{"id":590,"date":"2021-07-02T10:43:03","date_gmt":"2021-07-02T10:43:03","guid":{"rendered":"https:\/\/courses.lumenlearning.com\/suny-binghamton-envi101&#038;envi201\/chapter\/__unknown__-3\/"},"modified":"2021-08-01T19:50:22","modified_gmt":"2021-08-01T19:50:22","slug":"chapter-15","status":"publish","type":"chapter","link":"https:\/\/courses.lumenlearning.com\/suny-binghamton-envi101&envi201\/chapter\/chapter-15\/","title":{"raw":"Chapter 20 ~ Gaseous Air Pollution","rendered":"Chapter 20 ~ Gaseous Air Pollution"},"content":{"raw":"<div class=\"__UNKNOWN__\">\r\n<h2 class=\"import-Normal2\">Key Concepts<\/h2>\r\n<ol>\r\n \t<li class=\"import-Normal2\">After completing this chapter, you will be able to<\/li>\r\n \t<li class=\"import-Normal2\">Outline the major sources of emission of air pollutants associated with sulfur, nitrogen, and hydrocarbons.<\/li>\r\n \t<li class=\"import-Normal2\">Explain the difference between primary and secondary pollutants.<\/li>\r\n \t<li class=\"import-Normal2\">Contrast the environmental problems associated with stratospheric and tropospheric ozone.<\/li>\r\n \t<li class=\"import-Normal2\">Examine the importance of air pollutants to ecosystems and to human health.<\/li>\r\n \t<li class=\"import-Normal2\">Describe the patterns of pollution and ecological damage near point sources of air pollution.<\/li>\r\n<\/ol>\r\n<h1 class=\"import-Normal2\">Introduction<\/h1>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Gaseous air pollutants are emitted from various natural sources, such as volcanoes and forest fires. However, anthropogenic emissions of some gases may be greater than the natural ones, and are increasing because of population growth and industrialization.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">In ancient times, there was not much pollution. Nevertheless, even then local problems would have occurred. For instance, smoky wood fires used for cooking and warmth would likely have caused poor-quality air to occur inside of badly ventilated dwellings. Hunting cultures often used fire to drive game animals and improve local forage, and those burns would have resulted in large emissions of particulate carbon (soot), carbon dioxide, and other gases that would have temporarily impaired air quality. Overall, however, these effects were relatively minor.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Of course, as people became more numerous and industrialized, air pollution increasingly developed into a much bigger problem. When the Industrial Revolution began (around 1750), coal quickly became the major fuel used to generate heat and energy for machines, and that resulted in increasingly worse air pollution. The widespread use of coal led to severe pollution by sulfur dioxide (SO<sub>2<\/sub>) and soot in the industrial towns and cities of Europe and the Americas. Since 1900, burgeoning industrialization and new technologies such as power plants and automobiles have further increased the emissions of pollutants.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Air pollution can be especially severe in situations when the lower atmosphere is stable and calm. These conditions often occur beneath an atmospheric phenomenon called an inversion, in which a layer of cool air is trapped beneath a higher layer of warmer air (the more usual pattern is for temperature to cool with increasing altitude). An atmospheric inversion is a relatively stable condition that prevents polluted ground-level air from mixing with cleaner air from higher altitudes (see In Detail 20.1). If an atmospheric inversion is accompanied by fog, the pollution is known as smog (a word derived from \u201csmoke\u201d and \u201cfog\u201d). As recently as the 1950s, occasional so-called \u201ckiller smogs\u201d rich in SO<sub>2<\/sub>\u00a0and soot caused the deaths of thousands of urban people, and many more suffered from respiratory distress (pollution rich in SO<sub>2<\/sub>\u00a0is also called reducing smog). The most famous killer smogs occurred in London, Glasgow, some other industrial centers of Europe, and near Pittsburgh in the U.S.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Once scientists recognized the severe damage that was being caused by air pollution, governments began to pass laws to decrease the emissions. Pollution control became particularly vigorous after medical researchers discovered clear evidence of links between air quality and human diseases and deaths. Particular attention was paid to air pollution in urban environments, where the killer smogs were most frequent. Governments typically responded with important control actions, such as the following:<\/p>\r\n\r\n<ul>\r\n \t<li class=\"import-Normal2\">Switching from coal, which is a relatively \u201cdirty\u201d fossil fuel, to \u201ccleaner\u201d ones such as natural gas or oil, or to alternative energy technologies such as nuclear power and hydroelectricity<\/li>\r\n \t<li class=\"import-Normal2\">Constructing tall smokestacks to spread emissions over a much wider area so that ground-level exposures become less common and less intense \u2013 this tactic is the \u201cdilution solution to pollution\u201d<\/li>\r\n \t<li class=\"import-Normal2\">Centralizing energy production in large power plants to replace much of the relatively dirty and inefficient burning of coal in home fireplaces and furnaces, thereby permitting better control of emissions<\/li>\r\n \t<li class=\"import-Normal2\">Treating waste gases to remove some of their pollutant content, thereby reducing emissions to the atmosphere<\/li>\r\n<\/ul>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Because of these helpful regulatory actions, the importance of reducing smogs became much less in many countries. However, so-called oxidizing smog has become more important causes of damage in many regions. Oxidizing smog develops in the atmosphere through complex photochemical reactions in which hydrocarbons and nitrogen oxides are transformed into ozone (O<sub>3<\/sub>) and other gases. Ozone and other oxidizing gases harm vegetation and irritate the respiratory system and eyes of people. Oxidizing smog develops under sunny conditions if hydrocarbons and nitrogen oxides are present from automobile and industrial emissions, and especially if the presence of an atmospheric inversion reduces dispersion of the polluted air mass.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">In this chapter, we examine the most important gaseous pollutants. Their sources of emission, chemical transformations, and toxicity are described, and case studies are used to demonstrate the ecological damages that may be caused.<\/p>\r\n\r\n<div class=\"textbox shaded\">\r\n<h3 class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">In Detail 20.1. \u00a0Air Temperature Inversions<\/h3>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">Normally, the temperature of the atmosphere decreases with increasing altitude. Under certain conditions, however, a layer of relatively cool air may become trapped under a layer of warmer air, a phenomenon known as an atmospheric inversion (or temperature inversion; Figure 20.1).<\/p>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\"><img class=\"aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/5337\/2021\/07\/02104249\/image1.png\" alt=\"image\" width=\"624.533333333333px\" height=\"456.266666666667px\" \/><\/p>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">Figure 20.1. The figure above shows different characteristics of atmospheric inversion including air temperature, density stratification, height and intensity, as well as air motion. Source: Data and Figure from <a href=\"https:\/\/www.ag.ndsu.edu\/publications\/crops\/air-temperature-inversions-causes-characteristics-and-potential-effects-on-pesticide-spray-drift\">\u201cAir Temperature Inversions Causes, Characteristics, and Potential Effects on Pesticide Spray Drift\u201d by Andrew Thostenson, Jon W. Enz, and Vernon Hofman<\/a>\u00a0is licensed under <a href=\"https:\/\/creativecommons.org\/licenses\/by-nc-sa\/3.0\/\">CC-BY-NC-SA 3.0<\/a>.<\/p>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">An atmospheric inversion may develop on a clear, cloudless night. Under such conditions, the ground surface cools quickly as it radiates heat that was absorbed during the day. This can result in a layer of cool air occurring beneath a higher layer of warmer air. Hilly terrain is particularly vulnerable to developing atmospheric inversions because relatively dense cool air can flow downward from hilltops and accumulate in valleys. Sometimes during the summer, stable atmospheric conditions may develop at higher altitude, capping a still-mixing air mass at ground level.<\/p>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">An atmospheric inversion can be rather stable. Until it is dispersed by vigorous winds, it can trap and accumulate air pollutants that are emitted during the inversion event. Severe episodes of air pollution can occur when stable inversions develop and are maintained for several days.<\/p>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">Some places regularly develop less-persistent inversions, such as Los Angeles, Mexico City, and Greater Vancouver. In these places, the inversions develop in the morning but are typically dispersed during the afternoon. In the meantime, however, oxidizing air pollutants such as ozone can accumulate into a photochemical smog.<\/p>\r\n\r\n<\/div>\r\n<h1 class=\"import-Normal2\">Sulfur Gases<\/h1>\r\n<h2 class=\"import-Normal2\">Emissions and Transformations<\/h2>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Sulfur dioxide (SO<sub>2<\/sub>) is one of the most important of the gaseous air pollutants. SO<sub>2<\/sub>\u00a0is a colorless but pungent gas. Humans can detect its bitter taste at a concentration of only 0.3-1 ppm (parts per million; for SO<sub>2<\/sub>, 1 ppm = 2.6 mg\/m<sup>3<\/sup>). Hydrogen sulfide (H<sub>2<\/sub>S), another sulfur gas, can be detected as a foul odor, reminiscent of rotten eggs, at concentrations lower than 1 ppb (parts per billion; for H<sub>2<\/sub>S, 1 ppm = 1.4 mg\/m<sup>3<\/sup>) (unless otherwise indicated, specific data cited in this and other chapters in this section on environmental damages are from Freedman, 1995).<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">After they are emitted to the atmosphere, SO<sub>2<\/sub>\u00a0and H<sub>2<\/sub>S become oxidized to other compounds, and ultimately form sulfate (SO<sub>4<\/sub><sup>2\u2013<\/sup>; see In Detail 20.2). Because the sulfate ion carries negative charges, it is an anion (this refers to any ion, atom, or molecule with a negative charge). Because H<sub>2<\/sub>S is quickly oxidized to SO<sub>2<\/sub>, its atmospheric residence time is less than one day (this is the time to complete disappearance of an initial amount). SO<sub>2<\/sub>\u00a0oxidizes more slowly, at a rate of &lt; 1-5% per hour, depending on sunlight, humidity, strong oxidants such as ozone, and the presence of metal-containing particulates that may act as catalysts. A typical residence time of SO<sub>2<\/sub>\u00a0in the atmosphere is about four days. Consequently, SO<sub>2<\/sub>\u00a0may disperse a long distance from its point of emission before it becomes oxidized or is deposited to a terrestrial or aquatic surface. This kind of dispersal is referred to as long-range transportation of air pollution (LRTAP).<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Atmospheric sulfate, formed by the oxidation of SO<sub>2<\/sub>\u00a0or H<sub>2<\/sub>S, can combine with positively charged ions (cations) to form various compounds. Most atmospheric sulfate occurs as tiny particulates, especially ammonium sulfate ((NH<sub>4<\/sub>)<sub>2<\/sub>\u00a0SO<sub>4<\/sub>). This is the most prominent component, along with ammonium nitrate (NH<sub>4<\/sub>NO<sub>3<\/sub>), of the fine particulate haze that often impairs visibility in cities. Haze also occurs in some rural areas where pollutants have been imported by LRTAP from emission sources elsewhere. Other cations that combine with sulfate include calcium (Ca<sup>2+<\/sup>), magnesium (Mg<sup>2+<\/sup>), and sodium (Na<sup>+<\/sup>). Often, however, there are not enough of these cations to balance all of the negative charges of the sulfate (SO<sub>4<\/sub><sup>2\u2013<\/sup>) present. Under such conditions, hydrogen ions (H<sup>+<\/sup>) serve to balance some of the negative charges, resulting in an aerosol containing sulfuric acid (H<sub>2<\/sub>SO<sub>4<\/sub>), the most important component of acidic precipitation (see Chapter 23).<\/p>\r\n\r\n<h2 class=\"import-Normal2\">Emissions of Sulfur Gases<\/h2>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Volcanoes are natural sources of emission of sulfur gases. On average, volcanoes emit about 12-million tonnes of sulfur gases per year, of which 90% is SO<sub>2<\/sub>\u00a0and 10% is H<sub>2<\/sub>S. However, the enormous 1991 eruption of Mount Pinatubo in the Philippines emitted 7-10-million tonnes of SO<sub>2<\/sub>\u00a0(expressed as the sulfur content, or SO<sub>2<\/sub>-S). The much smaller eruption of Mount St. Helens in Washington State in 1980 vented about 0.2-million tonnes of SO<sub>2<\/sub>-S. Natural emissions of SO<sub>2<\/sub>\u00a0also occur during wildfires.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">The global anthropogenic emissions of SO<sub>2<\/sub>\u00a0are about 150-million tonnes per year, or 3.8-times the natural releases. Fossil-fuel combustion accounts for more than half of the anthropogenic emissions (Figure 20.2). Coal and petroleum contain mineral compounds of sulfur, such as pyrite (FeS<sub>2<\/sub>), as well as organic sulfur compounds. When these fuels are burned, the sulfur becomes oxidized to gaseous SO<sub>2<\/sub>, which may be vented to the atmosphere. Hard coals mined in eastern North America contain 1-12% sulfur, softer coals from western regions have &lt;0.3-1.5%, crude oil has 0.8-1.0% residual fuel oils such as bunker -C have 0.3-0.4%, and motor fuels such as diesel and gasoline have 0.04-0.05%. Other important sources of SO<sub>2 <\/sub>emissions are manufacturing processes (23% of global emissions), the smelting of metal ores (7%), and the burning of natural habitats during agricultural conversions (most of the rest).<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\"><img class=\"aligncenter\" \/><\/p>\r\n<img class=\"alignnone size-full wp-image-735\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/5337\/2021\/07\/05121527\/Picture16.png\" alt=\"\" width=\"1791\" height=\"783\" \/>\r\n<p class=\"import-Normal\">Figure 20.2. Global Anthropogenic SO<sub>2<\/sub> Emissions from 1850-2005. Source: <a href=\"https:\/\/acp.copernicus.org\/articles\/11\/1101\/2011\/acp-11-1101-2011.pdf\">Smith et al. 2011<\/a><\/p>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">Globally anthropogenic emissions of SO<sub>2<\/sub>\u00a0have increased enormously since the beginning of the Industrial Revolution. Emissions in 1860 were about 5-million tonnes, compared with about 150-million tonnes in 2000. Since then, most of the wealthier countries have invested heavily in clean-air technologies for power plants and other industrial users of coal and oil in order to reduce emissions of damaging SO<sub>2<\/sub>\u00a0to the atmosphere. The clean-air actions include the following:<\/p>\r\n\r\n<ul>\r\n \t<li class=\"import-Normal2\">The installation of technologies to capture SO<sub>2<\/sub>\u00a0from post-combustion waste gases (this is known as flue-gas desulphurization or scrubbing)<\/li>\r\n \t<li class=\"import-Normal2\">The removal of some of the sulfur content of fuels (known as fuel desulphurization or coal washing)<\/li>\r\n \t<li class=\"import-Normal2\">The installation of particulate-control devices (such as electrostatic precipitators) to greatly reduce the emissions of particulates (although this has little effect on SO<sub>2<\/sub>\u00a0emissions)<\/li>\r\n \t<li class=\"import-Normal2\">Switching to low- or no-sulfur fuels such as natural gas, or to no-sulfur energy technologies such as hydroelectricity and nuclear power (known as fuel-switching)<\/li>\r\n \t<li class=\"import-Normal2\">Energy conservation to reduce the overall demand for fuel and associated emissions of pollutants<\/li>\r\n \t<li class=\"import-Normal2\">Building taller smokestacks to disperse emissions of SO<sub>2<\/sub>\u00a0more widely, which helps to decrease the local ground-level pollution<\/li>\r\n<\/ul>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">However, future global emissions are bound to increase. China, India, and other rapidly industrializing countries supply much of their burgeoning energy needs by burning coal and petroleum fuels. In China, coal is the major source of industrial energy, accounting for 58% of the energy supply in 2019 (U.S. Energy Information Administration 2020). Due to increasing industrialization, emissions of SO<sub>2<\/sub>\u00a0in China increased from 10-million tonnes in 1980 to 34-million tonnes in 2000, a 3.4-fold increase in only 20 years.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">The amounts of SO<sub>2<\/sub>\u00a0emissions differ greatly among nations, depending on their population, their kind of industrialization, and the fuels they mostly use. For instance, Canadian emissions of SO<sub>2<\/sub>\u00a0are about 22% of those of the U.S. However, the population of Canada is only about 11% that of the U.S. Therefore, per-capita emissions of SO<sub>2<\/sub>\u00a0are about double in Canada than in the U.S.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">About 66% of Canadian emissions of SO<sub>2<\/sub>\u00a0are from large industrial sources, particularly metal smelters, while 24% are from \u201cfuel combustion,\u201d which is mostly fossil-fueled power plants. In comparison, 84% of U.S. emissions are from power plants, and 10% from industrial sources. Most of this difference is due to two factors: a relatively large proportion of electricity generation in Canada is from nuclear and hydro technologies, which do not emit SO<sub>2<\/sub>, and metal smelting is a major industry in Canada.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Because of human-health and environmental damages associated with SO<sub>2<\/sub>\u00a0and other air pollutants, most developed nations have acted to reduce their emissions. In Canada, emissions of SO<sub>2<\/sub> were reduced by about 41% between 1985 and 2012, compared with a 32% reduction in the U.S. (Figure 20.2). In both countries the reductions were achieved by several methods:<\/p>\r\n\r\n<ul>\r\n \t<li class=\"import-Normal2\">Switching to low- or no-sulfur fuels for some major uses, especially for electricity generation<\/li>\r\n \t<li class=\"import-Normal2\">Removing sulfur from some fuels prior to combustion, mostly by coal washing<\/li>\r\n \t<li class=\"import-Normal2\">Reducing energy demands through conservation<\/li>\r\n \t<li class=\"import-Normal2\">Installing scrubbers to remove SO<sub>2<\/sub>\u00a0from post-combustion waste gases before they are vented to the atmosphere<\/li>\r\n<\/ul>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">The large reductions of SO<sub>2 <\/sub>that have been achieved in North America during the past several decades cost many billions of dollars to achieve, and they should be regarded as an important \u201csuccess story\u201d of pollution control. Figure 20.3 depicts reduction in sulfur dioxide emissions for the U.S.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\"><img class=\"aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/5337\/2021\/07\/02104254\/image3.png\" alt=\"image\" width=\"715\" height=\"364\" \/><\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Figure 20.3. Reductions in Sulfur Dioxide Emissions in the U.S. from 2006 to 2015. Data from <a href=\"https:\/\/www.eia.gov\/todayinenergy\/detail.php?id=29812\">U.S. Energy Information Administration.<\/a><\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">In contrast to SO<sub>2<\/sub>, the global emissions of sulfide gases are mostly from natural sources. The largest sources are H<sub>2<\/sub>S emitted from anoxic sediment in shallow marine and inland waters, and dimethyl sulfide ((CH<sub>3<\/sub>)<sub>2<\/sub>S) produced by phytoplankton and out-gassed from oceanic waters. The natural emission of H<sub>2<\/sub>S is about 100-million tonnes per year, and dimethyl sulfide, 15-million tonnes per year (both expressed as sulfur equivalent, or as tonnes of S). Anthropogenic emissions of H<sub>2<\/sub>S are about 3-million tonnes per year, and are mostly from chemical industries, sewage-treatment plants, and livestock manure. The global emission of all sulfur-containing gases is equivalent to almost 300- million tonnes of sulfur per year. About half of the global emission is from anthropogenic sources. Clean air typically contains less than 0.2 ppb of SO<sub>2<\/sub>\u00a0or H<sub>2<\/sub>S. Concentrations of SO<sub>2<\/sub>\u00a0and H<sub>2<\/sub>S in air that is polluted by emissions are highly variable. They are typically about 0.2 ppm in urban atmospheres but can exceed 3 ppm close to large emission sources.<\/p>\r\n\r\n<h2 class=\"import-Normal2\">Toxicity of Sulfur Gases<\/h2>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Concentrations of H<sub>2<\/sub>S in the environment are rarely high enough to be toxic to plants. However, accidental emissions from sour-gas plants (where H<sub>2<\/sub>S is removed from natural gas) may cause local vegetation damage. In contrast, concentrations of SO<sub>2<\/sub>\u00a0in cities and near industrial sources are often high enough to injure wild and cultivated plants. Near certain metal smelters, vegetation has been severely damaged, as we examine later.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">An exposure to 0.7 ppm SO<sub>2<\/sub>\u00a0for one hour will result in acute injury to most plant species, as will 0.2 ppm over an eight-hour period. It is important to note, however, that certain species are extremely sensitive to SO<sub>2<\/sub>\u00a0exposures (they are hypersensitive) and can suffer acute injuries at concentrations lower than those just noted.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">In addition, plants will often exhibit a reduction in yield when exposed to concentrations of SO<sub>2<\/sub>\u00a0that are lower than those required to cause an acute injury. This type of response, which occurs without symptoms of acute tissue damage, is referred to as \u201chidden injury\u201d. Hidden injuries to wild and agricultural vegetation are measured by enclosing plants in experimental chambers and exposing them to either air containing ambient levels of SO<sub>2<\/sub>, or that that has been filtered through charcoal to remove that gas. If productivity is greater in the filtered air, it follows that the ambient SO<sub>2<\/sub>\u00a0was causing a hidden injury. Studies of pasture grasses have found that exposure to SO<sub>2<\/sub>\u00a0concentrations averaging only 0.04 ppm would cause hidden injuries as reductions of yield.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">The U.S. National Ambient Air Quality Standards (Table 20.1) sets the guideline for ambient SO<sub>2<\/sub>\u00a0in the atmosphere at 75 parts per billion over a one-hour exposure time (EPA 2020a), and 0.5 ppm over a three-hour exposure time.\u00a0These\u00a0guidelines\u00a0are\u00a0intended to protect human populations (particularly those sensitive to air pollutants, e.g., those with asthma, children, and the elderly) as well as to prevent\u00a0acute foliar (leaf) injuries agricultural plants. Although regions meeting these\u00a0guidelines\u00a0would not show much acute damage to vegetation, relatively sensitive species might be affected through hidden injuries, possibly resulting in significant losses of yield.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Table 20.1. National Ambient Air Quality Standards for Six Principal Pollutants. This table shows both the primary and secondary standards, which define the limits of the pollutants to minimize their harmful impacts on public health and the environment. Primary standards are the limits placed to protect public health, including protecting the \u201csensitive\u201d populations (asthmatics, children, and the elderly). Secondary standards concern public welfare and environmental protections. Source: <a href=\"https:\/\/www.epa.gov\/criteria-air-pollutants\/naaqs-table\">EPA<\/a>.<\/p>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\"><img class=\"aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/5337\/2021\/07\/02104255\/image4.png\" alt=\"image\" width=\"724\" height=\"794\" \/><\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Humans and most other animals are much less sensitive to SO<sub>2<\/sub>\u00a0than plants are. Guidelines for allowable exposures of people to SO<sub>2<\/sub>\u00a0and other potentially toxic gases accommodate the fact that, in terms of dose received, longer-term exposures to low concentrations can be as important as higher acute exposures.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Guidelines for occupational exposures to air pollutants are frequently greater than those for ambient exposures. In North America, it is recommended that occupational exposures to SO<sub>2<\/sub>\u00a0be no higher than 2 ppm (5.2 mg\/m<sup>3<\/sup>) over the long term, and no higher than 5 ppm (13 mg\/m<sup>3<\/sup>) for shorter exposures. However, some people are relatively sensitive to SO<sub>2<\/sub>, and concentrations less than 1 ppm (2.6 mg\/m<sup>3<\/sup>) may cause them to suffer asthma or other distresses related to impaired lung function. In addition, some studies have suggested that long-term exposures of large human populations to sulfate particulate aerosols (which are ultimately derived from gaseous SO<sub>2<\/sub>) in cities may result in small increases in the incidence of respiratory and circulatory diseases, most probably in hypersensitive people.<\/p>\r\n\r\n<div class=\"textbox shaded\">\r\n<h3 class=\"import-Normal2\" style=\"margin-right: 24pt;\">In Detail 20.2. Air Pollution Chemistry<\/h3>\r\n<p class=\"import-Normal2\" style=\"margin-right: 24pt;\">Air pollutants are emitted as particular chemicals, which may then be transformed into other compounds through reactions occurring in the atmosphere. Several examples follow.<\/p>\r\n\r\n<h2 class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">Oxidation of SO<sub>2<\/sub><\/h2>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">SO<sub>2<\/sub>\u00a0+ OH \u2192 HO\u2022SO<sub>2<\/sub>\u00a0(1)<\/p>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">HO\u2022SO<sub>2<\/sub>\u00a0+ O<sub>2<\/sub>\u00a0\u2192 HO<sub>2<\/sub>\u00a0+ SO<sub>3<\/sub>\u00a0(2)<\/p>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">SO<sub>3<\/sub>\u00a0+ H<sub>2<\/sub>O \u2192 H<sub>2<\/sub>SO<sub>4<\/sub>\u00a0(3)<\/p>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">H<sub>2<\/sub>SO<sub>4<\/sub>\u00a0\u2192 2H<sup>+<\/sup>\u00a0+ SO<sub>4<\/sub><sup>2\u2013<\/sup>\u00a0(in aqueous solution) (4)<\/p>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">Note that the SO<sub>4<\/sub><sup>2\u2013<\/sup>\u00a0produced is important as a constituent of acid rain and as particulate ammonium sulfate ((NH<sub>4<\/sub>)<sub>2<\/sub>SO<sub>4<\/sub>), which are important pollutants.<\/p>\r\n\r\n<h2 class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">Oxidation of NO<\/h2>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">NO + HO<sub>2<\/sub>\u00a0\u2192 NO<sub>2<\/sub>\u00a0+ OH (5)<\/p>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">NO<sub>2<\/sub>\u00a0+ OH \u2192 HNO<sub>3<\/sub>\u00a0(6)<\/p>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">HNO<sub>3<\/sub>\u00a0\u2192 H<sup>+<\/sup>\u00a0+ NO<sub>3<\/sub><sup>\u2013<\/sup> (in aqueous solution) (7)<\/p>\r\n<p class=\"import-Normal2\" style=\"layout-grid-mode: both; text-align: justify; text-justify: inter-ideograph; margin-right: 23.75pt;\">Similarly, the NO<sub>3<\/sub><sup>\u2013<\/sup> produced is important in acid rain and as particulate ammonium nitrate (NH<sub>4<\/sub>NO<sub>3<\/sub>).<\/p>\r\n\r\n<h2 class=\"import-Normal2\" style=\"layout-grid-mode: both; text-align: justify; text-justify: inter-ideograph; margin-right: 23.75pt;\">Formation and Destruction of Stratospheric O<sub>3<\/sub><\/h2>\r\n<p class=\"import-Normal2\" style=\"layout-grid-mode: both; text-align: justify; text-justify: inter-ideograph; margin-right: 23.75pt;\">O<sub>2<\/sub>\u00a0+ UV radiation \u2192 O + O (8) O + O \u2192 O<sub>2<\/sub>\u00a0(9)<\/p>\r\n<p class=\"import-Normal2\" style=\"layout-grid-mode: both; text-align: justify; text-justify: inter-ideograph; margin-right: 23.75pt;\">O + O<sub>2<\/sub>\u00a0\u2192 O<sub>3<\/sub>\u00a0(10)<\/p>\r\n<p class=\"import-Normal2\" style=\"layout-grid-mode: both; text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">O<sub>3<\/sub>\u00a0+ UV radiation \u2192 O<sub>2<\/sub>\u00a0+ O (11)<\/p>\r\n<p class=\"import-Normal2\" style=\"layout-grid-mode: both; text-align: justify; text-justify: inter-ideograph; margin-right: 23.75pt;\">Reaction 11 is an ultraviolet photodissociation of O<sub>3<\/sub>. Ozone can also be consumed by reactions with NO, NO<sub>2<\/sub>, N<sub>2<\/sub>O, and with ions or simple molecules of chlorine (especially ClO), bromine, and fluorine. These reactions are too complex to describe here.<\/p>\r\n\r\n<h2 class=\"import-Normal2\" style=\"layout-grid-mode: both; text-align: justify; text-justify: inter-ideograph; margin-right: 23.75pt;\">Formation and Destruction of Ground-Level O<sub>3<\/sub><\/h2>\r\n<p class=\"import-Normal2\" style=\"layout-grid-mode: both; text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">O + O<sub>2<\/sub>\u00a0\u2192 O<sub>3<\/sub>\u00a0(10)<\/p>\r\n<p class=\"import-Normal2\" style=\"layout-grid-mode: both; text-align: justify; text-justify: inter-ideograph; margin-right: 23.75pt;\">NO<sub>2<\/sub>\u00a0+ UV radiation \u2192 NO + O (12)<\/p>\r\n<p class=\"import-Normal2\" style=\"layout-grid-mode: both; text-align: justify; text-justify: inter-ideograph; margin-right: 23.75pt;\">NO + O<sub>3<\/sub>\u00a0\u2192 NO<sub>2<\/sub>\u00a0+ O<sub>2<\/sub>\u00a0(13)<\/p>\r\n<p class=\"import-Normal2\" style=\"layout-grid-mode: both; text-align: justify; text-justify: inter-ideograph; margin-right: 23.75pt;\">NO + RO<sub>2<\/sub>\u00a0\u2192 NO<sub>2<\/sub>\u00a0+ RO (14)<\/p>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">The formation of O<sub>3<\/sub>\u00a0(reaction 10) requires atomic O, formed by the photodissociation of NO<sub>2<\/sub>\u00a0(reaction 12). Ozone can be consumed by reaction with NO (an emitted gas), which regenerates NO<sub>2<\/sub>\u00a0(reaction 13). Atmospheric O<sub>3<\/sub>\u00a0can, however, accumulate if other reactions (such as reaction 14) convert NO to NO<sub>2<\/sub>, because these operate in competition with reaction 13 for NO. (The species RO<sub>2<\/sub>\u00a0includes various chemicals known as peroxy radicals, formed by the degradation of organic molecules by reaction with hydroxyl radicals, followed by the addition of molecular O<sub>2<\/sub>. RO is the chemically reduced form of RO<sub>2<\/sub>.)<\/p>\r\n\r\n<\/div>\r\n<h1 class=\"import-Normal2\">Nitrogen Gases<\/h1>\r\n<h2 class=\"import-Normal2\">Emissions and Transformations<\/h2>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">The most important of the nitrogen-containing gases are nitric oxide (NO), nitrogen dioxide (NO<sub>2<\/sub>), nitrous oxide (N<sub>2<\/sub>O), and ammonia (NH<sub>3<\/sub>). NO and NO<sub>2<\/sub>\u00a0are often considered together as a complex, referred to as NO<sub>x<\/sub>.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Ammonia (NH<sub>3<\/sub>), a colorless gas, is emitted mostly from wetlands, where it is produced during the anaerobic decomposition of dead biomass. Natural emissions of NH<sub>3<\/sub>\u00a0are about 1.2-billion tonnes per year. Sources of anthropogenic emissions include fossil-fuel combustion (4-million tonnes per year) and animal husbandry (0.2-million tonnes per year). The residence time of NH<sub>3<\/sub>\u00a0in the atmosphere is about seven days (the NH<sub>3<\/sub>\u00a0is eventually oxidized to nitrate).<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Nitrous oxide (N<sub>2<\/sub>O) is a colorless, non-toxic gas that produces a mild euphoria when inhaled. This gas is also known as \u201claughing gas\u201d and is used as a mild anesthetic in medicine, and sometimes as a recreational drug. Because N<sub>2<\/sub>O is a rather unreactive compound, it has a long residence time in the atmosphere of about four years. Most N<sub>2<\/sub>O emissions are associated with microbial denitrification in soil and water. These are equivalent to about 18-million tonnes per year, while industrial emissions are 12-million tonnes per year. Agricultural soil fertilized with nitrate can have high rates of N<sub>2<\/sub>O emission, and modern agricultural practices are thought to have increased global emissions by about 40% (Figure 20.4).<\/p>\r\n<img class=\"wp-image-746 aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/5337\/2021\/07\/05194436\/nitrous-oxide-emissions-by-sector.png\" alt=\"\" width=\"726\" height=\"440\" \/>\r\n\r\nFigure 20.4. Worldwide Nitrous Oxide Emissions by Sector. Nitrous oxide emissions are measured in tonnes of carbon dioxide equivalents (CO<sub>2<\/sub>e) based on a 100-year potential global warming value.\u00a0Source: visualization by\u00a0<a href=\"https:\/\/ourworldindata.org\/grapher\/nitrous-oxide-emissions-by-sector?country=~OWID_WRL\">OurWorldinData.org<\/a>\u00a0is licensed under <a href=\"https:\/\/creativecommons.org\/licenses\/by\/4.0\/deed.en_US\">CC BY 4.0<\/a>.\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Nitric oxide (NO) is a colorless and odorless gas, while nitrogen dioxide is reddish, pungent, and irritating to respiratory and eye membranes. Natural emissions of NO<sub>x<\/sub>\u00a0are about 430-million tonnes per year (expressed as NO; the same emissions expressed as NO<sub>2<\/sub>\u00a0are 658-million tonnes per year). The most important natural emissions of NO<sub>x<\/sub>\u00a0are due to bacterial denitrification of nitrate in soil, fixation of atmospheric nitrogen gas (N<sub>2<\/sub>) by lightning, and oxidation of biomass nitrogen during fires (see Chapter 5).<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Anthropogenic emissions of NO<sub>x<\/sub>, about 83-million tonnes per year (expressed as NO), result mostly from the combustion of fossil fuels, especially in automobiles and power plants. These emissions are mostly NO, which is secondarily oxidized to NO<sub>2<\/sub>\u00a0by reactions in the atmosphere. Ultimately, most atmospheric NO<sub>x<\/sub>\u00a0gases become oxidized to nitrate (NO<sub>3<\/sub><sup>\u2013<\/sup>), an ion that is important in the acidification of precipitation and ecosystems (Chapter 23).<\/p>\r\n\r\n<h2 class=\"import-Normal2\">Toxicity of Nitrogen Gases<\/h2>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">It is rare that concentrations of NH<sub>3<\/sub>\u00a0or NO<sub>x<\/sub>\u00a0gases are high enough to injure vegetation. The environmental damage associated with NO<sub>x<\/sub>\u00a0is focused on the photochemical reactions by which ozone, a much more toxic gas, is produced (see below), and also the acidification of precipitation and ecosystems.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Ambient concentrations of NH<sub>3<\/sub>\u00a0and NO<sub>x<\/sub>\u00a0are rarely high enough to bother humans. Guidelines for long-term exposures in an occupational setting are 25 ppm (34 mg\/m<sup>3<\/sup>) for NO and 5 ppm (10 mg\/m<sup>3<\/sup>) for NO<sub>2<\/sub>. Occupational guidelines for short-term exposures are 35 ppm (47 mg\/m<sup>3<\/sup>) and 5 ppm (10 mg\/m<sup>3<\/sup>), respectively. Intense occupational exposures to NO<sub>x<\/sub>\u00a0can cause impaired pulmonary function in humans.<\/p>\r\n\r\n<h1 class=\"import-Normal2\">Organic Gases and Vapors<\/h1>\r\n<h2 class=\"import-Normal2\">Emissions and Transformations<\/h2>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Hydrocarbons are a diverse group of chemicals whose molecular structures containing various combinations of hydrogen and carbon atoms. The simplest hydrocarbon is methane (CH<sub>4<\/sub>), a gas. Larger hydrocarbons with greater weight and more complex structure may occur as vapors, liquids, or solids. Other volatile organic compounds (VOCs) may contain oxygen, nitrogen, and other light elements in addition to carbon and hydrogen, and include alcohols, aldehydes, and phenols.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">The background concentration of methane in the atmosphere is about 1.7 ppm (1 ppm = 0.65 mg\/m<sup>3<\/sup>), while all other hydrocarbons and volatile organics together amount to less than 1 ppb. Most emissions of CH<sub>4<\/sub>\u00a0are natural and are associated with the fermentation of organic matter by microbes in anaerobic wetlands. Smaller amounts are out-gassed from deposits of fossil fuels, during wildfires, and from burping and flatulent ruminant animals (such as cows and sheep) and termites, which produce CH<sub>4<\/sub>\u00a0as they digest their plant foods. Of total global CH\u2084 emissions, 50-65 percent are emitted from human activities, including energy, industry, agriculture, and waste management activities (EPA, 2020b). In the U.S., the largest source of CH\u2084 emissions is the agriculture sector.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Atmospheric hydrocarbons other than CH<sub>4<\/sub>\u00a0are referred to as non-methane hydrocarbons. Natural emissions of these and many organics occur mainly as gases and vapors that evaporate from living vegetation, along with smaller quantities that out-gas from deposits of fossil fuels. The largest emissions from forests typically occur during hot, sunny days. Natural emissions of non-methane hydrocarbons are about 200-million tonnes per year, compared with anthropogenic emissions of 186-million tonnes per year. The most important anthropogenic sources are unburned fuel emitted from vehicles and aircraft, releases during fossil-fuel mining and refining, and evaporation of solvents.<\/p>\r\n\r\n<h2 class=\"import-Normal2\">Toxicity of Organic Gases and Vapors<\/h2>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Organic gases and vapors can be toxic, but atmospheric concentrations are rarely high enough to damage vegetation or animals. The environmental importance of these gases and vapors lies mainly in their role in the photochemical reactions that produce toxic ozone. In addition, CH<sub>4<\/sub> is an important greenhouse gas that affects global warming (Chapter 21). In some workplaces, however, relatively toxic organics such as benzene and formaldehyde may be important pollutants.<\/p>\r\n\r\n<h2 class=\"import-Normal2\">Ozone<\/h2>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">There are two different ozone-related environmental issues: (1) O<sub>3<\/sub>\u00a0in the stratosphere and (2) O<sub>3<\/sub>\u00a0in the troposphere (ground-level ozone). High concentrations of ozone are naturally present in the upper-atmospheric layer known as the stratosphere, which begins at about 8-17 km above the Earth\u2019s surface, depending on the latitude and season. Stratospheric O<sub>3<\/sub>\u00a0causes no damage and is not an air pollutant. Rather, by absorbing solar ultraviolet radiation, stratospheric\u00a0O<sub>3 <\/sub>helps to protect organisms on the surface of the planet from many damaging effects of exposure to this harmful part of the electromagnetic spectrum. In contrast, O<sub>3<\/sub> in the lower\u00a0atmosphere (the troposphere) is an important air pollutant that damages vegetation, materials, and human health. Ozone is removed from the atmosphere by interactions with other gases, organic vapors, and terrestrial and aquatic surfaces (including vegetation).<\/p>\r\n\r\n<h3 class=\"import-Normal2\">Ground-Level Ozone<\/h3>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Ground-level ozone (O<sub>3<\/sub>) is the most damaging of the so-called photochemical air pollutants. Less important are peroxyacetyl nitrate (PAN), hydrogen peroxide (H<sub>2<\/sub>O<sub>2<\/sub>), and other oxidant gases. Oxidizing smog is rich in O<sub>3<\/sub>\u00a0and the other oxidant gases. These chemicals are secondary pollutants, meaning they are not actually emitted to the atmosphere (as are primary pollutants such as SO<sub>2<\/sub>\u00a0and NO<sub>x<\/sub>). Instead, they are synthesized within the atmosphere by photochemical reactions (chemical reactions that require light, especially ultraviolet wavelengths; Figure 20.5). These proceed at faster rates and result in a buildup of oxidants if NO<sub>x<\/sub>\u00a0and hydrocarbons are present in high concentrations, a condition that is typically due to anthropogenic emissions.<\/p>\r\n<img class=\"size-full wp-image-724 aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/5337\/2021\/07\/05112603\/how-ozone-forms-diagram.png\" alt=\"\" width=\"650\" height=\"516\" \/>\r\n\r\nFigure 20.5. Ground Level Ozone Formation. Ground level ozone is not emitted directly into the atmosphere, but instead is synthesized by photochemical reactions. Source: used with permission from the <a href=\"https:\/\/www.pca.state.mn.us\/air\/ozone\">Minnesota Pollution Control Agency<\/a>.\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Some regions tend to develop a weak atmospheric inversion in the morning. Because an inversion is relatively stable and resists the in-mixing of cleaner air from above or beyond, this condition encourages the development of oxidizing smog during the morning and early afternoon. Later in the day, the inversion is typically broken up by stronger winds, and the air pollution is dispersed. Such inversions and their ozone-rich smog are common phenomena around the Los Angeles basin, Mexico City, Vancouver, and elsewhere.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">The concentrations of ground-level O<sub>3<\/sub>\u00a0vary greatly among different regions of North America. Average concentrations in the southwestern U.S. are relatively high, at about 100 ppb (1 ppb = 2 \u00b5g\/m<sup>3<\/sup>), and they generally range from 40\u201360 ppb in other regions of the U.S. and in southern Canada.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Canada, the U.S., and other countries have developed air quality standards for O<sub>3<\/sub>. These are intended to reflect concentrations that would prevent severe damage to agricultural and wild vegetation. For some time, the O<sub>3<\/sub>\u00a0standard in the U.S. was 80 ppb (160 \u00b5g\/m<sup>3<\/sup>) (for an average one-hour exposure), but in 1979 this was relaxed to 120 ppb (240 \u00b5g\/m<sup>3<\/sup>). The authorities made the change because the original standard of 80 ppb was frequently exceeded over large regions and so was essentially unenforceable. In fact, even the 120 ppb criterion is commonly exceeded in some regions, particularly in the southwestern U.S.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">The Los Angeles basin suffers especially intense photochemical air pollution. Concentrations of O<sub>3<\/sub>\u00a0can exceed 500 ppb (one-hour average), and they typically exceed 100 ppb for more than 15 days during the summer. Maximum O<sub>3<\/sub>\u00a0concentrations are lower in other cities of North America, typically reaching up to 150-250 ppb (one-hour average). These concentrations are well within the range at which O<sub>3<\/sub>\u00a0can cause acute injury to plants, which is why O<sub>3<\/sub>\u00a0is such an important air pollutant. The emissions of ozone precursors (NO<sub>x<\/sub>\u00a0and hydrocarbons) occur mainly in cities, but extensive ecological damage is caused when polluted air masses are transported to rural areas dominated by agricultural or natural vegetation.<\/p>\r\n\r\n<h3 class=\"import-Normal2\">Toxicity of Ozone<\/h3>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Humans and some animals are sensitive to O<sub>3<\/sub>, which can irritate and damage membranes of the eyes and respiratory system and cause a loss of lung functioning. The guideline for long-term exposure to O<sub>3 <\/sub>in an occupational setting is 100 ppb (196 \u00b5g\/m<sup>3<\/sup>), and it is 300 ppb (589 \u00b5g\/m<sup>3<\/sup>) for short-term exposures. However, sensitive people can be affected by O<sub>3<\/sub>-related symptoms at lower concentrations. Exposure to O<sub>3<\/sub>\u00a0can result in asthmatic attacks and can exacerbate bronchitis and emphysema.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Ozone causes important damage to wild and agricultural plants over widespread areas. Foliar injuries are often distinctive to O<sub>3<\/sub>, and they diminish the photosynthetic capacity of plants and thereby reduce their productivity. Acute injuries are caused to most species by two- to four-hour exposures to 200-300 ppb O<sub>3<\/sub>, while long-term exposures to only 40-100 ppb may cause hidden injuries (and reduced yield). However, many species are more sensitive and suffer acute and hidden injuries at lower concentrations. Some varieties of tobacco (<em>Nicotiana tobacco<\/em>), for example, can suffer acute foliar injuries from a two- to three-hour exposure to only 50-60 ppb, and spinach (<em>Spinacea oleracea<\/em>), from one to two hours at 60-80 ppb. Sensitive species of conifer trees may suffer acute injuries from exposures to 80 ppb O<sub>3<\/sub>\u00a0over 12 hours.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Researchers have grown agricultural plants in experimental chambers that received ambient air, or air filtered through charcoal, which removes any O<sub>3<\/sub>. These studies have been useful in defining the extent of damage caused to agricultural crops by exposure to ambient O<sub>3<\/sub>. One series of field experiments demonstrated that crop yields were reduced in all regions of the U.S. The worst damage occurred in the southwest, where sunny conditions and large emissions of NO<sub>x<\/sub>\u00a0and hydrocarbons result in especially high O<sub>3<\/sub>\u00a0concentrations. That study estimated that crop damage due to O<sub>3<\/sub>\u00a0was equivalent to 2\u20134% of the total agricultural yield in the U.S., with economic losses equivalent to more than $5 billion per year. Because O<sub>3<\/sub>-related damage to vegetation occurs over extensive areas of North America, it is by far the most important air pollutant in agriculture. Ozone is probably also the leading air pollutant causing damage to forests and other natural ecosystems.<\/p>\r\n\r\n<h3 class=\"import-Normal2\">Stratospheric Ozone<\/h3>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">In contrast to ground-level ozone, ozone in the stratosphere protects life on Earth from the damaging effects of solar ultraviolet (UV) radiation. This is the reason why the fact that stratospheric ozone is being destroyed by anthropogenic emissions of certain gases is cause for alarm.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Ozone is produced in the stratosphere by natural photochemical reactions. They involve the absorption of solar UV radiation by oxygen molecules (O<sub>2<\/sub>), which creates highly reactive oxygen atoms (O) that join with other O<sub>2<\/sub>\u00a0molecules to form O<sub>3<\/sub>\u00a0(see In Detail 20.2). These reactions proceed relatively quickly in the stratosphere because high-energy UV radiation is abundant there. As a result, O<sub>3<\/sub>\u00a0concentrations are typically 200-300 ppb in the stratosphere, about 10 times greater than in the ambient troposphere.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Stratospheric O<sub>3<\/sub>\u00a0provides a critical environmental service. It efficiently absorbs most of the incoming high-energy UV radiation, which can be extremely damaging to organisms. In particular, DNA is a strong absorber of UV and can be damaged by this radiation. This can increase the risk of developing skin cancers, including melanoma, an often-fatal malignancy. Other health risks from UV exposure include the development of cataracts in the eyes and suppression of the immune system. UV radiation also damages plants, in part because chlorophyll (the key photosynthetic pigment) is degraded by UV absorption, which may lead to decreases in productivity. The waxy covering of the cuticle of foliage is also damaged by UV radiation.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Stratospheric O<sub>3<\/sub>\u00a0can be destroyed by various processes, including reactions with the trace gases NO<sub>x <\/sub>and N<sub>2<\/sub>O and with reactive ions of bromine, chlorine, and fluorine. Because of anthropogenic emissions, the concentrations of some of these O<sub>3<\/sub>-consuming chemicals have been increasing in the stratosphere, leading to concerns about the depletion of stratospheric O<sub>3<\/sub>. It is widely believed that emissions of chlorofluorocarbons (CFCs), particularly the industrial gases known as freons, have been especially important in this regard. Because CFCs are extremely unreactive in the troposphere, they eventually migrate up to the stratosphere, where they are bombarded with UV radiation and slowly degrade (photodissociate) to release free chlorine. The chlorine efficiently reacts with and destroys O<sub>3<\/sub>.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">The O<sub>3<\/sub>-destroying reactions proceed most effectively under extremely cold and stagnant conditions in the stratosphere, such as those occurring above polar latitudes at the end of the Antarctic and Arctic winters. These polar-focused O<sub>3<\/sub>\u00a0depletions result in the development of so-called ozone holes during the early springtime. These phenomena have been observed regularly since the early 1980s. The O<sub>3<\/sub>\u00a0holes over Antarctica are particularly extensive and typically involve decreases of the O<sub>3<\/sub>\u00a0concentration of 30-50% during the spring. Smaller depletions of O<sub>3<\/sub>\u00a0occur above the Arctic, including northern Canada. The affected areas in the Northern Hemisphere are much smaller than their counterparts in Antarctica.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">The sizes of the ozone holes in Antarctica vary from year to year, but there has been a trend of strong increases since 1980, when the first accurate data began to be collected (Figure 20.6). Although the seasonal losses of O<sub>3<\/sub>\u00a0only take place over polar regions, lower latitudes are also affected when the O<sub>3<\/sub>-depleted air becomes dispersed during the breakup of the holes. This temporarily reduces the stratospheric O<sub>3<\/sub>\u00a0concentrations throughout the hemisphere, though not nearly to the same degree as occurs in the holes themselves.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\"><img class=\" wp-image-719 aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/5337\/2021\/07\/05104131\/Picture11.png\" alt=\"\" width=\"746\" height=\"473\" \/><\/p>\r\n<p class=\"import-Normal0\" style=\"margin-right: 24pt;\">Figure 20.6. Antarctic Ozone Hole Area. Changes in the maximum and minimum annual size of the ozone \u201chole\u201d over Antarctica.\u00a0Source: visualization by\u00a0<a href=\"https:\/\/ourworldindata.org\/grapher\/antarctic-ozone-hole-area?country=~OWID_WRL\">OurWorldinData.org<\/a>, data from <a href=\"https:\/\/ozonewatch.gsfc.nasa.gov\/meteorology\/annual_data.html\">NASA Ozone Watch,<\/a>\u00a0is licensed under <a href=\"https:\/\/creativecommons.org\/licenses\/by\/4.0\/deed.en_US\">CC BY 4.0<\/a>.<\/p>\r\n\r\n<div class=\"textbox shaded\">\r\n<h3 class=\"import-Normal2\" style=\"margin-right: 24pt;\">Environmental Issues 20.1. The Montreal Protocol \u2013 A Success of Regulatory Action<\/h3>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">Soon after it became widely recognized that emissions of chlorofluorocarbons (CFCs) and other chemicals were degrading the stratospheric ozone layer, world governments took action to deal with the problem. In 1987, the United Nations Environment Program (UNEP) organized an international meeting in Montreal, where intense negotiations led to a treaty called The Montreal Protocol on Substances That Deplete the Ozone Layer. The Montreal Protocol is an international agreement that committed all parties (signatory nations) to a schedule for phasing out the production and use of CFCs and other substances known to be harmful to the ozone layer. The treaty required the signatory nations to freeze their production and consumption of CFCs at 1986 levels by 1989, and to further reduce them to 50% of 1986 levels by 1998.<\/p>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">Initially, the governments of many countries were reluctant to ratify the protocol because they did not want to impose strict controls on the manufacturing and use of chemicals they thought were necessary for the functioning of their economies. This was particularly true for nations of the European Community, the former Soviet Union, and Japan. However, Canada, the U.S., Norway, and Sweden strongly advocated control measures, and they managed to convince the reluctant nations to phase out their use of ozone-depleting substances. The Montreal Protocol came into force on January 1, 1989, and was then ratified by 40 countries, which accounted for about 82% of the global use of CFCs.<\/p>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">The Montreal Protocol was subsequently improved by a series of amendments to eliminate the use of halons by 1994; of CFCs, methyl chloroform, HBFCs (hydrobromofluorocarbons), and carbon tetrachloride by 1996; of methyl bromide by 2010; and of HCFCs (hydrochlorofluorocarbons) by 2030. The amended protocol was ratified by many additional countries, including China and India, huge nations that had not participated in the initial negotiations. By 2009, 197 countries were parties to the Montreal Protocol, making it the first such treaty to achieve universal approval. The amendments also established the Montreal Protocol Multilateral Fund to provide financial support to help developing nations become rapidly less dependent on ozone-depleting chemicals.<\/p>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">The Montreal Protocol and its subsequent amendments have been called a \u201csuccess story\u201d in the regulatory control of pollution. Many developed countries accelerated and surpassed their original reduction targets, and less-developed countries have committed to not allowing the use of ozone-depleting substances in their economies. This success was achieved because of the following:<\/p>\r\n\r\n<ol>\r\n \t<li class=\"import-Normal2\" style=\"text-align: justify;\">There was international recognition of a clear threat to the global environment<\/li>\r\n \t<li class=\"import-Normal2\" style=\"text-align: justify;\">The threat was associated with particular substances that could be easily controlled, as they were manufactured in only a few places and were used for relatively discrete purposes<\/li>\r\n \t<li class=\"import-Normal2\" style=\"text-align: justify;\">Economically acceptable substitutes were quickly developed to replace the uses of ozone-depleting substances<\/li>\r\n<\/ol>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">In summary, rigorous information, effective international and national institutions, a spirit of cooperation, effective leadership by inspired leaders, and the availability of alternative technologies combined to bridge political differences in favor of the pursuit of a shared environmental interest. This is why the Montreal Protocol and its implementation are a success story of environmental regulatory action.<\/p>\r\n\r\n<\/div>\r\n<h1 class=\"import-Normal2\">Air Pollution and Health<\/h1>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">An extraordinary case of a natural emission of gas causing human deaths involved the release of a large volume of CO<sub>2<\/sub>\u00a0from a lake in Cameroon, West Africa. Lake Nyos is a 200-m-deep volcanic lake in which the deep waters are naturally supersaturated with CO<sub>2<\/sub>, similar to bottled soda water. One night in 1986, a large amount of sediment apparently slumped into the steep-sided lake, causing some of its bottom water to churn to the surface. The water de-gassed its CO<sub>2<\/sub>\u00a0content as a dense air mass, which then flowed into low areas in the surrounding landscape. The CO<sub>2<\/sub>-rich air asphyxiated about 1,700 sleeping people and 3,500 livestock as far as 25 km from the lake, plus uncounted wild animals. Atmospheric CO<sub>2<\/sub>\u00a0is capable of causing severe toxicity at concentrations greater than 8-10%; its \u201cnormal\u201d level is about 0.04%. Plants are much less vulnerable to CO<sub>2<\/sub>\u00a0toxicity, so no vegetation was damaged by this rare and astonishing natural event.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Anthropogenic emissions of other gaseous pollutants have sometimes caused increases in human mortality and diseases. Some people, especially those with chronic respiratory or heart diseases, are especially vulnerable to the effects of air pollution. Exposures of people to toxic gases can occur within several contexts, including the following.<\/p>\r\n\r\n<ul>\r\n \t<li class=\"import-Normal2\">The ambient environment: The urban atmosphere typically contains relatively high concentrations of potentially toxic chemicals. This is true in general, but air quality is especially bad during smog events, often caused by poor dispersion during an atmospheric inversion (Image 20.1). Consequently, city people living their normal lives are routinely exposed to higher concentrations of air pollutants than those living in cleaner, rural environments.<\/li>\r\n \t<li class=\"import-Normal2\">The working environment: Many people are exposed to high concentrations of pollutants as a consequence of their occupation. Of course, the specific exposures depend on the job \u2013 workers in metal smelters may be exposed to sulfur dioxide and metallic particulates, auto mechanics may be affected by exhaust fumes containing carbon monoxide and hydrocarbons, and laboratory workers may inhale various organic solvents.<\/li>\r\n \t<li class=\"import-Normal2\">The indoor environment: Buildings are often contaminated by gases and fumes. For example, space heaters, furnaces, and fireplaces burning wood, kerosene, or fuel oil may emit carbon monoxide into the indoor environment. All high-temperature combustions emit nitric oxide, and many synthetic materials and fabrics vent formaldehyde and other organic vapors. These chemicals can accumulate if indoor air is not exchanged frequently with cleaner, outdoor air.<\/li>\r\n \t<li class=\"import-Normal2\">Tobacco smoke: The smoking of tobacco is a leading source of easily avoidable air pollution. Smoking is also the most important cause of preventable diseases, especially lung cancer and heart disease (see Chapter 19). People inhale a great variety of toxic gases and fumes when they smoke tobacco (and also marijuana). In addition, non-smokers are indirectly exposed to lower concentrations of those chemicals because of the lingering residues of \u201csecond-hand smoke\u201d that may occur in indoor atmospheres.<\/li>\r\n<\/ul>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\"><img class=\"aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/5337\/2021\/07\/02104259\/image6.jpeg\" alt=\"image\" width=\"770\" height=\"333\" \/><\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Image 20.1. Smog in Denver, Colorado. Smog is becoming a growing problem in the western United States due to increased pollution from Asia. Source: National Renewable Energy Laboratory via <a href=\"https:\/\/research.noaa.gov\/News\/Scientist-Profile\/ArtMID\/536\/ArticleID\/226\/Rural-West-sees-more-smog-now-scientists-may-know-why\">NOAA<\/a>.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">All of these exposures to air pollutants have important implications for human health. However, the pollution of the ambient urban environment is the focus of the following paragraphs.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Since the beginning of the Industrial Revolution in Western Europe in the mid-18th century, people living in cities and working in certain types of factories have been exposed to high concentrations of air pollutants. Especially important have been sulfur dioxide, soot, and other emissions associated with the combustion of coal and other fossil fuels. The most severe exposures to pollutants in urban environments typically occurred during prolonged atmospheric inversions, which prevent the dispersion of emissions and result in smogs rich in SO<sub>2<\/sub>\u00a0and particulates.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Coal has long been used in many places to heat homes and other buildings. The associated emissions have been regarded as a problem in cities and towns in Europe since at least 1500. With the beginning of the Industrial Revolution, which initially used coal as its principal energy source, air pollution worsened markedly. The first convincing link between air pollution and a substantial increase in the death rate of an exposed human population was made in 1909, in relation to a noxious smog during an inversion in Glasgow, Scotland, when about one-thousand deaths may have been caused.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">The most infamous \u201ckiller smog\u201d in North America occurred in 1948 in Donora, Pennsylvania. An inversion and fog persisted in the Donora Valley for four days, but emissions from several factories continued, resulting in a build-up of high concentrations of SO<sub>2<\/sub>\u00a0and particulates in the atmosphere. The smog resulted in increased mortality in the local population (20 deaths in a population of only 14 100). An additional 43% of the population became ill, 10% severely so. The most common symptoms were irritation of the eyes and respiratory tract, sometimes accompanied by coughing, headache, and vomiting.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">The world\u2019s most notorious killer smog afflicted London, England, in 1952, when an extensive inversion and fog stabilized over southern England. In London, emissions of pollutants, mostly from coal combustion, transformed the natural \u201cwhite fog\u201d into a venomous \u201cblack fog.\u201d Visibility was terrible \u2013 people lost their way while walking or driving, even falling off wharves into the Thames River, and airplanes became lost while trying to taxi at the airport. The smog lasted for four days, but it was followed by another 14 days with a higher-than-usual death rate. Overall, about 3,900 deaths were attributed to this episode of noxious pollution. Most of the affected people were elderly or very young, or had pre-existing respiratory or heart diseases.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Until the early 1960s, severe episodes of urban air pollution were common in the cities of North America and Western Europe. Most of the smogs were caused by the widespread burning of coal in fireplaces and furnaces in homes, electrical utilities, and factories. The poor-quality urban air affected the health of people and animals and also damaged vegetation. In many cities, only certain kinds of plants that can tolerate air pollution could grow. Examples of pollution-tolerant trees that are commonly grown in urban America include black locust (<em>Robinia pseudoacacia<\/em>), honey locust (<em>Gleditsia triacanthos<\/em>), salt cedar (<em>Tamarix<\/em>), linden (<em>Tilia europaea<\/em>), tree-of-heaven (<em>Ailanthus altissima<\/em>), and ginkgo (<em>Ginkgo biloba<\/em>) (Heggestad et al., 1972).<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">To deal with the problems of this kind of smog, governments brought in legislation that has required large reductions in the emissions of air pollutants, particularly in cities. In Canada, for example, the enactment of various federal, provincial, and municipal laws related to air emissions has substantially improved urban air quality. Air quality has been similarly improved under legislation enacted in the U.S., Britain, and other wealthier countries since the 1960s.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Of course, the killer smogs were particularly severe events of air pollution. More typically, the urban atmosphere is contaminated by much smaller concentrations of SO<sub>2<\/sub>, NO<sub>x<\/sub>, O<sub>3<\/sub>, volatile organic compounds, and particulates. Many studies have investigated the effects of chronic exposures to those lower exposures to air contaminants on human health. The results of some studies suggest that modern urban air quality is sufficiently degraded to cause chronic damage to human health, especially by increasing the incidences of lung disease, asthma, and eye irritation. However, other studies have not found this to be the case. In any event, effective actions have been taken in the U.S. and other relatively wealthy nations. Visibly threatening, even lethal, episodes of air pollution like those described above no longer occur in those countries, although they could return if control standards were relaxed.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Unfortunately, in the cities of countries with rapidly growing economies, such as Brazil, China, India, Indonesia, and Mexico, poorly regulated industrial and urban growth is resulting in awful declines in air quality. Although not yet well studied in terms of human diseases, these appear to be modern tragedies of urban air pollution.<\/p>\r\n\r\n<div class=\"textbox shaded\">\r\n<h3 class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">American Focus 20.1. Smog in American Cities<\/h3>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">Smog is a serious problem in many cities and also in some rural areas because of LRTAP from urban areas. Smog is typically characterized as a noxious mixture of pollutants visible as a brownish-yellow or greyish-white haze. The key components are the following:<\/p>\r\n\r\n<ul>\r\n \t<li class=\"import-Normal2\" style=\"text-align: justify;\">O<sub>3<\/sub>\u00a0gas, along with SO<sub>2<\/sub>\u00a0and NO<sub>x<\/sub><\/li>\r\n \t<li class=\"import-Normal2\" style=\"text-align: justify;\">Organic vapors<\/li>\r\n \t<li class=\"import-Normal2\" style=\"text-align: justify;\">Fine particulates (&lt; 10 \u00b5m diameter), including acidic droplets of H<sub>2<\/sub>SO<sub>4<\/sub>\u00a0and HNO<sub>3<\/sub>, particulates of NH<sub>4<\/sub>NO<sub>3<\/sub>\u00a0and (NH<sub>4<\/sub>)<sub>2<\/sub>SO<sub>4<\/sub>, and organics from diesel exhaust and other combustion sources<\/li>\r\n<\/ul>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">Smog is widely regarded as a major cause of environmental damage, because it causes toxicity to vegetation and deteriorates building surfaces and other materials. Smog is also known to cause diseases and discomfort in many people. The elderly and children are especially vulnerable, as are people with existing heart or lung diseases (particularly asthma, bronchitis, and emphysema). Even healthy adults, however, may be affected on days with severe smog. The key causes of toxicity are ozone, other gases, and the finest particulates (&lt;2.5 \u00b5m), which can penetrate into the smallest lung cavities (known as alveoli) and cause irritation and other problems.<\/p>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">However, the data showing an association of smog and human diseases are epidemiological \u2013 that is, they involve discovering statistical relationships among the concentrations of atmospheric pollutants and the prevalence of certain maladies. In the U.S. for example, there is a predictable increase in hospital admissions of people suffering from respiratory ailments at times when concentrations of ozone and\/or sulfate particulates are high. Although it is rarely possible to link a specific disease in a particular person to an exposure to air pollution, it is estimated with no change in regulatory controls, ozone and particulate pollution will lead to 1,000 to 4,300 additional premature deaths each year by 2050 (CDC, 2020).<\/p>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">Because of the importance of smog as a stressor of urban Americans, state governments have initiated programs to monitor air pollutants and predict their concentrations so that \u201csmog alerts\u201d can be issued to the public. For example, New York State Department of Environmental Conservation and the State Department of Health issued an advisory for ozone in the Long Island region in 2019 with recommendations on ways to reduce ozone pollution such as using mass transit instead of individual cars and increasing use of fans to circulate air (DEC, 2019). These advisories encourage people to use different energy-saving and pollution-reducing steps, and provide warnings for specific times of the day when the pollutant threat will be the greatest.<\/p>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">In 2020, Los Angeles experienced some of its worst air quality and smog events (Figure 20.7). Historically, this city has suffered from poor air quality and, still today, it remains one of the most polluted regions in the U.S. Throughout the year, Los Angeles averaged an air quality index rating of \u201cModerate,\u201d however on September 6, 2020, the air quality index ranged from \u201cUnhealthy\u201d to \u201cVery Unhealthy\u201d (EPA 2020). This poor air quality, specifically the particulate pollution levels, causes over 9,000 deaths each year in California (Frias, 2016). Los Angeles still has much work to do to meet the U.S. EPA\u2019s national air quality standards and the California Ambient Air Quality Standards.<\/p>\r\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\"><img class=\"aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/5337\/2021\/07\/02104301\/image7.png\" alt=\"image\" width=\"659.066666666667px\" height=\"366.733333333333px\" \/><\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 24pt;\">Figure 20.7. Archived Map of Air Quality Index Records. This map details the record for the U.S. Air Quality Index for September 6, 2020. This date was the worst day of air quality for Los Angeles in 2020. On this date, Los Angeles air quality ranged from \u201cUnhealthy\u201d to \u201cVery Unhealthy.\u201d Source: <a href=\"https:\/\/gispub.epa.gov\/airnow\/\">EPA<\/a>.<\/p>\r\n\r\n<\/div>\r\n<h1 class=\"import-Normal2\">Conclusions<\/h1>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Gaseous air pollutants, such as sulfur dioxide and nitric oxide, are emitted from a variety of sources, which range from large power plants and smelters to individual automobiles and home furnaces. In contrast, secondary pollutants such as ozone are not emitted but are formed in the atmosphere by photochemical reactions involving sunlight and emitted oxides of nitrogen and hydrocarbons. If their concentrations are high enough, gaseous pollutants (often in combination with particulates) can be a risk to human health, and they may cause severe ecological damage. Because these risks are now well known, many governments have taken steps to reduce the emissions of the most important air pollutants. This is particularly the case for relatively developed countries, such as the U.S. Although the emissions of air pollutants in wealthy countries remain large, they are generally stabilizing or even decreasing. However, in rapidly growing economies, such as China and India, hasty and poorly controlled industrialization is resulting in rapidly worsening air pollution.<\/p>\r\n\r\n<h1 class=\"import-Normal2\">Questions for Review<\/h1>\r\n<ol>\r\n \t<li class=\"import-Normal2\">Compare the natural and anthropogenic emissions of sulfur and nitrogen compounds. Why do the sources of emission vary between regions and countries?<\/li>\r\n \t<li class=\"import-Normal2\">Why are high concentrations of ozone in the lower atmosphere considered an environmental problem? Why does this differ from the stratosphere, where too little ozone is a problem?<\/li>\r\n \t<li class=\"import-Normal2\">Explain the differences between primary and secondary air pollutants? Give examples of each.<\/li>\r\n \t<li class=\"import-Normal2\">Why has air pollution decreased so much in the eastern U.S., and what have been the ecological responses to this environmental improvement?<\/li>\r\n<\/ol>\r\n<h1 class=\"import-Normal2\">Questions for Discussion<\/h1>\r\n<ol>\r\n \t<li class=\"import-Normal2\">Existing clean-air technologies could be used to greatly reduce the emissions of air pollutants everywhere. Considering the damage that pollutants cause to human health, ecosystems, and other values, why are these technologies not being used more extensively? Consider factors associated with economics, politics, scientific uncertainty about pollution damage, and the benefits of having cleaner air. Contrast the lack of action with the successes achieved in controlling the emissions of ozone-depleting substances through the Montreal Protocol.<\/li>\r\n \t<li class=\"import-Normal2\">Epidemiological (statistical) research suggests that human health may be affected by ambient levels of air pollutants in urban areas, particularly through increased incidences of respiratory diseases, such as asthma. However, the statistical data are rather weak, and only a relatively small proportion of the urban population appears to be affected. What are some issues that decision makers must consider when deliberating about additional controls on the release of air pollutants in urban areas?<\/li>\r\n<\/ol>\r\n<h1 class=\"import-Normal2\">Exploring Issues<\/h1>\r\n<ol>\r\n \t<li class=\"import-Normal2\">You have been asked to assess the potential ecological effects of building a new metal smelter in a region that is now wilderness. The smelter will emit sulfur dioxide to the atmosphere. Based on what you know about pollution damage, what would be the most important considerations to incorporate into the environmental impact assessment? Focus on the potential effects on terrestrial and aquatic ecosystems.<\/li>\r\n<\/ol>\r\n<h1 class=\"import-Normal2\">References Cited and Further Reading<\/h1>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Anderson, S.O. and K.M. Sarma. 2005. Protecting the Ozone Layer: The United Nations History. Earthscan Publications, London, UK.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Ayres, J. and R.L. Maynard. 2006. Air Pollution and Health. World Scientific Publishing Company.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Barker, J.R. and D.T. Tingey. 1992. Air Pollution Effects on Biodiversity. Van Nostrand Reinhold, New York, NY.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Brimblecombe, P. 1996. Air Composition and Chemistry. 2nd ed. Cambridge University Press, Cambridge, UK.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Brimblecombe, P. 2005. The Effects of Air Pollution on the Built Environment. Imperial College Press, London, UK.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Centers for Disease Control and Prevention. 2020. Air Pollution. Climate and Health, Centers for Disease Control and Prevention. <a class=\"rId23\">https:\/\/www.cdc.gov\/climateandhealth\/effects\/air_pollution.htm<\/a>. Accessed June 14, 2021.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Frias, L. 2016. County of Los Angeles Public Health, Environmental Health. <a class=\"rId24\">http:\/\/publichealth.lacounty.gov\/eh\/tea\/toxicepi\/criteriaairpollutants.htm<\/a>. Accessed June 14, 2021.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Department of Environmental Conservation (DEC) 2019. Air Quality Health Advisory Issued for Long Island. Department of Environmental Conservation, New York. <a class=\"rId25\">https:\/\/www.dec.ny.gov\/press\/117675.html<\/a>. Accessed June 14, 2021.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Environmental Protection Agency (EPA). 2019. Our Nation\u2019s Air. <a class=\"rId26\" href=\"#home\"><span class=\"import-Hyperlink\">https:\/\/gispub.epa.gov\/air\/trendsreport\/2020\/#home<\/span><\/a>. Accessed June 14, 2021.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Environmental Protection Agency (EPA). 2020a. NAAQS Table. <a class=\"rId27\">https:\/\/www.epa.gov\/criteria-air-pollutants\/naaqs-table<\/a>. Accessed June 14, 2021.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Environmental Protection Agency (EPA). 2020b. Overview of Greenhouse Gases, Methane Emissions. <a class=\"rId28\" href=\"#methane\">https:\/\/www.epa.gov\/ghgemissions\/overview-greenhouse-gases#methane<\/a>. Accessed June 14, 2021.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Environmental Protection Agency (EPA). 2020. Interactive Map of Air Quality. AirNow, U.S. Air Quality Index. <a class=\"rId29\">https:\/\/gispub.epa.gov\/airnow\/<\/a>. Accessed June 14, 2021.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Freedman, B. 1995. Environmental Ecology. 2nd ed. Academic Press, San Diego, CA.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Heggestad, H.E., Santamour, F.S., and Bernstein, L. 1972. Plants that will withstand pollution and reduce it. American Society of Landscape Architects Foundation, United States Department of Agriculture. 16-22 <a class=\"rId30\">https:\/\/naldc.nal.usda.gov\/catalog\/IND79000653<\/a>.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Hemond, H.F. and E.J. Fechner. 2014. Chemical Fate and Transport in the Environment. 3rd ed. Academic Press, San Diego, CA.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Hester, R.E. and R.M. Harrison. 1998. Air Pollution and Health. Royal Society of Chemistry, Cambridge, UK.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Holgate, S.T., J.M. Samet, R.L. Maynard, and H.S. Koren (eds.). 1999. Air Pollution and Health. Academic Press, San Diego, CA.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Parson. E. 2003. Protecting the Ozone Layer: Science and Strategy. Oxford University Press, Oxford, UK.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Pepper, I.L., C.P. Gerba, and M.L. Brusseau (eds.). 2006. Pollution Science, 2nd ed. Academic Press, San Diego, CA.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Roberts, T.M. 1984. Effects of air pollutants in agriculture and forestry. Atmospheric Environment, 18: 629-652.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Seinfeld, J.H. and S.H. Pandis. 2006. Atmospheric Chemistry and Physics: From Air Pollution to Climate Change, 2nd ed. Wiley-Interscience, New York, NY.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Shriner, D.S. 1990. Responses of vegetation to atmospheric deposition and air pollution. In Acidic Deposition: State of Science and Technology. Vol. III. Terrestrial, Materials, Health, and Visibility Effects. Superintendent of Documents, U.S. Government Printing Office, Washington, DC.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Thostenson, A., J.W. Enz, and V. Hofman. 2019. \u201cAir Temperature Inversions Causes, Characteristics, and Potential Effects on Pesticide Spray Drifts.\u201d North Dakota State University. <a class=\"rId31\"><span class=\"import-Hyperlink\">https:\/\/www.ag.ndsu.edu\/publications\/crops\/air-temperature-inversions-causes-characteristics-and-potential-effects-on-pesticide-spray-drift<\/span><\/a>. Accessed June 14, 2021.<\/p>\r\nU.S. Energy Information Association. 2017. Sulfur Dioxide emissions from U.S. power plants have fallen faster than coal generation. February 3, 2017. <a class=\"rId33\"><span class=\"import-Hyperlink\">https:\/\/www.eia.gov\/todayinenergy\/detail.php?id=29812<\/span><\/a>. Accessed June 14, 2021.\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">U.S. Energy Information Association. 2020. International Energy Statistics, China. September 30, 2020. <a class=\"rId32\">https:\/\/www.eia.gov\/international\/analysis\/country\/CHN<\/a>. Accessed June 14, 2021.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Vallero, D. 2014. Fundamentals of Air Pollution, 5th ed. Academic Press, San Diego. Wark, K. Jr., C.F. Warner, and W.T. Davis. 1998. Air Pollution: Its Origin and Control. 3rd ed. Addison-Wesley, Menlo Park, CA.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Watson, W.Y. and D.H. Richardson. 1972. Appreciating the potential of a devastated land. Forestry Chronicle, 48: 312-315.<\/p>\r\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Wise, W. 2001. Killer Smog: The World\u2019s Worst Air Pollution Disaster. Author\u2019s Guild, New York, NY.<\/p>\r\n\r\n<\/div>","rendered":"<div class=\"__UNKNOWN__\">\n<h2 class=\"import-Normal2\">Key Concepts<\/h2>\n<ol>\n<li class=\"import-Normal2\">After completing this chapter, you will be able to<\/li>\n<li class=\"import-Normal2\">Outline the major sources of emission of air pollutants associated with sulfur, nitrogen, and hydrocarbons.<\/li>\n<li class=\"import-Normal2\">Explain the difference between primary and secondary pollutants.<\/li>\n<li class=\"import-Normal2\">Contrast the environmental problems associated with stratospheric and tropospheric ozone.<\/li>\n<li class=\"import-Normal2\">Examine the importance of air pollutants to ecosystems and to human health.<\/li>\n<li class=\"import-Normal2\">Describe the patterns of pollution and ecological damage near point sources of air pollution.<\/li>\n<\/ol>\n<h1 class=\"import-Normal2\">Introduction<\/h1>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Gaseous air pollutants are emitted from various natural sources, such as volcanoes and forest fires. However, anthropogenic emissions of some gases may be greater than the natural ones, and are increasing because of population growth and industrialization.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">In ancient times, there was not much pollution. Nevertheless, even then local problems would have occurred. For instance, smoky wood fires used for cooking and warmth would likely have caused poor-quality air to occur inside of badly ventilated dwellings. Hunting cultures often used fire to drive game animals and improve local forage, and those burns would have resulted in large emissions of particulate carbon (soot), carbon dioxide, and other gases that would have temporarily impaired air quality. Overall, however, these effects were relatively minor.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Of course, as people became more numerous and industrialized, air pollution increasingly developed into a much bigger problem. When the Industrial Revolution began (around 1750), coal quickly became the major fuel used to generate heat and energy for machines, and that resulted in increasingly worse air pollution. The widespread use of coal led to severe pollution by sulfur dioxide (SO<sub>2<\/sub>) and soot in the industrial towns and cities of Europe and the Americas. Since 1900, burgeoning industrialization and new technologies such as power plants and automobiles have further increased the emissions of pollutants.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Air pollution can be especially severe in situations when the lower atmosphere is stable and calm. These conditions often occur beneath an atmospheric phenomenon called an inversion, in which a layer of cool air is trapped beneath a higher layer of warmer air (the more usual pattern is for temperature to cool with increasing altitude). An atmospheric inversion is a relatively stable condition that prevents polluted ground-level air from mixing with cleaner air from higher altitudes (see In Detail 20.1). If an atmospheric inversion is accompanied by fog, the pollution is known as smog (a word derived from \u201csmoke\u201d and \u201cfog\u201d). As recently as the 1950s, occasional so-called \u201ckiller smogs\u201d rich in SO<sub>2<\/sub>\u00a0and soot caused the deaths of thousands of urban people, and many more suffered from respiratory distress (pollution rich in SO<sub>2<\/sub>\u00a0is also called reducing smog). The most famous killer smogs occurred in London, Glasgow, some other industrial centers of Europe, and near Pittsburgh in the U.S.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Once scientists recognized the severe damage that was being caused by air pollution, governments began to pass laws to decrease the emissions. Pollution control became particularly vigorous after medical researchers discovered clear evidence of links between air quality and human diseases and deaths. Particular attention was paid to air pollution in urban environments, where the killer smogs were most frequent. Governments typically responded with important control actions, such as the following:<\/p>\n<ul>\n<li class=\"import-Normal2\">Switching from coal, which is a relatively \u201cdirty\u201d fossil fuel, to \u201ccleaner\u201d ones such as natural gas or oil, or to alternative energy technologies such as nuclear power and hydroelectricity<\/li>\n<li class=\"import-Normal2\">Constructing tall smokestacks to spread emissions over a much wider area so that ground-level exposures become less common and less intense \u2013 this tactic is the \u201cdilution solution to pollution\u201d<\/li>\n<li class=\"import-Normal2\">Centralizing energy production in large power plants to replace much of the relatively dirty and inefficient burning of coal in home fireplaces and furnaces, thereby permitting better control of emissions<\/li>\n<li class=\"import-Normal2\">Treating waste gases to remove some of their pollutant content, thereby reducing emissions to the atmosphere<\/li>\n<\/ul>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Because of these helpful regulatory actions, the importance of reducing smogs became much less in many countries. However, so-called oxidizing smog has become more important causes of damage in many regions. Oxidizing smog develops in the atmosphere through complex photochemical reactions in which hydrocarbons and nitrogen oxides are transformed into ozone (O<sub>3<\/sub>) and other gases. Ozone and other oxidizing gases harm vegetation and irritate the respiratory system and eyes of people. Oxidizing smog develops under sunny conditions if hydrocarbons and nitrogen oxides are present from automobile and industrial emissions, and especially if the presence of an atmospheric inversion reduces dispersion of the polluted air mass.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">In this chapter, we examine the most important gaseous pollutants. Their sources of emission, chemical transformations, and toxicity are described, and case studies are used to demonstrate the ecological damages that may be caused.<\/p>\n<div class=\"textbox shaded\">\n<h3 class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">In Detail 20.1. \u00a0Air Temperature Inversions<\/h3>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">Normally, the temperature of the atmosphere decreases with increasing altitude. Under certain conditions, however, a layer of relatively cool air may become trapped under a layer of warmer air, a phenomenon known as an atmospheric inversion (or temperature inversion; Figure 20.1).<\/p>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\"><img decoding=\"async\" class=\"aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/5337\/2021\/07\/02104249\/image1.png\" alt=\"image\" width=\"624.533333333333px\" height=\"456.266666666667px\" \/><\/p>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">Figure 20.1. The figure above shows different characteristics of atmospheric inversion including air temperature, density stratification, height and intensity, as well as air motion. Source: Data and Figure from <a href=\"https:\/\/www.ag.ndsu.edu\/publications\/crops\/air-temperature-inversions-causes-characteristics-and-potential-effects-on-pesticide-spray-drift\">\u201cAir Temperature Inversions Causes, Characteristics, and Potential Effects on Pesticide Spray Drift\u201d by Andrew Thostenson, Jon W. Enz, and Vernon Hofman<\/a>\u00a0is licensed under <a href=\"https:\/\/creativecommons.org\/licenses\/by-nc-sa\/3.0\/\">CC-BY-NC-SA 3.0<\/a>.<\/p>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">An atmospheric inversion may develop on a clear, cloudless night. Under such conditions, the ground surface cools quickly as it radiates heat that was absorbed during the day. This can result in a layer of cool air occurring beneath a higher layer of warmer air. Hilly terrain is particularly vulnerable to developing atmospheric inversions because relatively dense cool air can flow downward from hilltops and accumulate in valleys. Sometimes during the summer, stable atmospheric conditions may develop at higher altitude, capping a still-mixing air mass at ground level.<\/p>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">An atmospheric inversion can be rather stable. Until it is dispersed by vigorous winds, it can trap and accumulate air pollutants that are emitted during the inversion event. Severe episodes of air pollution can occur when stable inversions develop and are maintained for several days.<\/p>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">Some places regularly develop less-persistent inversions, such as Los Angeles, Mexico City, and Greater Vancouver. In these places, the inversions develop in the morning but are typically dispersed during the afternoon. In the meantime, however, oxidizing air pollutants such as ozone can accumulate into a photochemical smog.<\/p>\n<\/div>\n<h1 class=\"import-Normal2\">Sulfur Gases<\/h1>\n<h2 class=\"import-Normal2\">Emissions and Transformations<\/h2>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Sulfur dioxide (SO<sub>2<\/sub>) is one of the most important of the gaseous air pollutants. SO<sub>2<\/sub>\u00a0is a colorless but pungent gas. Humans can detect its bitter taste at a concentration of only 0.3-1 ppm (parts per million; for SO<sub>2<\/sub>, 1 ppm = 2.6 mg\/m<sup>3<\/sup>). Hydrogen sulfide (H<sub>2<\/sub>S), another sulfur gas, can be detected as a foul odor, reminiscent of rotten eggs, at concentrations lower than 1 ppb (parts per billion; for H<sub>2<\/sub>S, 1 ppm = 1.4 mg\/m<sup>3<\/sup>) (unless otherwise indicated, specific data cited in this and other chapters in this section on environmental damages are from Freedman, 1995).<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">After they are emitted to the atmosphere, SO<sub>2<\/sub>\u00a0and H<sub>2<\/sub>S become oxidized to other compounds, and ultimately form sulfate (SO<sub>4<\/sub><sup>2\u2013<\/sup>; see In Detail 20.2). Because the sulfate ion carries negative charges, it is an anion (this refers to any ion, atom, or molecule with a negative charge). Because H<sub>2<\/sub>S is quickly oxidized to SO<sub>2<\/sub>, its atmospheric residence time is less than one day (this is the time to complete disappearance of an initial amount). SO<sub>2<\/sub>\u00a0oxidizes more slowly, at a rate of &lt; 1-5% per hour, depending on sunlight, humidity, strong oxidants such as ozone, and the presence of metal-containing particulates that may act as catalysts. A typical residence time of SO<sub>2<\/sub>\u00a0in the atmosphere is about four days. Consequently, SO<sub>2<\/sub>\u00a0may disperse a long distance from its point of emission before it becomes oxidized or is deposited to a terrestrial or aquatic surface. This kind of dispersal is referred to as long-range transportation of air pollution (LRTAP).<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Atmospheric sulfate, formed by the oxidation of SO<sub>2<\/sub>\u00a0or H<sub>2<\/sub>S, can combine with positively charged ions (cations) to form various compounds. Most atmospheric sulfate occurs as tiny particulates, especially ammonium sulfate ((NH<sub>4<\/sub>)<sub>2<\/sub>\u00a0SO<sub>4<\/sub>). This is the most prominent component, along with ammonium nitrate (NH<sub>4<\/sub>NO<sub>3<\/sub>), of the fine particulate haze that often impairs visibility in cities. Haze also occurs in some rural areas where pollutants have been imported by LRTAP from emission sources elsewhere. Other cations that combine with sulfate include calcium (Ca<sup>2+<\/sup>), magnesium (Mg<sup>2+<\/sup>), and sodium (Na<sup>+<\/sup>). Often, however, there are not enough of these cations to balance all of the negative charges of the sulfate (SO<sub>4<\/sub><sup>2\u2013<\/sup>) present. Under such conditions, hydrogen ions (H<sup>+<\/sup>) serve to balance some of the negative charges, resulting in an aerosol containing sulfuric acid (H<sub>2<\/sub>SO<sub>4<\/sub>), the most important component of acidic precipitation (see Chapter 23).<\/p>\n<h2 class=\"import-Normal2\">Emissions of Sulfur Gases<\/h2>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Volcanoes are natural sources of emission of sulfur gases. On average, volcanoes emit about 12-million tonnes of sulfur gases per year, of which 90% is SO<sub>2<\/sub>\u00a0and 10% is H<sub>2<\/sub>S. However, the enormous 1991 eruption of Mount Pinatubo in the Philippines emitted 7-10-million tonnes of SO<sub>2<\/sub>\u00a0(expressed as the sulfur content, or SO<sub>2<\/sub>-S). The much smaller eruption of Mount St. Helens in Washington State in 1980 vented about 0.2-million tonnes of SO<sub>2<\/sub>-S. Natural emissions of SO<sub>2<\/sub>\u00a0also occur during wildfires.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">The global anthropogenic emissions of SO<sub>2<\/sub>\u00a0are about 150-million tonnes per year, or 3.8-times the natural releases. Fossil-fuel combustion accounts for more than half of the anthropogenic emissions (Figure 20.2). Coal and petroleum contain mineral compounds of sulfur, such as pyrite (FeS<sub>2<\/sub>), as well as organic sulfur compounds. When these fuels are burned, the sulfur becomes oxidized to gaseous SO<sub>2<\/sub>, which may be vented to the atmosphere. Hard coals mined in eastern North America contain 1-12% sulfur, softer coals from western regions have &lt;0.3-1.5%, crude oil has 0.8-1.0% residual fuel oils such as bunker -C have 0.3-0.4%, and motor fuels such as diesel and gasoline have 0.04-0.05%. Other important sources of SO<sub>2 <\/sub>emissions are manufacturing processes (23% of global emissions), the smelting of metal ores (7%), and the burning of natural habitats during agricultural conversions (most of the rest).<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\"><img decoding=\"async\" class=\"aligncenter\" src=\"src\" alt=\"image\" \/><\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone size-full wp-image-735\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/5337\/2021\/07\/05121527\/Picture16.png\" alt=\"\" width=\"1791\" height=\"783\" \/><\/p>\n<p class=\"import-Normal\">Figure 20.2. Global Anthropogenic SO<sub>2<\/sub> Emissions from 1850-2005. Source: <a href=\"https:\/\/acp.copernicus.org\/articles\/11\/1101\/2011\/acp-11-1101-2011.pdf\">Smith et al. 2011<\/a><\/p>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">Globally anthropogenic emissions of SO<sub>2<\/sub>\u00a0have increased enormously since the beginning of the Industrial Revolution. Emissions in 1860 were about 5-million tonnes, compared with about 150-million tonnes in 2000. Since then, most of the wealthier countries have invested heavily in clean-air technologies for power plants and other industrial users of coal and oil in order to reduce emissions of damaging SO<sub>2<\/sub>\u00a0to the atmosphere. The clean-air actions include the following:<\/p>\n<ul>\n<li class=\"import-Normal2\">The installation of technologies to capture SO<sub>2<\/sub>\u00a0from post-combustion waste gases (this is known as flue-gas desulphurization or scrubbing)<\/li>\n<li class=\"import-Normal2\">The removal of some of the sulfur content of fuels (known as fuel desulphurization or coal washing)<\/li>\n<li class=\"import-Normal2\">The installation of particulate-control devices (such as electrostatic precipitators) to greatly reduce the emissions of particulates (although this has little effect on SO<sub>2<\/sub>\u00a0emissions)<\/li>\n<li class=\"import-Normal2\">Switching to low- or no-sulfur fuels such as natural gas, or to no-sulfur energy technologies such as hydroelectricity and nuclear power (known as fuel-switching)<\/li>\n<li class=\"import-Normal2\">Energy conservation to reduce the overall demand for fuel and associated emissions of pollutants<\/li>\n<li class=\"import-Normal2\">Building taller smokestacks to disperse emissions of SO<sub>2<\/sub>\u00a0more widely, which helps to decrease the local ground-level pollution<\/li>\n<\/ul>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">However, future global emissions are bound to increase. China, India, and other rapidly industrializing countries supply much of their burgeoning energy needs by burning coal and petroleum fuels. In China, coal is the major source of industrial energy, accounting for 58% of the energy supply in 2019 (U.S. Energy Information Administration 2020). Due to increasing industrialization, emissions of SO<sub>2<\/sub>\u00a0in China increased from 10-million tonnes in 1980 to 34-million tonnes in 2000, a 3.4-fold increase in only 20 years.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">The amounts of SO<sub>2<\/sub>\u00a0emissions differ greatly among nations, depending on their population, their kind of industrialization, and the fuels they mostly use. For instance, Canadian emissions of SO<sub>2<\/sub>\u00a0are about 22% of those of the U.S. However, the population of Canada is only about 11% that of the U.S. Therefore, per-capita emissions of SO<sub>2<\/sub>\u00a0are about double in Canada than in the U.S.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">About 66% of Canadian emissions of SO<sub>2<\/sub>\u00a0are from large industrial sources, particularly metal smelters, while 24% are from \u201cfuel combustion,\u201d which is mostly fossil-fueled power plants. In comparison, 84% of U.S. emissions are from power plants, and 10% from industrial sources. Most of this difference is due to two factors: a relatively large proportion of electricity generation in Canada is from nuclear and hydro technologies, which do not emit SO<sub>2<\/sub>, and metal smelting is a major industry in Canada.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Because of human-health and environmental damages associated with SO<sub>2<\/sub>\u00a0and other air pollutants, most developed nations have acted to reduce their emissions. In Canada, emissions of SO<sub>2<\/sub> were reduced by about 41% between 1985 and 2012, compared with a 32% reduction in the U.S. (Figure 20.2). In both countries the reductions were achieved by several methods:<\/p>\n<ul>\n<li class=\"import-Normal2\">Switching to low- or no-sulfur fuels for some major uses, especially for electricity generation<\/li>\n<li class=\"import-Normal2\">Removing sulfur from some fuels prior to combustion, mostly by coal washing<\/li>\n<li class=\"import-Normal2\">Reducing energy demands through conservation<\/li>\n<li class=\"import-Normal2\">Installing scrubbers to remove SO<sub>2<\/sub>\u00a0from post-combustion waste gases before they are vented to the atmosphere<\/li>\n<\/ul>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">The large reductions of SO<sub>2 <\/sub>that have been achieved in North America during the past several decades cost many billions of dollars to achieve, and they should be regarded as an important \u201csuccess story\u201d of pollution control. Figure 20.3 depicts reduction in sulfur dioxide emissions for the U.S.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/5337\/2021\/07\/02104254\/image3.png\" alt=\"image\" width=\"715\" height=\"364\" \/><\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Figure 20.3. Reductions in Sulfur Dioxide Emissions in the U.S. from 2006 to 2015. Data from <a href=\"https:\/\/www.eia.gov\/todayinenergy\/detail.php?id=29812\">U.S. Energy Information Administration.<\/a><\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">In contrast to SO<sub>2<\/sub>, the global emissions of sulfide gases are mostly from natural sources. The largest sources are H<sub>2<\/sub>S emitted from anoxic sediment in shallow marine and inland waters, and dimethyl sulfide ((CH<sub>3<\/sub>)<sub>2<\/sub>S) produced by phytoplankton and out-gassed from oceanic waters. The natural emission of H<sub>2<\/sub>S is about 100-million tonnes per year, and dimethyl sulfide, 15-million tonnes per year (both expressed as sulfur equivalent, or as tonnes of S). Anthropogenic emissions of H<sub>2<\/sub>S are about 3-million tonnes per year, and are mostly from chemical industries, sewage-treatment plants, and livestock manure. The global emission of all sulfur-containing gases is equivalent to almost 300- million tonnes of sulfur per year. About half of the global emission is from anthropogenic sources. Clean air typically contains less than 0.2 ppb of SO<sub>2<\/sub>\u00a0or H<sub>2<\/sub>S. Concentrations of SO<sub>2<\/sub>\u00a0and H<sub>2<\/sub>S in air that is polluted by emissions are highly variable. They are typically about 0.2 ppm in urban atmospheres but can exceed 3 ppm close to large emission sources.<\/p>\n<h2 class=\"import-Normal2\">Toxicity of Sulfur Gases<\/h2>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Concentrations of H<sub>2<\/sub>S in the environment are rarely high enough to be toxic to plants. However, accidental emissions from sour-gas plants (where H<sub>2<\/sub>S is removed from natural gas) may cause local vegetation damage. In contrast, concentrations of SO<sub>2<\/sub>\u00a0in cities and near industrial sources are often high enough to injure wild and cultivated plants. Near certain metal smelters, vegetation has been severely damaged, as we examine later.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">An exposure to 0.7 ppm SO<sub>2<\/sub>\u00a0for one hour will result in acute injury to most plant species, as will 0.2 ppm over an eight-hour period. It is important to note, however, that certain species are extremely sensitive to SO<sub>2<\/sub>\u00a0exposures (they are hypersensitive) and can suffer acute injuries at concentrations lower than those just noted.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">In addition, plants will often exhibit a reduction in yield when exposed to concentrations of SO<sub>2<\/sub>\u00a0that are lower than those required to cause an acute injury. This type of response, which occurs without symptoms of acute tissue damage, is referred to as \u201chidden injury\u201d. Hidden injuries to wild and agricultural vegetation are measured by enclosing plants in experimental chambers and exposing them to either air containing ambient levels of SO<sub>2<\/sub>, or that that has been filtered through charcoal to remove that gas. If productivity is greater in the filtered air, it follows that the ambient SO<sub>2<\/sub>\u00a0was causing a hidden injury. Studies of pasture grasses have found that exposure to SO<sub>2<\/sub>\u00a0concentrations averaging only 0.04 ppm would cause hidden injuries as reductions of yield.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">The U.S. National Ambient Air Quality Standards (Table 20.1) sets the guideline for ambient SO<sub>2<\/sub>\u00a0in the atmosphere at 75 parts per billion over a one-hour exposure time (EPA 2020a), and 0.5 ppm over a three-hour exposure time.\u00a0These\u00a0guidelines\u00a0are\u00a0intended to protect human populations (particularly those sensitive to air pollutants, e.g., those with asthma, children, and the elderly) as well as to prevent\u00a0acute foliar (leaf) injuries agricultural plants. Although regions meeting these\u00a0guidelines\u00a0would not show much acute damage to vegetation, relatively sensitive species might be affected through hidden injuries, possibly resulting in significant losses of yield.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Table 20.1. National Ambient Air Quality Standards for Six Principal Pollutants. This table shows both the primary and secondary standards, which define the limits of the pollutants to minimize their harmful impacts on public health and the environment. Primary standards are the limits placed to protect public health, including protecting the \u201csensitive\u201d populations (asthmatics, children, and the elderly). Secondary standards concern public welfare and environmental protections. Source: <a href=\"https:\/\/www.epa.gov\/criteria-air-pollutants\/naaqs-table\">EPA<\/a>.<\/p>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/5337\/2021\/07\/02104255\/image4.png\" alt=\"image\" width=\"724\" height=\"794\" \/><\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Humans and most other animals are much less sensitive to SO<sub>2<\/sub>\u00a0than plants are. Guidelines for allowable exposures of people to SO<sub>2<\/sub>\u00a0and other potentially toxic gases accommodate the fact that, in terms of dose received, longer-term exposures to low concentrations can be as important as higher acute exposures.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Guidelines for occupational exposures to air pollutants are frequently greater than those for ambient exposures. In North America, it is recommended that occupational exposures to SO<sub>2<\/sub>\u00a0be no higher than 2 ppm (5.2 mg\/m<sup>3<\/sup>) over the long term, and no higher than 5 ppm (13 mg\/m<sup>3<\/sup>) for shorter exposures. However, some people are relatively sensitive to SO<sub>2<\/sub>, and concentrations less than 1 ppm (2.6 mg\/m<sup>3<\/sup>) may cause them to suffer asthma or other distresses related to impaired lung function. In addition, some studies have suggested that long-term exposures of large human populations to sulfate particulate aerosols (which are ultimately derived from gaseous SO<sub>2<\/sub>) in cities may result in small increases in the incidence of respiratory and circulatory diseases, most probably in hypersensitive people.<\/p>\n<div class=\"textbox shaded\">\n<h3 class=\"import-Normal2\" style=\"margin-right: 24pt;\">In Detail 20.2. Air Pollution Chemistry<\/h3>\n<p class=\"import-Normal2\" style=\"margin-right: 24pt;\">Air pollutants are emitted as particular chemicals, which may then be transformed into other compounds through reactions occurring in the atmosphere. Several examples follow.<\/p>\n<h2 class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">Oxidation of SO<sub>2<\/sub><\/h2>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">SO<sub>2<\/sub>\u00a0+ OH \u2192 HO\u2022SO<sub>2<\/sub>\u00a0(1)<\/p>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">HO\u2022SO<sub>2<\/sub>\u00a0+ O<sub>2<\/sub>\u00a0\u2192 HO<sub>2<\/sub>\u00a0+ SO<sub>3<\/sub>\u00a0(2)<\/p>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">SO<sub>3<\/sub>\u00a0+ H<sub>2<\/sub>O \u2192 H<sub>2<\/sub>SO<sub>4<\/sub>\u00a0(3)<\/p>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">H<sub>2<\/sub>SO<sub>4<\/sub>\u00a0\u2192 2H<sup>+<\/sup>\u00a0+ SO<sub>4<\/sub><sup>2\u2013<\/sup>\u00a0(in aqueous solution) (4)<\/p>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">Note that the SO<sub>4<\/sub><sup>2\u2013<\/sup>\u00a0produced is important as a constituent of acid rain and as particulate ammonium sulfate ((NH<sub>4<\/sub>)<sub>2<\/sub>SO<sub>4<\/sub>), which are important pollutants.<\/p>\n<h2 class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">Oxidation of NO<\/h2>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">NO + HO<sub>2<\/sub>\u00a0\u2192 NO<sub>2<\/sub>\u00a0+ OH (5)<\/p>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">NO<sub>2<\/sub>\u00a0+ OH \u2192 HNO<sub>3<\/sub>\u00a0(6)<\/p>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">HNO<sub>3<\/sub>\u00a0\u2192 H<sup>+<\/sup>\u00a0+ NO<sub>3<\/sub><sup>\u2013<\/sup> (in aqueous solution) (7)<\/p>\n<p class=\"import-Normal2\" style=\"layout-grid-mode: both; text-align: justify; text-justify: inter-ideograph; margin-right: 23.75pt;\">Similarly, the NO<sub>3<\/sub><sup>\u2013<\/sup> produced is important in acid rain and as particulate ammonium nitrate (NH<sub>4<\/sub>NO<sub>3<\/sub>).<\/p>\n<h2 class=\"import-Normal2\" style=\"layout-grid-mode: both; text-align: justify; text-justify: inter-ideograph; margin-right: 23.75pt;\">Formation and Destruction of Stratospheric O<sub>3<\/sub><\/h2>\n<p class=\"import-Normal2\" style=\"layout-grid-mode: both; text-align: justify; text-justify: inter-ideograph; margin-right: 23.75pt;\">O<sub>2<\/sub>\u00a0+ UV radiation \u2192 O + O (8) O + O \u2192 O<sub>2<\/sub>\u00a0(9)<\/p>\n<p class=\"import-Normal2\" style=\"layout-grid-mode: both; text-align: justify; text-justify: inter-ideograph; margin-right: 23.75pt;\">O + O<sub>2<\/sub>\u00a0\u2192 O<sub>3<\/sub>\u00a0(10)<\/p>\n<p class=\"import-Normal2\" style=\"layout-grid-mode: both; text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">O<sub>3<\/sub>\u00a0+ UV radiation \u2192 O<sub>2<\/sub>\u00a0+ O (11)<\/p>\n<p class=\"import-Normal2\" style=\"layout-grid-mode: both; text-align: justify; text-justify: inter-ideograph; margin-right: 23.75pt;\">Reaction 11 is an ultraviolet photodissociation of O<sub>3<\/sub>. Ozone can also be consumed by reactions with NO, NO<sub>2<\/sub>, N<sub>2<\/sub>O, and with ions or simple molecules of chlorine (especially ClO), bromine, and fluorine. These reactions are too complex to describe here.<\/p>\n<h2 class=\"import-Normal2\" style=\"layout-grid-mode: both; text-align: justify; text-justify: inter-ideograph; margin-right: 23.75pt;\">Formation and Destruction of Ground-Level O<sub>3<\/sub><\/h2>\n<p class=\"import-Normal2\" style=\"layout-grid-mode: both; text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">O + O<sub>2<\/sub>\u00a0\u2192 O<sub>3<\/sub>\u00a0(10)<\/p>\n<p class=\"import-Normal2\" style=\"layout-grid-mode: both; text-align: justify; text-justify: inter-ideograph; margin-right: 23.75pt;\">NO<sub>2<\/sub>\u00a0+ UV radiation \u2192 NO + O (12)<\/p>\n<p class=\"import-Normal2\" style=\"layout-grid-mode: both; text-align: justify; text-justify: inter-ideograph; margin-right: 23.75pt;\">NO + O<sub>3<\/sub>\u00a0\u2192 NO<sub>2<\/sub>\u00a0+ O<sub>2<\/sub>\u00a0(13)<\/p>\n<p class=\"import-Normal2\" style=\"layout-grid-mode: both; text-align: justify; text-justify: inter-ideograph; margin-right: 23.75pt;\">NO + RO<sub>2<\/sub>\u00a0\u2192 NO<sub>2<\/sub>\u00a0+ RO (14)<\/p>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">The formation of O<sub>3<\/sub>\u00a0(reaction 10) requires atomic O, formed by the photodissociation of NO<sub>2<\/sub>\u00a0(reaction 12). Ozone can be consumed by reaction with NO (an emitted gas), which regenerates NO<sub>2<\/sub>\u00a0(reaction 13). Atmospheric O<sub>3<\/sub>\u00a0can, however, accumulate if other reactions (such as reaction 14) convert NO to NO<sub>2<\/sub>, because these operate in competition with reaction 13 for NO. (The species RO<sub>2<\/sub>\u00a0includes various chemicals known as peroxy radicals, formed by the degradation of organic molecules by reaction with hydroxyl radicals, followed by the addition of molecular O<sub>2<\/sub>. RO is the chemically reduced form of RO<sub>2<\/sub>.)<\/p>\n<\/div>\n<h1 class=\"import-Normal2\">Nitrogen Gases<\/h1>\n<h2 class=\"import-Normal2\">Emissions and Transformations<\/h2>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">The most important of the nitrogen-containing gases are nitric oxide (NO), nitrogen dioxide (NO<sub>2<\/sub>), nitrous oxide (N<sub>2<\/sub>O), and ammonia (NH<sub>3<\/sub>). NO and NO<sub>2<\/sub>\u00a0are often considered together as a complex, referred to as NO<sub>x<\/sub>.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Ammonia (NH<sub>3<\/sub>), a colorless gas, is emitted mostly from wetlands, where it is produced during the anaerobic decomposition of dead biomass. Natural emissions of NH<sub>3<\/sub>\u00a0are about 1.2-billion tonnes per year. Sources of anthropogenic emissions include fossil-fuel combustion (4-million tonnes per year) and animal husbandry (0.2-million tonnes per year). The residence time of NH<sub>3<\/sub>\u00a0in the atmosphere is about seven days (the NH<sub>3<\/sub>\u00a0is eventually oxidized to nitrate).<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Nitrous oxide (N<sub>2<\/sub>O) is a colorless, non-toxic gas that produces a mild euphoria when inhaled. This gas is also known as \u201claughing gas\u201d and is used as a mild anesthetic in medicine, and sometimes as a recreational drug. Because N<sub>2<\/sub>O is a rather unreactive compound, it has a long residence time in the atmosphere of about four years. Most N<sub>2<\/sub>O emissions are associated with microbial denitrification in soil and water. These are equivalent to about 18-million tonnes per year, while industrial emissions are 12-million tonnes per year. Agricultural soil fertilized with nitrate can have high rates of N<sub>2<\/sub>O emission, and modern agricultural practices are thought to have increased global emissions by about 40% (Figure 20.4).<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"wp-image-746 aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/5337\/2021\/07\/05194436\/nitrous-oxide-emissions-by-sector.png\" alt=\"\" width=\"726\" height=\"440\" \/><\/p>\n<p>Figure 20.4. Worldwide Nitrous Oxide Emissions by Sector. Nitrous oxide emissions are measured in tonnes of carbon dioxide equivalents (CO<sub>2<\/sub>e) based on a 100-year potential global warming value.\u00a0Source: visualization by\u00a0<a href=\"https:\/\/ourworldindata.org\/grapher\/nitrous-oxide-emissions-by-sector?country=~OWID_WRL\">OurWorldinData.org<\/a>\u00a0is licensed under <a href=\"https:\/\/creativecommons.org\/licenses\/by\/4.0\/deed.en_US\">CC BY 4.0<\/a>.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Nitric oxide (NO) is a colorless and odorless gas, while nitrogen dioxide is reddish, pungent, and irritating to respiratory and eye membranes. Natural emissions of NO<sub>x<\/sub>\u00a0are about 430-million tonnes per year (expressed as NO; the same emissions expressed as NO<sub>2<\/sub>\u00a0are 658-million tonnes per year). The most important natural emissions of NO<sub>x<\/sub>\u00a0are due to bacterial denitrification of nitrate in soil, fixation of atmospheric nitrogen gas (N<sub>2<\/sub>) by lightning, and oxidation of biomass nitrogen during fires (see Chapter 5).<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Anthropogenic emissions of NO<sub>x<\/sub>, about 83-million tonnes per year (expressed as NO), result mostly from the combustion of fossil fuels, especially in automobiles and power plants. These emissions are mostly NO, which is secondarily oxidized to NO<sub>2<\/sub>\u00a0by reactions in the atmosphere. Ultimately, most atmospheric NO<sub>x<\/sub>\u00a0gases become oxidized to nitrate (NO<sub>3<\/sub><sup>\u2013<\/sup>), an ion that is important in the acidification of precipitation and ecosystems (Chapter 23).<\/p>\n<h2 class=\"import-Normal2\">Toxicity of Nitrogen Gases<\/h2>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">It is rare that concentrations of NH<sub>3<\/sub>\u00a0or NO<sub>x<\/sub>\u00a0gases are high enough to injure vegetation. The environmental damage associated with NO<sub>x<\/sub>\u00a0is focused on the photochemical reactions by which ozone, a much more toxic gas, is produced (see below), and also the acidification of precipitation and ecosystems.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Ambient concentrations of NH<sub>3<\/sub>\u00a0and NO<sub>x<\/sub>\u00a0are rarely high enough to bother humans. Guidelines for long-term exposures in an occupational setting are 25 ppm (34 mg\/m<sup>3<\/sup>) for NO and 5 ppm (10 mg\/m<sup>3<\/sup>) for NO<sub>2<\/sub>. Occupational guidelines for short-term exposures are 35 ppm (47 mg\/m<sup>3<\/sup>) and 5 ppm (10 mg\/m<sup>3<\/sup>), respectively. Intense occupational exposures to NO<sub>x<\/sub>\u00a0can cause impaired pulmonary function in humans.<\/p>\n<h1 class=\"import-Normal2\">Organic Gases and Vapors<\/h1>\n<h2 class=\"import-Normal2\">Emissions and Transformations<\/h2>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Hydrocarbons are a diverse group of chemicals whose molecular structures containing various combinations of hydrogen and carbon atoms. The simplest hydrocarbon is methane (CH<sub>4<\/sub>), a gas. Larger hydrocarbons with greater weight and more complex structure may occur as vapors, liquids, or solids. Other volatile organic compounds (VOCs) may contain oxygen, nitrogen, and other light elements in addition to carbon and hydrogen, and include alcohols, aldehydes, and phenols.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">The background concentration of methane in the atmosphere is about 1.7 ppm (1 ppm = 0.65 mg\/m<sup>3<\/sup>), while all other hydrocarbons and volatile organics together amount to less than 1 ppb. Most emissions of CH<sub>4<\/sub>\u00a0are natural and are associated with the fermentation of organic matter by microbes in anaerobic wetlands. Smaller amounts are out-gassed from deposits of fossil fuels, during wildfires, and from burping and flatulent ruminant animals (such as cows and sheep) and termites, which produce CH<sub>4<\/sub>\u00a0as they digest their plant foods. Of total global CH\u2084 emissions, 50-65 percent are emitted from human activities, including energy, industry, agriculture, and waste management activities (EPA, 2020b). In the U.S., the largest source of CH\u2084 emissions is the agriculture sector.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Atmospheric hydrocarbons other than CH<sub>4<\/sub>\u00a0are referred to as non-methane hydrocarbons. Natural emissions of these and many organics occur mainly as gases and vapors that evaporate from living vegetation, along with smaller quantities that out-gas from deposits of fossil fuels. The largest emissions from forests typically occur during hot, sunny days. Natural emissions of non-methane hydrocarbons are about 200-million tonnes per year, compared with anthropogenic emissions of 186-million tonnes per year. The most important anthropogenic sources are unburned fuel emitted from vehicles and aircraft, releases during fossil-fuel mining and refining, and evaporation of solvents.<\/p>\n<h2 class=\"import-Normal2\">Toxicity of Organic Gases and Vapors<\/h2>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Organic gases and vapors can be toxic, but atmospheric concentrations are rarely high enough to damage vegetation or animals. The environmental importance of these gases and vapors lies mainly in their role in the photochemical reactions that produce toxic ozone. In addition, CH<sub>4<\/sub> is an important greenhouse gas that affects global warming (Chapter 21). In some workplaces, however, relatively toxic organics such as benzene and formaldehyde may be important pollutants.<\/p>\n<h2 class=\"import-Normal2\">Ozone<\/h2>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">There are two different ozone-related environmental issues: (1) O<sub>3<\/sub>\u00a0in the stratosphere and (2) O<sub>3<\/sub>\u00a0in the troposphere (ground-level ozone). High concentrations of ozone are naturally present in the upper-atmospheric layer known as the stratosphere, which begins at about 8-17 km above the Earth\u2019s surface, depending on the latitude and season. Stratospheric O<sub>3<\/sub>\u00a0causes no damage and is not an air pollutant. Rather, by absorbing solar ultraviolet radiation, stratospheric\u00a0O<sub>3 <\/sub>helps to protect organisms on the surface of the planet from many damaging effects of exposure to this harmful part of the electromagnetic spectrum. In contrast, O<sub>3<\/sub> in the lower\u00a0atmosphere (the troposphere) is an important air pollutant that damages vegetation, materials, and human health. Ozone is removed from the atmosphere by interactions with other gases, organic vapors, and terrestrial and aquatic surfaces (including vegetation).<\/p>\n<h3 class=\"import-Normal2\">Ground-Level Ozone<\/h3>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Ground-level ozone (O<sub>3<\/sub>) is the most damaging of the so-called photochemical air pollutants. Less important are peroxyacetyl nitrate (PAN), hydrogen peroxide (H<sub>2<\/sub>O<sub>2<\/sub>), and other oxidant gases. Oxidizing smog is rich in O<sub>3<\/sub>\u00a0and the other oxidant gases. These chemicals are secondary pollutants, meaning they are not actually emitted to the atmosphere (as are primary pollutants such as SO<sub>2<\/sub>\u00a0and NO<sub>x<\/sub>). Instead, they are synthesized within the atmosphere by photochemical reactions (chemical reactions that require light, especially ultraviolet wavelengths; Figure 20.5). These proceed at faster rates and result in a buildup of oxidants if NO<sub>x<\/sub>\u00a0and hydrocarbons are present in high concentrations, a condition that is typically due to anthropogenic emissions.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"size-full wp-image-724 aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/5337\/2021\/07\/05112603\/how-ozone-forms-diagram.png\" alt=\"\" width=\"650\" height=\"516\" \/><\/p>\n<p>Figure 20.5. Ground Level Ozone Formation. Ground level ozone is not emitted directly into the atmosphere, but instead is synthesized by photochemical reactions. Source: used with permission from the <a href=\"https:\/\/www.pca.state.mn.us\/air\/ozone\">Minnesota Pollution Control Agency<\/a>.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Some regions tend to develop a weak atmospheric inversion in the morning. Because an inversion is relatively stable and resists the in-mixing of cleaner air from above or beyond, this condition encourages the development of oxidizing smog during the morning and early afternoon. Later in the day, the inversion is typically broken up by stronger winds, and the air pollution is dispersed. Such inversions and their ozone-rich smog are common phenomena around the Los Angeles basin, Mexico City, Vancouver, and elsewhere.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">The concentrations of ground-level O<sub>3<\/sub>\u00a0vary greatly among different regions of North America. Average concentrations in the southwestern U.S. are relatively high, at about 100 ppb (1 ppb = 2 \u00b5g\/m<sup>3<\/sup>), and they generally range from 40\u201360 ppb in other regions of the U.S. and in southern Canada.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Canada, the U.S., and other countries have developed air quality standards for O<sub>3<\/sub>. These are intended to reflect concentrations that would prevent severe damage to agricultural and wild vegetation. For some time, the O<sub>3<\/sub>\u00a0standard in the U.S. was 80 ppb (160 \u00b5g\/m<sup>3<\/sup>) (for an average one-hour exposure), but in 1979 this was relaxed to 120 ppb (240 \u00b5g\/m<sup>3<\/sup>). The authorities made the change because the original standard of 80 ppb was frequently exceeded over large regions and so was essentially unenforceable. In fact, even the 120 ppb criterion is commonly exceeded in some regions, particularly in the southwestern U.S.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">The Los Angeles basin suffers especially intense photochemical air pollution. Concentrations of O<sub>3<\/sub>\u00a0can exceed 500 ppb (one-hour average), and they typically exceed 100 ppb for more than 15 days during the summer. Maximum O<sub>3<\/sub>\u00a0concentrations are lower in other cities of North America, typically reaching up to 150-250 ppb (one-hour average). These concentrations are well within the range at which O<sub>3<\/sub>\u00a0can cause acute injury to plants, which is why O<sub>3<\/sub>\u00a0is such an important air pollutant. The emissions of ozone precursors (NO<sub>x<\/sub>\u00a0and hydrocarbons) occur mainly in cities, but extensive ecological damage is caused when polluted air masses are transported to rural areas dominated by agricultural or natural vegetation.<\/p>\n<h3 class=\"import-Normal2\">Toxicity of Ozone<\/h3>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Humans and some animals are sensitive to O<sub>3<\/sub>, which can irritate and damage membranes of the eyes and respiratory system and cause a loss of lung functioning. The guideline for long-term exposure to O<sub>3 <\/sub>in an occupational setting is 100 ppb (196 \u00b5g\/m<sup>3<\/sup>), and it is 300 ppb (589 \u00b5g\/m<sup>3<\/sup>) for short-term exposures. However, sensitive people can be affected by O<sub>3<\/sub>-related symptoms at lower concentrations. Exposure to O<sub>3<\/sub>\u00a0can result in asthmatic attacks and can exacerbate bronchitis and emphysema.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Ozone causes important damage to wild and agricultural plants over widespread areas. Foliar injuries are often distinctive to O<sub>3<\/sub>, and they diminish the photosynthetic capacity of plants and thereby reduce their productivity. Acute injuries are caused to most species by two- to four-hour exposures to 200-300 ppb O<sub>3<\/sub>, while long-term exposures to only 40-100 ppb may cause hidden injuries (and reduced yield). However, many species are more sensitive and suffer acute and hidden injuries at lower concentrations. Some varieties of tobacco (<em>Nicotiana tobacco<\/em>), for example, can suffer acute foliar injuries from a two- to three-hour exposure to only 50-60 ppb, and spinach (<em>Spinacea oleracea<\/em>), from one to two hours at 60-80 ppb. Sensitive species of conifer trees may suffer acute injuries from exposures to 80 ppb O<sub>3<\/sub>\u00a0over 12 hours.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Researchers have grown agricultural plants in experimental chambers that received ambient air, or air filtered through charcoal, which removes any O<sub>3<\/sub>. These studies have been useful in defining the extent of damage caused to agricultural crops by exposure to ambient O<sub>3<\/sub>. One series of field experiments demonstrated that crop yields were reduced in all regions of the U.S. The worst damage occurred in the southwest, where sunny conditions and large emissions of NO<sub>x<\/sub>\u00a0and hydrocarbons result in especially high O<sub>3<\/sub>\u00a0concentrations. That study estimated that crop damage due to O<sub>3<\/sub>\u00a0was equivalent to 2\u20134% of the total agricultural yield in the U.S., with economic losses equivalent to more than $5 billion per year. Because O<sub>3<\/sub>-related damage to vegetation occurs over extensive areas of North America, it is by far the most important air pollutant in agriculture. Ozone is probably also the leading air pollutant causing damage to forests and other natural ecosystems.<\/p>\n<h3 class=\"import-Normal2\">Stratospheric Ozone<\/h3>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">In contrast to ground-level ozone, ozone in the stratosphere protects life on Earth from the damaging effects of solar ultraviolet (UV) radiation. This is the reason why the fact that stratospheric ozone is being destroyed by anthropogenic emissions of certain gases is cause for alarm.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Ozone is produced in the stratosphere by natural photochemical reactions. They involve the absorption of solar UV radiation by oxygen molecules (O<sub>2<\/sub>), which creates highly reactive oxygen atoms (O) that join with other O<sub>2<\/sub>\u00a0molecules to form O<sub>3<\/sub>\u00a0(see In Detail 20.2). These reactions proceed relatively quickly in the stratosphere because high-energy UV radiation is abundant there. As a result, O<sub>3<\/sub>\u00a0concentrations are typically 200-300 ppb in the stratosphere, about 10 times greater than in the ambient troposphere.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Stratospheric O<sub>3<\/sub>\u00a0provides a critical environmental service. It efficiently absorbs most of the incoming high-energy UV radiation, which can be extremely damaging to organisms. In particular, DNA is a strong absorber of UV and can be damaged by this radiation. This can increase the risk of developing skin cancers, including melanoma, an often-fatal malignancy. Other health risks from UV exposure include the development of cataracts in the eyes and suppression of the immune system. UV radiation also damages plants, in part because chlorophyll (the key photosynthetic pigment) is degraded by UV absorption, which may lead to decreases in productivity. The waxy covering of the cuticle of foliage is also damaged by UV radiation.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Stratospheric O<sub>3<\/sub>\u00a0can be destroyed by various processes, including reactions with the trace gases NO<sub>x <\/sub>and N<sub>2<\/sub>O and with reactive ions of bromine, chlorine, and fluorine. Because of anthropogenic emissions, the concentrations of some of these O<sub>3<\/sub>-consuming chemicals have been increasing in the stratosphere, leading to concerns about the depletion of stratospheric O<sub>3<\/sub>. It is widely believed that emissions of chlorofluorocarbons (CFCs), particularly the industrial gases known as freons, have been especially important in this regard. Because CFCs are extremely unreactive in the troposphere, they eventually migrate up to the stratosphere, where they are bombarded with UV radiation and slowly degrade (photodissociate) to release free chlorine. The chlorine efficiently reacts with and destroys O<sub>3<\/sub>.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">The O<sub>3<\/sub>-destroying reactions proceed most effectively under extremely cold and stagnant conditions in the stratosphere, such as those occurring above polar latitudes at the end of the Antarctic and Arctic winters. These polar-focused O<sub>3<\/sub>\u00a0depletions result in the development of so-called ozone holes during the early springtime. These phenomena have been observed regularly since the early 1980s. The O<sub>3<\/sub>\u00a0holes over Antarctica are particularly extensive and typically involve decreases of the O<sub>3<\/sub>\u00a0concentration of 30-50% during the spring. Smaller depletions of O<sub>3<\/sub>\u00a0occur above the Arctic, including northern Canada. The affected areas in the Northern Hemisphere are much smaller than their counterparts in Antarctica.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">The sizes of the ozone holes in Antarctica vary from year to year, but there has been a trend of strong increases since 1980, when the first accurate data began to be collected (Figure 20.6). Although the seasonal losses of O<sub>3<\/sub>\u00a0only take place over polar regions, lower latitudes are also affected when the O<sub>3<\/sub>-depleted air becomes dispersed during the breakup of the holes. This temporarily reduces the stratospheric O<sub>3<\/sub>\u00a0concentrations throughout the hemisphere, though not nearly to the same degree as occurs in the holes themselves.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\"><img loading=\"lazy\" decoding=\"async\" class=\"wp-image-719 aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/5337\/2021\/07\/05104131\/Picture11.png\" alt=\"\" width=\"746\" height=\"473\" \/><\/p>\n<p class=\"import-Normal0\" style=\"margin-right: 24pt;\">Figure 20.6. Antarctic Ozone Hole Area. Changes in the maximum and minimum annual size of the ozone \u201chole\u201d over Antarctica.\u00a0Source: visualization by\u00a0<a href=\"https:\/\/ourworldindata.org\/grapher\/antarctic-ozone-hole-area?country=~OWID_WRL\">OurWorldinData.org<\/a>, data from <a href=\"https:\/\/ozonewatch.gsfc.nasa.gov\/meteorology\/annual_data.html\">NASA Ozone Watch,<\/a>\u00a0is licensed under <a href=\"https:\/\/creativecommons.org\/licenses\/by\/4.0\/deed.en_US\">CC BY 4.0<\/a>.<\/p>\n<div class=\"textbox shaded\">\n<h3 class=\"import-Normal2\" style=\"margin-right: 24pt;\">Environmental Issues 20.1. The Montreal Protocol \u2013 A Success of Regulatory Action<\/h3>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">Soon after it became widely recognized that emissions of chlorofluorocarbons (CFCs) and other chemicals were degrading the stratospheric ozone layer, world governments took action to deal with the problem. In 1987, the United Nations Environment Program (UNEP) organized an international meeting in Montreal, where intense negotiations led to a treaty called The Montreal Protocol on Substances That Deplete the Ozone Layer. The Montreal Protocol is an international agreement that committed all parties (signatory nations) to a schedule for phasing out the production and use of CFCs and other substances known to be harmful to the ozone layer. The treaty required the signatory nations to freeze their production and consumption of CFCs at 1986 levels by 1989, and to further reduce them to 50% of 1986 levels by 1998.<\/p>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">Initially, the governments of many countries were reluctant to ratify the protocol because they did not want to impose strict controls on the manufacturing and use of chemicals they thought were necessary for the functioning of their economies. This was particularly true for nations of the European Community, the former Soviet Union, and Japan. However, Canada, the U.S., Norway, and Sweden strongly advocated control measures, and they managed to convince the reluctant nations to phase out their use of ozone-depleting substances. The Montreal Protocol came into force on January 1, 1989, and was then ratified by 40 countries, which accounted for about 82% of the global use of CFCs.<\/p>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">The Montreal Protocol was subsequently improved by a series of amendments to eliminate the use of halons by 1994; of CFCs, methyl chloroform, HBFCs (hydrobromofluorocarbons), and carbon tetrachloride by 1996; of methyl bromide by 2010; and of HCFCs (hydrochlorofluorocarbons) by 2030. The amended protocol was ratified by many additional countries, including China and India, huge nations that had not participated in the initial negotiations. By 2009, 197 countries were parties to the Montreal Protocol, making it the first such treaty to achieve universal approval. The amendments also established the Montreal Protocol Multilateral Fund to provide financial support to help developing nations become rapidly less dependent on ozone-depleting chemicals.<\/p>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">The Montreal Protocol and its subsequent amendments have been called a \u201csuccess story\u201d in the regulatory control of pollution. Many developed countries accelerated and surpassed their original reduction targets, and less-developed countries have committed to not allowing the use of ozone-depleting substances in their economies. This success was achieved because of the following:<\/p>\n<ol>\n<li class=\"import-Normal2\" style=\"text-align: justify;\">There was international recognition of a clear threat to the global environment<\/li>\n<li class=\"import-Normal2\" style=\"text-align: justify;\">The threat was associated with particular substances that could be easily controlled, as they were manufactured in only a few places and were used for relatively discrete purposes<\/li>\n<li class=\"import-Normal2\" style=\"text-align: justify;\">Economically acceptable substitutes were quickly developed to replace the uses of ozone-depleting substances<\/li>\n<\/ol>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">In summary, rigorous information, effective international and national institutions, a spirit of cooperation, effective leadership by inspired leaders, and the availability of alternative technologies combined to bridge political differences in favor of the pursuit of a shared environmental interest. This is why the Montreal Protocol and its implementation are a success story of environmental regulatory action.<\/p>\n<\/div>\n<h1 class=\"import-Normal2\">Air Pollution and Health<\/h1>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">An extraordinary case of a natural emission of gas causing human deaths involved the release of a large volume of CO<sub>2<\/sub>\u00a0from a lake in Cameroon, West Africa. Lake Nyos is a 200-m-deep volcanic lake in which the deep waters are naturally supersaturated with CO<sub>2<\/sub>, similar to bottled soda water. One night in 1986, a large amount of sediment apparently slumped into the steep-sided lake, causing some of its bottom water to churn to the surface. The water de-gassed its CO<sub>2<\/sub>\u00a0content as a dense air mass, which then flowed into low areas in the surrounding landscape. The CO<sub>2<\/sub>-rich air asphyxiated about 1,700 sleeping people and 3,500 livestock as far as 25 km from the lake, plus uncounted wild animals. Atmospheric CO<sub>2<\/sub>\u00a0is capable of causing severe toxicity at concentrations greater than 8-10%; its \u201cnormal\u201d level is about 0.04%. Plants are much less vulnerable to CO<sub>2<\/sub>\u00a0toxicity, so no vegetation was damaged by this rare and astonishing natural event.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Anthropogenic emissions of other gaseous pollutants have sometimes caused increases in human mortality and diseases. Some people, especially those with chronic respiratory or heart diseases, are especially vulnerable to the effects of air pollution. Exposures of people to toxic gases can occur within several contexts, including the following.<\/p>\n<ul>\n<li class=\"import-Normal2\">The ambient environment: The urban atmosphere typically contains relatively high concentrations of potentially toxic chemicals. This is true in general, but air quality is especially bad during smog events, often caused by poor dispersion during an atmospheric inversion (Image 20.1). Consequently, city people living their normal lives are routinely exposed to higher concentrations of air pollutants than those living in cleaner, rural environments.<\/li>\n<li class=\"import-Normal2\">The working environment: Many people are exposed to high concentrations of pollutants as a consequence of their occupation. Of course, the specific exposures depend on the job \u2013 workers in metal smelters may be exposed to sulfur dioxide and metallic particulates, auto mechanics may be affected by exhaust fumes containing carbon monoxide and hydrocarbons, and laboratory workers may inhale various organic solvents.<\/li>\n<li class=\"import-Normal2\">The indoor environment: Buildings are often contaminated by gases and fumes. For example, space heaters, furnaces, and fireplaces burning wood, kerosene, or fuel oil may emit carbon monoxide into the indoor environment. All high-temperature combustions emit nitric oxide, and many synthetic materials and fabrics vent formaldehyde and other organic vapors. These chemicals can accumulate if indoor air is not exchanged frequently with cleaner, outdoor air.<\/li>\n<li class=\"import-Normal2\">Tobacco smoke: The smoking of tobacco is a leading source of easily avoidable air pollution. Smoking is also the most important cause of preventable diseases, especially lung cancer and heart disease (see Chapter 19). People inhale a great variety of toxic gases and fumes when they smoke tobacco (and also marijuana). In addition, non-smokers are indirectly exposed to lower concentrations of those chemicals because of the lingering residues of \u201csecond-hand smoke\u201d that may occur in indoor atmospheres.<\/li>\n<\/ul>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/5337\/2021\/07\/02104259\/image6.jpeg\" alt=\"image\" width=\"770\" height=\"333\" \/><\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Image 20.1. Smog in Denver, Colorado. Smog is becoming a growing problem in the western United States due to increased pollution from Asia. Source: National Renewable Energy Laboratory via <a href=\"https:\/\/research.noaa.gov\/News\/Scientist-Profile\/ArtMID\/536\/ArticleID\/226\/Rural-West-sees-more-smog-now-scientists-may-know-why\">NOAA<\/a>.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">All of these exposures to air pollutants have important implications for human health. However, the pollution of the ambient urban environment is the focus of the following paragraphs.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Since the beginning of the Industrial Revolution in Western Europe in the mid-18th century, people living in cities and working in certain types of factories have been exposed to high concentrations of air pollutants. Especially important have been sulfur dioxide, soot, and other emissions associated with the combustion of coal and other fossil fuels. The most severe exposures to pollutants in urban environments typically occurred during prolonged atmospheric inversions, which prevent the dispersion of emissions and result in smogs rich in SO<sub>2<\/sub>\u00a0and particulates.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Coal has long been used in many places to heat homes and other buildings. The associated emissions have been regarded as a problem in cities and towns in Europe since at least 1500. With the beginning of the Industrial Revolution, which initially used coal as its principal energy source, air pollution worsened markedly. The first convincing link between air pollution and a substantial increase in the death rate of an exposed human population was made in 1909, in relation to a noxious smog during an inversion in Glasgow, Scotland, when about one-thousand deaths may have been caused.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">The most infamous \u201ckiller smog\u201d in North America occurred in 1948 in Donora, Pennsylvania. An inversion and fog persisted in the Donora Valley for four days, but emissions from several factories continued, resulting in a build-up of high concentrations of SO<sub>2<\/sub>\u00a0and particulates in the atmosphere. The smog resulted in increased mortality in the local population (20 deaths in a population of only 14 100). An additional 43% of the population became ill, 10% severely so. The most common symptoms were irritation of the eyes and respiratory tract, sometimes accompanied by coughing, headache, and vomiting.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">The world\u2019s most notorious killer smog afflicted London, England, in 1952, when an extensive inversion and fog stabilized over southern England. In London, emissions of pollutants, mostly from coal combustion, transformed the natural \u201cwhite fog\u201d into a venomous \u201cblack fog.\u201d Visibility was terrible \u2013 people lost their way while walking or driving, even falling off wharves into the Thames River, and airplanes became lost while trying to taxi at the airport. The smog lasted for four days, but it was followed by another 14 days with a higher-than-usual death rate. Overall, about 3,900 deaths were attributed to this episode of noxious pollution. Most of the affected people were elderly or very young, or had pre-existing respiratory or heart diseases.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Until the early 1960s, severe episodes of urban air pollution were common in the cities of North America and Western Europe. Most of the smogs were caused by the widespread burning of coal in fireplaces and furnaces in homes, electrical utilities, and factories. The poor-quality urban air affected the health of people and animals and also damaged vegetation. In many cities, only certain kinds of plants that can tolerate air pollution could grow. Examples of pollution-tolerant trees that are commonly grown in urban America include black locust (<em>Robinia pseudoacacia<\/em>), honey locust (<em>Gleditsia triacanthos<\/em>), salt cedar (<em>Tamarix<\/em>), linden (<em>Tilia europaea<\/em>), tree-of-heaven (<em>Ailanthus altissima<\/em>), and ginkgo (<em>Ginkgo biloba<\/em>) (Heggestad et al., 1972).<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">To deal with the problems of this kind of smog, governments brought in legislation that has required large reductions in the emissions of air pollutants, particularly in cities. In Canada, for example, the enactment of various federal, provincial, and municipal laws related to air emissions has substantially improved urban air quality. Air quality has been similarly improved under legislation enacted in the U.S., Britain, and other wealthier countries since the 1960s.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Of course, the killer smogs were particularly severe events of air pollution. More typically, the urban atmosphere is contaminated by much smaller concentrations of SO<sub>2<\/sub>, NO<sub>x<\/sub>, O<sub>3<\/sub>, volatile organic compounds, and particulates. Many studies have investigated the effects of chronic exposures to those lower exposures to air contaminants on human health. The results of some studies suggest that modern urban air quality is sufficiently degraded to cause chronic damage to human health, especially by increasing the incidences of lung disease, asthma, and eye irritation. However, other studies have not found this to be the case. In any event, effective actions have been taken in the U.S. and other relatively wealthy nations. Visibly threatening, even lethal, episodes of air pollution like those described above no longer occur in those countries, although they could return if control standards were relaxed.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Unfortunately, in the cities of countries with rapidly growing economies, such as Brazil, China, India, Indonesia, and Mexico, poorly regulated industrial and urban growth is resulting in awful declines in air quality. Although not yet well studied in terms of human diseases, these appear to be modern tragedies of urban air pollution.<\/p>\n<div class=\"textbox shaded\">\n<h3 class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">American Focus 20.1. Smog in American Cities<\/h3>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">Smog is a serious problem in many cities and also in some rural areas because of LRTAP from urban areas. Smog is typically characterized as a noxious mixture of pollutants visible as a brownish-yellow or greyish-white haze. The key components are the following:<\/p>\n<ul>\n<li class=\"import-Normal2\" style=\"text-align: justify;\">O<sub>3<\/sub>\u00a0gas, along with SO<sub>2<\/sub>\u00a0and NO<sub>x<\/sub><\/li>\n<li class=\"import-Normal2\" style=\"text-align: justify;\">Organic vapors<\/li>\n<li class=\"import-Normal2\" style=\"text-align: justify;\">Fine particulates (&lt; 10 \u00b5m diameter), including acidic droplets of H<sub>2<\/sub>SO<sub>4<\/sub>\u00a0and HNO<sub>3<\/sub>, particulates of NH<sub>4<\/sub>NO<sub>3<\/sub>\u00a0and (NH<sub>4<\/sub>)<sub>2<\/sub>SO<sub>4<\/sub>, and organics from diesel exhaust and other combustion sources<\/li>\n<\/ul>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">Smog is widely regarded as a major cause of environmental damage, because it causes toxicity to vegetation and deteriorates building surfaces and other materials. Smog is also known to cause diseases and discomfort in many people. The elderly and children are especially vulnerable, as are people with existing heart or lung diseases (particularly asthma, bronchitis, and emphysema). Even healthy adults, however, may be affected on days with severe smog. The key causes of toxicity are ozone, other gases, and the finest particulates (&lt;2.5 \u00b5m), which can penetrate into the smallest lung cavities (known as alveoli) and cause irritation and other problems.<\/p>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">However, the data showing an association of smog and human diseases are epidemiological \u2013 that is, they involve discovering statistical relationships among the concentrations of atmospheric pollutants and the prevalence of certain maladies. In the U.S. for example, there is a predictable increase in hospital admissions of people suffering from respiratory ailments at times when concentrations of ozone and\/or sulfate particulates are high. Although it is rarely possible to link a specific disease in a particular person to an exposure to air pollution, it is estimated with no change in regulatory controls, ozone and particulate pollution will lead to 1,000 to 4,300 additional premature deaths each year by 2050 (CDC, 2020).<\/p>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">Because of the importance of smog as a stressor of urban Americans, state governments have initiated programs to monitor air pollutants and predict their concentrations so that \u201csmog alerts\u201d can be issued to the public. For example, New York State Department of Environmental Conservation and the State Department of Health issued an advisory for ozone in the Long Island region in 2019 with recommendations on ways to reduce ozone pollution such as using mass transit instead of individual cars and increasing use of fans to circulate air (DEC, 2019). These advisories encourage people to use different energy-saving and pollution-reducing steps, and provide warnings for specific times of the day when the pollutant threat will be the greatest.<\/p>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\">In 2020, Los Angeles experienced some of its worst air quality and smog events (Figure 20.7). Historically, this city has suffered from poor air quality and, still today, it remains one of the most polluted regions in the U.S. Throughout the year, Los Angeles averaged an air quality index rating of \u201cModerate,\u201d however on September 6, 2020, the air quality index ranged from \u201cUnhealthy\u201d to \u201cVery Unhealthy\u201d (EPA 2020). This poor air quality, specifically the particulate pollution levels, causes over 9,000 deaths each year in California (Frias, 2016). Los Angeles still has much work to do to meet the U.S. EPA\u2019s national air quality standards and the California Ambient Air Quality Standards.<\/p>\n<p class=\"import-Normal2\" style=\"text-align: justify; text-justify: inter-ideograph; margin-right: 24pt;\"><img decoding=\"async\" class=\"aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/5337\/2021\/07\/02104301\/image7.png\" alt=\"image\" width=\"659.066666666667px\" height=\"366.733333333333px\" \/><\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 24pt;\">Figure 20.7. Archived Map of Air Quality Index Records. This map details the record for the U.S. Air Quality Index for September 6, 2020. This date was the worst day of air quality for Los Angeles in 2020. On this date, Los Angeles air quality ranged from \u201cUnhealthy\u201d to \u201cVery Unhealthy.\u201d Source: <a href=\"https:\/\/gispub.epa.gov\/airnow\/\">EPA<\/a>.<\/p>\n<\/div>\n<h1 class=\"import-Normal2\">Conclusions<\/h1>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Gaseous air pollutants, such as sulfur dioxide and nitric oxide, are emitted from a variety of sources, which range from large power plants and smelters to individual automobiles and home furnaces. In contrast, secondary pollutants such as ozone are not emitted but are formed in the atmosphere by photochemical reactions involving sunlight and emitted oxides of nitrogen and hydrocarbons. If their concentrations are high enough, gaseous pollutants (often in combination with particulates) can be a risk to human health, and they may cause severe ecological damage. Because these risks are now well known, many governments have taken steps to reduce the emissions of the most important air pollutants. This is particularly the case for relatively developed countries, such as the U.S. Although the emissions of air pollutants in wealthy countries remain large, they are generally stabilizing or even decreasing. However, in rapidly growing economies, such as China and India, hasty and poorly controlled industrialization is resulting in rapidly worsening air pollution.<\/p>\n<h1 class=\"import-Normal2\">Questions for Review<\/h1>\n<ol>\n<li class=\"import-Normal2\">Compare the natural and anthropogenic emissions of sulfur and nitrogen compounds. Why do the sources of emission vary between regions and countries?<\/li>\n<li class=\"import-Normal2\">Why are high concentrations of ozone in the lower atmosphere considered an environmental problem? Why does this differ from the stratosphere, where too little ozone is a problem?<\/li>\n<li class=\"import-Normal2\">Explain the differences between primary and secondary air pollutants? Give examples of each.<\/li>\n<li class=\"import-Normal2\">Why has air pollution decreased so much in the eastern U.S., and what have been the ecological responses to this environmental improvement?<\/li>\n<\/ol>\n<h1 class=\"import-Normal2\">Questions for Discussion<\/h1>\n<ol>\n<li class=\"import-Normal2\">Existing clean-air technologies could be used to greatly reduce the emissions of air pollutants everywhere. Considering the damage that pollutants cause to human health, ecosystems, and other values, why are these technologies not being used more extensively? Consider factors associated with economics, politics, scientific uncertainty about pollution damage, and the benefits of having cleaner air. Contrast the lack of action with the successes achieved in controlling the emissions of ozone-depleting substances through the Montreal Protocol.<\/li>\n<li class=\"import-Normal2\">Epidemiological (statistical) research suggests that human health may be affected by ambient levels of air pollutants in urban areas, particularly through increased incidences of respiratory diseases, such as asthma. However, the statistical data are rather weak, and only a relatively small proportion of the urban population appears to be affected. What are some issues that decision makers must consider when deliberating about additional controls on the release of air pollutants in urban areas?<\/li>\n<\/ol>\n<h1 class=\"import-Normal2\">Exploring Issues<\/h1>\n<ol>\n<li class=\"import-Normal2\">You have been asked to assess the potential ecological effects of building a new metal smelter in a region that is now wilderness. The smelter will emit sulfur dioxide to the atmosphere. Based on what you know about pollution damage, what would be the most important considerations to incorporate into the environmental impact assessment? Focus on the potential effects on terrestrial and aquatic ecosystems.<\/li>\n<\/ol>\n<h1 class=\"import-Normal2\">References Cited and Further Reading<\/h1>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Anderson, S.O. and K.M. Sarma. 2005. Protecting the Ozone Layer: The United Nations History. Earthscan Publications, London, UK.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Ayres, J. and R.L. Maynard. 2006. Air Pollution and Health. World Scientific Publishing Company.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Barker, J.R. and D.T. Tingey. 1992. Air Pollution Effects on Biodiversity. Van Nostrand Reinhold, New York, NY.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Brimblecombe, P. 1996. Air Composition and Chemistry. 2nd ed. Cambridge University Press, Cambridge, UK.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Brimblecombe, P. 2005. The Effects of Air Pollution on the Built Environment. Imperial College Press, London, UK.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Centers for Disease Control and Prevention. 2020. Air Pollution. Climate and Health, Centers for Disease Control and Prevention. <a class=\"rId23\">https:\/\/www.cdc.gov\/climateandhealth\/effects\/air_pollution.htm<\/a>. Accessed June 14, 2021.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Frias, L. 2016. County of Los Angeles Public Health, Environmental Health. <a class=\"rId24\">http:\/\/publichealth.lacounty.gov\/eh\/tea\/toxicepi\/criteriaairpollutants.htm<\/a>. Accessed June 14, 2021.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Department of Environmental Conservation (DEC) 2019. Air Quality Health Advisory Issued for Long Island. Department of Environmental Conservation, New York. <a class=\"rId25\">https:\/\/www.dec.ny.gov\/press\/117675.html<\/a>. Accessed June 14, 2021.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Environmental Protection Agency (EPA). 2019. Our Nation\u2019s Air. <a class=\"rId26\" href=\"#home\"><span class=\"import-Hyperlink\">https:\/\/gispub.epa.gov\/air\/trendsreport\/2020\/#home<\/span><\/a>. Accessed June 14, 2021.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Environmental Protection Agency (EPA). 2020a. NAAQS Table. <a class=\"rId27\">https:\/\/www.epa.gov\/criteria-air-pollutants\/naaqs-table<\/a>. Accessed June 14, 2021.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Environmental Protection Agency (EPA). 2020b. Overview of Greenhouse Gases, Methane Emissions. <a class=\"rId28\" href=\"#methane\">https:\/\/www.epa.gov\/ghgemissions\/overview-greenhouse-gases#methane<\/a>. Accessed June 14, 2021.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Environmental Protection Agency (EPA). 2020. Interactive Map of Air Quality. AirNow, U.S. Air Quality Index. <a class=\"rId29\">https:\/\/gispub.epa.gov\/airnow\/<\/a>. Accessed June 14, 2021.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Freedman, B. 1995. Environmental Ecology. 2nd ed. Academic Press, San Diego, CA.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Heggestad, H.E., Santamour, F.S., and Bernstein, L. 1972. Plants that will withstand pollution and reduce it. American Society of Landscape Architects Foundation, United States Department of Agriculture. 16-22 <a class=\"rId30\">https:\/\/naldc.nal.usda.gov\/catalog\/IND79000653<\/a>.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Hemond, H.F. and E.J. Fechner. 2014. Chemical Fate and Transport in the Environment. 3rd ed. Academic Press, San Diego, CA.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Hester, R.E. and R.M. Harrison. 1998. Air Pollution and Health. Royal Society of Chemistry, Cambridge, UK.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Holgate, S.T., J.M. Samet, R.L. Maynard, and H.S. Koren (eds.). 1999. Air Pollution and Health. Academic Press, San Diego, CA.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Parson. E. 2003. Protecting the Ozone Layer: Science and Strategy. Oxford University Press, Oxford, UK.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Pepper, I.L., C.P. Gerba, and M.L. Brusseau (eds.). 2006. Pollution Science, 2nd ed. Academic Press, San Diego, CA.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Roberts, T.M. 1984. Effects of air pollutants in agriculture and forestry. Atmospheric Environment, 18: 629-652.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Seinfeld, J.H. and S.H. Pandis. 2006. Atmospheric Chemistry and Physics: From Air Pollution to Climate Change, 2nd ed. Wiley-Interscience, New York, NY.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Shriner, D.S. 1990. Responses of vegetation to atmospheric deposition and air pollution. In Acidic Deposition: State of Science and Technology. Vol. III. Terrestrial, Materials, Health, and Visibility Effects. Superintendent of Documents, U.S. Government Printing Office, Washington, DC.<\/p>\n<p class=\"import-Normal2\" style=\"margin-right: 12pt;\">Thostenson, A., J.W. Enz, and V. 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