Acid rain

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The term acid rain or more accurately acid precipitation is commonly used to mean the deposition of acidic components in rain, snow, dew, or dry particles.^[1] Acid rain occurs when sulfur dioxide and nitrogen oxides are emitted into the atmosphere, undergo chemical transformations, and are absorbed by water droplets in clouds. The droplets then fall to earth as rain, snow, mist, dry dust, hail, or sleet. This increases the acidity of the soil, and affects the chemical balance of lakes and streams.^[2]

The term "acid rain" is often used more generally to include all forms of acid deposition — both wet deposition, where acidic gases and particles are removed by rain or other precipitation, and dry deposition removal of gases and particles to the Earth's surface in the absence of precipitation.^[3]

Acid rain is defined as any type of precipitation with a pH that is unusually low.^[4] Dissolved carbon dioxide dissociates to form weak carbonic acid giving a pH of approximately 5.6 at typical atmospheric concentrations of CO₂.^[5] Therefore a pH of less than 5.6 has sometimes been used as a definition of acid rain.^[6] However, natural sources of acidity mean that in remote areas, rain has a pH which is between 4.5 and 5.6 with an average value of 5.0 and so rain with a pH of less than 5 is a more appropriate definition.^[7] The US EPA says, "Acid rain is a serious environmental problem that affects large parts of the US and Canada" ^[8] Acid rain accelerates weathering in carbonate rocks and accelerates building weathering. It also contributes to acidification of rivers, streams, and forest damage at high elevations. When the acid builds up in rivers and streams, it can kill fish.

[edit] History and trends

Evidence for an increase in the levels of acid rain comes from analyzing layers of glacial ice. These show a sudden decrease in pH from the start of the Industrial Revolution of 6 to 4.5 or 4. Other information has been gathered from studying organisms known as diatoms which inhabit ponds. Over the years these die and are deposited in layers of sediment on the bottoms of the ponds. Diatoms thrive in certain pH levels, so the numbers of diatoms found in sediment layers of increasing depth give an indication of the change in pH over the years.^[9]

Since the industrial revolution, emissions of sulfur and nitrogen oxides to the atmosphere have increased.^[10] Occasional pH readings of well below 2.4 (the acidity of vinegar) have been reported in industrialized areas.^[10] Industrial acid rain is a substantial problem in the People's Republic of China^[11], Eastern Europe, Russia and areas down-wind from them. These areas all burn sulfur-containing coal to generate heat and electricity.^[12] The problem of acid rain not only has increased with population and industrial growth, but has become more widespread. The use of tall smokestacks to reduce local pollution has contributed to the spread of acid rain by releasing gases into regional atmospheric circulation. Often deposition occurs a considerable distance downwind of the emissions, with mountainous regions tending to receive the most (simply because of their higher rainfall). An example of this effect is the low pH of rain (compared to the local emissions) which falls in Scandinavia.^[13]

Acid rain was first found in Manchester, England. In 1852, Robert Angus Smith found the relationship between acid rain and atmospheric pollution.^[5] Though acid rain was discovered in 1852, it wasn't until the late 1960s that scientists began widely observing and studying the phenomenon. Canadian Harold Harvey was among the first to research a "dead" lake. Public awareness of acid rain in the U.S increased in the 1990s after the New York Times promulgated reports from the Hubbard Brook Experimental Forest in New Hampshire of the myriad deleterious environmental effects demonstrated to result from it.^[14]

[edit] Emissions of chemicals leading to acidification

The most important gas which leads to acidification is sulfur dioxide. Emissions of nitrogen oxides which are oxidized to form nitric acid are of increasing importance due to stricter controls on emissions of sulfur containing compounds. 70 Tg(S) per year in the form of SO₂ comes from fossil fuel combustion and industry, 2.8 Tg(S) from wildfires and 7-8 Tg(S) per year from volcanoes.^[15]

[edit] Natural phenomena

The principal natural phenomena that contribute acid-producing gases to the atmosphere are emissions from volcanoes and those from biological processes that occur on the land, in wetlands, and in the oceans. The major biological source of sulfur containing compounds is dimethyl sulfide.

The effects of acidic deposits have been detected in glacial ice thousands of years old in remote parts of the globe.

[edit] Human activity

The principal cause of acid rain is sulfuric and nitrogen compounds from human sources, such as electricity generation, factories and motor vehicles. Coal power plants are one of the most polluting. The gases can be carried hundreds of kilometres in the atmosphere before they are converted to acids and deposited. Factories used to have short funnels to let out smoke, but this caused many problems, so now, factories have longer smoke funnels. The problem with this is those pollutants get carried far off, where it creates more destruction.

[edit] Chemistry in cloud droplets

When clouds are present the loss rate of SO₂ is faster than can be explained by gas phase chemistry alone. This is due to reactions in the liquid water droplets

Hydrolysis

Sulfur dioxide dissolves in water and then, like carbon dioxide, hydrolyses in a series of equilibrium reactions:

SO₂ (g)+ H₂O ⇌ SO₂·H₂O

SO₂·H₂O ⇌ H⁺+HSO₃^-

HSO₃^- ⇌ H⁺+SO₃^2-

Oxidation

There are a large number of aqueous reactions that oxidize sulfur from S(IV) to S(VI), leading to the formation of sulfuric acid. The most important oxidation reactions are with ozone, hydrogen peroxide and oxygen (reactions with oxygen are catalysed by iron and manganese in the cloud droplets).

For more information see Seinfeld and Pandis (1998).^[5]

[edit] Acid deposition

[edit] Wet deposition

Wet deposition of acids occurs when any form of precipitation (rain, snow, etc) removes acids from the atmosphere and delivers it to the Earth's surface. This can result from the deposition of acids produced in the raindrops (see aqueous phase chemistry above) or by the precipitation removing the acids either in clouds or below clouds. Wet removal of both gases and aerosol are both of importance for wet deposition.

[edit] Dry deposition

Acid deposition also occurs via dry deposition in the absence of precipitation. This can be responsible for as much as 20 to 60% of total acid deposition.^[6] This occurs when particles and gases stick to the ground, plants or other surfaces.

[edit] Adverse effects

Acid rain has been shown to have adverse impacts on forests, freshwaters and soils, killing off insect and aquatic lifeforms as well as causing damage to buildings and having possible impacts on human health.

[edit] Surface waters and aquatic animals

Both the lower pH and higher aluminum concentrations in surface water that occur as a result of acid rain can cause damage to fish and other aquatic animals. At pHs lower than 5 most fish eggs will not hatch and lower pHs can kill adult fish. As lakes become more acidic biodiversity is reduced. Acid rain has eliminated insect life and some fish species, including the brook trout in some Appalachian streams and creeks.^[16] There has been some debate on the extent to which man-made causes of lake acidity have cause fish kills - for example Edward Krug.^[17].

[edit] Soils

Soil biology can be seriously damaged by acid rain. Some tropical microbes can quickly consume acids^[18] but other microbes are unable to tolerate low pHs and are killed. The enzymes of these microbes are denatured (changed in shape so they no longer function) by the acid. The hydronium ions of acid rain also mobilize toxins and leach away essential nutrients and minerals^[19]

[edit] Forests and other vegetation

Acid rain can slow the growth of forests, cause leaves and needles to turn brown and fall off and die. In extreme cases trees or whole areas of forest can die. The death of trees is not usually a direct result of acid rain, often it weakens trees and makes them more susceptible to other threats. Damage to soils (see above) can also cause problems. High altitude forests are especially vulnerable as they are often surrounded by clouds and fog which are more acidic than rain.

Other plants can also be damaged by acid rain but the effect on food crops is minimized by the application of fertilizers to replace lost nutrients. In cultivated areas, limestone may also be added to increase the ability of the soil to keep the pH stable, but this tactic is largely unusable in the case of wilderness lands. Acid Rain depletes minerals from the soil and then it stunts the growth of the plant.

[edit] Human health

Some scientists have suggested direct links to human health, but none have been proven.^[2]. However, fine particles, a large fraction of which are formed from the same gases as acid rain (sulfur dioxide and nitrogen dioxide), have been shown to cause illness and premature deaths such as cancer and other deadly diseases^[20] For more information on the health effects of aerosol see: Particulate#Health effects.

[edit] Other adverse effects

Acid rain can also cause damage to certain building materials and historical monuments. Acid rain can cause weathering on ancient and valuable statues and has caused considerable damage. This is because the sulfuric acid in the rain chemically reacts with the calcium compounds in the stones (limestone, sandstone, marble and granite) to create gypsum, which then flakes off. This is also commonly seen on old gravestones where the acid rain can cause the inscription to become completely illegible. Acid rain also causes an increased rate of oxidation for iron.^[21] Visibility is also reduced by sulfate and nitrate in the atmosphere.^[22]

[edit] Prevention methods

Main article: Automobile emissions control

[edit] Technical solutions

In the United States, many coal-burning power plants use Flue gas desulfurization (FGD) to remove sulfur-containing gases from their stack gases. An example of FGD is the wet scrubber which is commonly used in the U.S. and many other countries. A wet scrubber is basically a reaction tower equipped with a fan that extracts hot smoke stack gases from a power plant into the tower. Lime or limestone in slurry form is also injected into the tower to mix with the stack gases and combine with the sulfur dioxide present. The calcium carbonate of the limestone produces pH-neutral calcium sulfate that is physically removed from the scrubber. That is, the scrubber turns sulfur pollution into industrial sulfates.

In some areas the sulfates are sold to chemical companies as gypsum when the purity of calcium sulfate is high. In others, they are placed in landfill. However, the effects of acid rain can last for generations, as the effects of pH level change can stimulate the continued leaching of undesirable chemicals into otherwise pristine water sources, killing off vulnerable insect and fish species and blocking efforts to restore native life.

[edit] International treaties

A number of international treaties on the long range transport of atmospheric pollutants have been agreed e.g. Sulphur Emissions Reduction Protocol under the Convention on Long-Range Transboundary Air Pollution.

[edit] Emissions trading

A more recent regulatory scheme involves emissions trading. In this scheme, every current polluting facility is given an emissions license that becomes part of capital equipment. Operators can then install pollution control equipment, and sell parts of their emissions licenses. The intention of this is to give operators economic incentives to install pollution controls.