or federal government) Detail needed: > Plant, unit, process, stack (emission release point) > Pollutants

> Operation schedule (for example, 7 days a week, 24 hr/day) > Location, stack parameters, control device info, Process description (for example, SCC), Facility description (for example, NAICS code) Point source locations are identified using either latitude/longitude or Universal Transverse Mercator (UTM) coordinates. These sources can be located by overall facility coordinates or stackspecific coordinates. Point sources include stack emissions and fugitives (non-stacks within the facility). Fugitive emissions may be greater for some facilities than stack emissions. Generally, discernible industrial facilities are easy to identify as point sources. They have easy to recognize emission points and will be required to obtain permits to be constructed and operate. Confusion can sometimes occur in defining what facilities are treated as point sources in terms of smaller sources that do not have easy to recognize smoke stacks and visible pollution (e.g., smaller VOC sources like printers). Point sources will usually be defined by an actual or potential emissions threshold and this can vary by region. For example, in the U.S., a VOC point source in one state may be one emitting a minimum of 10 tons/yr, while in another country the same source may have a point source threshold of 50 tons/yr. This can bring up issues of emissions double counting, which will be discussed later in this section. 2.5.4.2. Nonpoint Sources Stationary industrial, commercial, institutional facilities and businesses that are too small or numerous to be categorized as a point source Examples: dry cleaners, gasoline stations Nonpoint sources emit over a geographic area versus point sources that emit over a geographic point > Examples: residential cooking and heating, wind erosion of vacant lots and agricultural lands, dust from vehicle travel over paved and unpaved roads, consumer solvent use, wildfires Nonpoint Source Considerations May be defined based on: > Thresholds > Regulations Detail needed:

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> County level > Pollutants > Process description (for example, SCC) Includes source categories that overlap with point source inventory > Point source inventories often include small sources such as dry cleaners and gas stations > Due to differences in source type definitions and inventory procedures used, the potential for double counting of point and nonpoint source emissions exists > As required, point source contributions to some nonpoint source categories must be removed from nonpoint inventories In many areas, nonpoint sources are defined as having emissions below some minimum threshold. They are inventoried as a source category group and not individually. It is possible for a source type to exist as both a point and nonpoint source. For example, the rotogravure graphic arts print shop on the corner could be a nonpoint source, but the rotogravure facility printing the largest magazine in the country may be significant enough to be treated as a point source. Both may be rotogravure printers, but they do not have the same emissions characteristics and are not inventoried the same way, even though both are printers. A good point source air toxics inventory may include many smaller facilities such as gas stations, degreasers, Stage I, and dry cleaners. Point source thresholds will determine if a category is inventoried as a point or nonpoint source. Note that some nonpoint source categories, for example wind erosion and wildfires, may be considered under the natural sources source type, depending on the particular needs or preferences of the inventory developers. An important consideration of which categories are within a given source type is if comparisons are made between inventories. Can have some point source categories (or portions) in nonpoint inventory. Example: Graphic arts. 2.5.4.3. Mobile Sources Pollutants VOC, PM, CO, Lead, NOx, SO2 Greenhouse Gases: CO2, N2O, CH4 20 volatile organic and metal air toxics Diesel particulate matter and diesel exhaust organic gases Includes Onroad and Nonroad Sources

*Onroad Onroad - Vehicles found on roads and highways. Fuel types - Vehicles may operate on any fuel, including petrol, diesel, propane, methanol, and electricity Vehicle classifications depend on methodology used to estimate emissions: > Passenger vehicles, trucks and vans > Heavy duty trucks with trailers > Buses and motor homes > Taxis > Two and three-wheeled vehicles designed for onroad use Emission Types include: > Exhaust emissions > Evaporative emissions Exhaust emissions: emissions released from the tailpipe of the vehicle Evaporative emissions: emissions released through evaporative processes from vehicle points such as the fuel tank, fuel lines, carburetor, and crank case.

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*Nonroad Nonroad - Mobile sources not found on roads Specific categories of nonroad sources vary between inventories > Aircraft (may be included in nonpoint sources) > Locomotives (may be included in nonpoint sources) > Boats and other marine vessels (may be included in nonpoint sources) > 2/4 stroke engines in construction, industrial, and agricultural equipment, lawn and garden equipment, etc.

Aircraft emissions correlate with airports and can include airport support vehicles (baggage carts, aircraft pushback vehicles, auxiliary power units and aircraft refueling) as well. Vessels include both inland commercial and recreational vessels and oceanic vessels such as fishing boats, cruise ships, military ships, tug boats, private vessels, commercial marine freight/cargo vessels.

Construction equipment can include tractors, bulldozers, backhoes, etc. Industrial equipment can include forklifts and other in-plant vehicles. Agricultural equipment involves tractors, harvesters, combines, etc. Lawn and garden relates to portable equipment for private residential, commercial, and industrial activities. Mobile Source Considerations Contribution by source category varies geographically May be defined by regulations Detail needed: > County level > Pollutants Process description (for example, SCC) 2.5.5. Natural Sources Natural biological and geological phenomenon which generate air emissions (nonanthropogenic) Biogenic emissions: > VOC emissions from vegetation Geogenic emissions: > NOx emissions from soil (denitrification) > SOx emissions from volcanoes > and geothermal activity May include wind erosion, wildfires Wind erosion and wildfires may be included in either/or the nonpoint or natural source type 2.5.6. Indoor Sources Indoor air can become contaminated from numerous sources Indoor air can have significantly higher concentrations of air pollutants than outdoor air

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For many years, study of air pollution focused almost entirely on outdoor air. Outbreak of Legionnaires disease during summer of 1976 helped refocus attention on indoor air problems. People spend 80 90 % of their time indoors in homes, schools, places of work, entertainment, etc. The % of time spent indoors tends to be greatest for people who are most susceptible to risks of air pollution elderly, very young and those who are ill. Indoor environments are less self-cleansing. Indoor environments are often tightly sealed with constant temperatures that promote air stagnation. Airborne pollutants can reach high concentrations more quickly than outdoor pollutants and can persist for longer periods of time if the air is not properly ventilated. 2.5.7. Other Types of Sources

There are a number of other important sources of air pollutants that arent so easy to categorize or count Accidental releases Long-range transport of air pollutants Historical background (for example, carbon tetrachloride) 2.6. Emission Inventory Characteristics: What is Air Quality Modeling? Determination of ambient air concentrations and deposition of pollutants by mathematically simulating their fate & transport in the atmosphere Why Model? Too costly to monitor for every pollutant everywhere > However, limited monitoring data are needed to confirm modeling results To predict what will happen > New source > New strategies > Future Growth Can tell you what sources are contributing to the ambient air concentrations includes transport from other areas

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Modeling Inventories Modeling inventories have more specific requirements than other more general tracking inventories Modeling inventories need > Geographically resolved emissions (gridded or specific dimensions) spatial allocation of emissions > Hourly time resolution temporal allocation of emissions > Pollutant species (model species) to meet needs of AQ model chemical/physical algorithms *Risk assessors want modeled species to match health effects data > Quality Assurance/Quality Control of data > All sources represented Anthropogenic, Biogenic (grid models) Important to convey that good quality modeling parameters are essential in developing modeling inventories, since without them, the results of the modeling process can be very flawed and misleading. General Tracking Inventories (e.g., national scale): Point source locations are identified using either latitude/longitude or Universal Transverse Mercator (UTM) coordinates. These sources can be located by overall facility coordinates or stack-specific coordinates. Nonpoint, mobile, and natural emissions typically allocated to some geographic area such as a province or municipality. Modeling Inventories: Point source locations based on stack-specific Lat/Longs or UTM coordinates.. Nonpoint, mobile, and natural emissions allocated to small grid cells (e.g., 1 to 10 km2), onroad mobile also allocated based on roadway links.

Allocations based on activity data (e.g., gasoline sales) or activity surrogate (e.g., land use data) parameters.