Acid rain

The effects of acid rain in the Jizera Mountains of the Czech Republic

Acid rain (or more accurately acid precipitation) 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, or sleet. This can increase the acidity of the soil, and affect the chemical balance of lakes and streams. The term "acid rain" is sometimes 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. Acid rain is defined as any type of precipitation with a pH that is unusually low. Dissolved carbon dioxide dissociates to form weak carbonic acid giving a pH of approximately 5.6 at typical atmospheric concentrations of CO₂. Therefore a pH of <5.6 has sometimes been used as a definition of acid rain. 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 <5 is a more appropriate definition.

The US EPA says, "Acid rain is a serious environmental problem that affects large parts of the US and Canada" 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.

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 pHs, so the numbers of diatoms found in layers of increasing depth give an indication of the change in pH over the years.

Since the industrial revolution, emissions of sulfur and nitrogen oxides to the atmosphere have increased. Occasional pH readings of well below 2.4 (the acidity of vinegar) have been reported in industrialized areas. Industrial acid rain is a substantial problem in the People's Republic of China, Eastern Europe, Russia and areas down-wind from them. These areas all burn sulfur-containing coal to generate heat and electricity. 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.

Acid rain was first reported in Manchester, England, which was an important city during the Industrial Revolution. In 1852, Robert Angus Smith found the relationship between acid rain and atmospheric pollution. The term "acid rain" was used for the first time by him in 1872. 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.

Emissions of chemicals leading to acidification

Volcanic injection.

The most important gas which leads to acidification is sulfur dioxide. Emissions of nitrogen oxides which are oxidised 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.

Natural emissions

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.

Human emissions

The principal cause of acid rain is sulfur and nitrogen compounds from human sources, such as electricity generation, factories and motor vehicles. The gases can be carried hundreds of miles in the atmosphere before they are converted to acids and deposited.

Gas phase chemistry

In the gas phase sulfur dioxide is oxidized by reaction with the hydroxyl radical via a termolecular reaction:

SO₂ + OH· → HOSO₂·

which is followed by:

HOSO₂· + O₂ → HO₂· + SO₃

In the presence of water sulfur trioxide is converted rapidly to sulfuric acid:

SO₃ + H₂O → H₂SO₄

Nitric acid is formed by the reaction of OH with Nitrogen dioxide:

NO₂ + OH· → HNO₃

For more information see Seinfeld and Pandis (1998).

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 of sulfur which oxidise it 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).

Aerosol formation

In the gas phase sulfuric and nitric can condense on existing aerosols or nucleate to form new aerosols. The nucleation process is an important source of new particles in the atmosphere and so emissions of sulfur containing compounds, as well as causing acidification also have a climate effect.

Acid deposition

Processes involved in acid deposition (note that only SO₂ and NO_x play a significant role in acid rain).

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.

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. This occurs when particles and gases stick to the ground, plants or other surfaces.

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.

Surface Waters and Aquatic Animals

Both the lower pH and higher aluminium 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.

Soils

Soil biology can be seriously damaged by acid rain. Some tropical microbes can quickly consume acids but other types of microbe 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 .

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 minimised 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.

Human health

Some scientists have suggested direct links to human health, but none have been proven.. 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. For more information on the health effects of aerosol see: Particulate#Health effects.

Other adverse effects

Acid rain can also cause damage to certain building materials and historical monuments. Acid rain can cause erosion on ancient and valuable statues and has caused considerable damage. This is because the sulfuric acid in the rain chemically reacts with the calcium 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. Visibility is also reduced by sulfate and nitrate in the atmosphere.

Prevention methods

Main article: emissions control

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 smoky 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.

International treaties

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

Emissions trading

An even more benign 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 main effect of this is to give operators real economic incentives to install pollution controls. Since public interest groups can retire the licenses by purchasing them, the net result is a continuously decreasing and more diffused set of pollution sources. At the same time, no particular operator is ever forced to spend money without a return of value from commercial sale of assets.

Further reading

• John McCormick, Acid Earth: The Global Threat of Acid Pollution (London: Earthscan, 1997).

External links

• National Acid Precipitation Assessment Program - a 98-page report to Congress
• Acid rain for schools
• U.S. Environmental Protection Agency - New England Acid Rain Program (superficial)
• Acid Rain (more depth than ref. above)
• U.S. Geological Survey - What is acid rain?
• Acid rain analysis - freeware for simulation and evaluation of titration curves and pH calculations
• CBC Digital Archives – Acid Rain: Pollution and Politics
• Larssen, Thorjørn et al. “Acid Rain in China”. Environmental Science and Technology, 40:2, 2006, pp 418-425.
• Assortment of Summaries on Acid Rain
• [http://www.hubbardbrook.org/education/Glossary/AcidRain.pdf Hubbard Brook Acid Rain Revisited

See also

• List of environment topics

Caroline says: hi