Acid rain how it is formed, composition, reactions and effects

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Alexander Pearson
Acid rain how it is formed, composition, reactions and effects

The acid rain It is the wet or dry precipitation of substances that generate a pH lower than 5.6. This precipitation can be wet (diluted in rainwater) or dry (depositions of particles or aerosols).

The term "acid rain" was first proposed by the English researcher Robert Angus Smith in 1850, in the middle of the Industrial Revolution. The most abundant acids that are formed in the atmosphere are nitric and sulfuric by oxidation of natural or artificial pollutants..

Acid rain map. Source: Alfredsito94 [CC BY-SA 4.0 (https://creativecommons.org/licenses/by-sa/4.0)]

The most relevant pollutants are oxides: NO2, NO3, SO2, whose natural sources are volcanic eruptions, forest fires and bacterial degradation. Artificial sources are gas emissions resulting from the burning of fossil fuels (industrial activity and automotive traffic).

Acid rain causes negative impacts on the environment such as acidification of soils and waters, affecting living beings, including humans. Likewise, soils and water are contaminated with heavy metals, and eutrophication occurs in water bodies..

At the vegetation level, direct damage to the leaves occurs and plant growth is affected. In addition, soil acidification immobilizes nutrients and affects mycorrhizae (soil fungi). Similarly, buildings, machinery, monuments and works of art exposed to the elements are seriously oxidized or eroded by the effect of precipitated acids..

To remedy the effect of acid rain, some essential measures can be taken such as protecting the monuments and correcting the acidification of soils and waters. However, the basic solution for acid rain is to reduce the emission into the atmosphere of chemical compounds that are precursors to the formation of acids..

Article index

  • 1 How is acid rain formed?
    • 1.1 Precursor chemicals
    • 1.2 Tropospheric process and acids produced
    • 1.3 Precipitation
  • 2 Composition
  • 3 Chemical reactions of acid rain
    • 3.1 Formation of sulfuric acid (H2SO4)
    • 3.2 Formation of nitric acid (HNO3)
  • 4 Effects on the environment
    • 4.1 Soil acidification and its effects on vegetation
    • 4.2 Effect on aquifers and human health
    • 4.3 Deterioration of buildings, monuments and materials
  • 5 Flora and fauna
    • 5.1 Plants and animals in lentic bodies of water
    • 5.2 Vegetation and nutrient availability
    • 5.3 Direct damage to plants and animals
  • 6 Solutions
    • 6.1 Reduce emissions
    • 6.2 Apply acidity correction measures
    • 6.3 Surface protection
  • 7 References

How acid rain is formed?

Acid fog due to SO2 emissions from the PDVSA refinery in Curaçao. Source: HdeK [CC BY-SA 3.0 (https://creativecommons.org/licenses/by-sa/3.0)]

Chemical precursor agents

The acid rain phenomenon begins with the emission into the atmosphere of chemical compounds that are precursors to the formation of acids. These compounds can be emitted by natural or artificial sources.

Natural sources include volcanic eruptions, vegetation fires, and ocean emissions. As artificial sources act industrial emissions, emissions from combustion motor vehicles or the burning of waste.

These sources emit various compounds that can generate acids in the atmosphere. However, the most important are nitrogen oxides and sulfur oxides.

Nitrogen oxides are known as NOx, and include nitrogen dioxide (NO2) and nitrous oxide (NO). For its part, sulfur oxide is SO2 or sulfur dioxide.

Tropospheric process and acids produced

The phenomenon of acid rain occurs in the troposphere (atmospheric zone that goes from the earth's surface to a height of 16 km).

In the troposphere, air currents can carry these compounds over any part of the planet, making it a global problem. In this process, nitrogen and sulfur oxides interact with other compounds to form nitric acid and sulfuric acid respectively..

Reaction support

Chemical reactions can be carried out either on solid particles in suspension or in drops of water in suspension..

Nitric acid is formed mainly in the gas phase, due to its low solubility in water. For its part, sulfuric acid is more soluble in water, being the main constituent of acid rain.

Nitric acid

For the formation of nitric acid (HNO3), nitrogen oxides react with water, with radicals such as OH (to a lesser extent with HO2 and CH3O2), or with tropospheric ozone (O3).

Sulfuric acid

In the case of the production of sulfuric acid (H2SO4) the radicals OH, HO2, CH3O2, water and ozone also participate. Additionally, it can be formed by reacting with hydrogen peroxide (H2O2) and various metal oxides..

Carbonic acid

H2CO3 is formed thanks to the photochemical reaction of carbon dioxide with atmospheric water.

Hydrochloric acid

HCl represents only 2% of acid rain, and its precursor is methyl chloride (ClCH3). This compound comes from the oceans and is oxidized by OH radicals to form hydrochloric acid..

Precipitation

Once the acidic compounds (nitric acid or sulfuric acid, and to a lesser extent hydrochloric acid) have been formed, they will precipitate.

Precipitation can be by deposition of the suspended particles in which the acidification reaction has taken place in the gas phase. Another way is that in the rain the condensed water where the acids were formed precipitates.

Composition

The natural acidity of rain is close to a pH of 5.6, although in some uncontaminated areas values ​​of 5. These low pH values ​​have been associated with the presence of acids of natural origin..

It is considered that depending on the pH level, rain can be classified into:

a) Slightly acidic (pH between 4.7 and 5.6)
b) Medium acidic (pH between 4.3 and 4.7)
c) Strongly acidic (pH less than or equal to 4.3).

If the rain has a concentration> 1.3 mg / L of nitrates and> 3 mg / L in the case of sulfates, the contamination is considered to be high.

Acid rain is composed in more than two thirds of cases by the presence of sulfuric acid, followed in abundance by nitric acid. Other components that can contribute to the acidity of the rain are hydrochloric acid and carbonic acid..

Chemical reactions of acid rain

Formation of sulfuric acid (H2SO4)

Sulfuric acid production can occur in the gas phase or in the liquid phase.

Gas phase

Only 3-4% of SO2 is oxidized in the gas phase to produce sulfuric acid. There are many routes for the formation of sulfuric acid from gaseous precursors, here the reaction of SO2 with tropospheric ozone is shown.

The reaction occurs in two stages:

1.- Sulfur dioxide reacts with tropospheric ozone generating sulfur trioxide and releasing oxygen.

SO2 + O3 = SO3 + O2

2.- Then the sulfur trioxide is oxidized with water vapor and produces sulfuric acid.

SO3 + H2O = H2SO4

Liquid phase

Sulfuric acid can be produced in several ways in the drops of water that will form the rain:

1.- SO2 dissolves in water generating sulfurous acid, and this is oxidized by hydrogen peroxide:

SO2 + H2O = H2SO2

H2SO2 + H2O2 = H2SO4 + H2O

2.- Photocatalytic mechanism: In this case metal oxide particles (iron, zinc, titanium) are activated thanks to the action of sunlight (photochemical activation) and oxidize SO2 generating sulfuric acid.

Nitric acid (HNO3) formation

Tropospheric ozone O3 produces the transformation of NO2 to HNO3 in a three-stage process:

1.- NO2 + O3 = NO3 + O2
2.- NO3 + NO2 = N2O5
3.- N2O5 + H2O = 2HNO3

Effects on the environment

Effect of acid rain in a forest in the Jizera Mountains in the Czech Republic. Source: Lovecz [Public domain]

Soil acidification and its effects on vegetation

The effect of acid rain on the soil varies depending on its composition. For example, soils of calcareous, basaltic and igneous origin have a greater capacity to neutralize acidity..

For their part, soils rich in quartz as an inert material are not capable of regulating the acid content. Thus, in soils where acid rain increases acidity, metal ions that are toxic to plants and animals are released and carried away..

A relevant case is the dissolution of aluminosilicates, which release aluminum ions that are very harmful to vegetation..

In general, the acidity of the soil reduces the availability of nutrients for plants. In addition, it promotes the release and washing of calcium, which causes deficiencies in plants.

Effect on aquifers and human health

In most cases, acid rain does not look or taste different from normal rain, nor does it generate sensations on the skin. Its effects on human health are indirect, and it rarely causes skin damage due to extreme acidity..

One of the problems with acid rain is that by lowering pH values ​​below 5, heavy metals are released and carried away. These pollutants such as aluminum and cadmium can enter underground aquifers.

If the water from these contaminated aquifers passes into wells used for human consumption, it can cause serious damage to health.

Deterioration of buildings, monuments and materials

Gargoyle damaged by acid rain. Source: Nino Barbieri [CC BY-SA 3.0 (http://creativecommons.org/licenses/by-sa/3.0/)]

Calcareous type stones

Constructions, monuments and sculptures made with limestone or marble are severely affected by acid rain. This is quite serious, since many historical buildings and works of art are built with these materials..

In the case of limestone, acid rain causes dissolution of limestone and causes recrystallization of calcite. This recrystallization produces whitish tones on the surface..

In the specific case of rain with sulfuric acid, the phenomenon of sulfation occurs. Through this process, the rock surface is transformed into gypsum and CO2 is released..

Marble, although more resistant, is also affected by acid rain. In this case, the exfoliation of the stone occurs, which is why superficial layers of it are detached.

Other non-corrosive materials

In some buildings the structural deterioration is minor, but also with negative effects. For example, dry acid deposits make walls dirty, increasing maintenance costs.

Metals

Acid rain causes corrosion of metals due to the phenomenon of oxidation. This causes enormous economic losses, since structures, equipment, machinery and vehicles with metal parts are seriously affected..

Flora and fauna

Fish killed by acid rain. Source: United States Fish and Wildlife Service. [Public domain]

Acid rain modifies the natural balance of aquatic and terrestrial ecosystems.

Plants and animals in lentic bodies of water

Lentic bodies of water are more susceptible to acidification, because they are closed ecosystems. In addition, the accumulation of acids in the water has negative consequences on the life it harbors..

Another consequence of acidification is the precipitation of nitrates through rain, which causes eutrophication in bodies of water. Excess nutrients reduce available oxygen and negatively affect aquatic animal survival.

Another indirect negative effect is the entrainment of heavy metal ions from the terrestrial environment into water bodies. These ions are released into the soil by the action of hydronium ions when the acidity increases..

Vegetation and nutrient availability

The most serious problems caused by soil acidification are the immobility of essential nutrients and the increase in toxic metals..

For example, aluminum and magnesium are released from soil particles by being replaced by hydrogen. Aluminum affects the structure and function of the roots and reduces the absorption of calcium essential for plants.

On the other hand, soil acidification causes damage to mycorrhizae (root-associated fungi), which are essential in the dynamics of the forest..

Direct damage to plants and animals

Sulfuric acid causes direct damage to leaves by degrading chlorophyll and producing chlorosis (yellowing of the leaf). In some species growth and production of viable seeds decrease.

Amphibians (frogs and toads) are particularly susceptible to the effects of acidity in the water. Some damages are direct injuries and decreased defense against pathogens (especially skin fungi).

Solutions

Reduce emissions

The bottom line for acid rain is to reduce releases to the environment of acid precursor chemicals. The most important of these are sulfur and nitrogen oxides.

However, this has some difficulties, since it implies affecting the economic and development interests of companies and countries. For example, one of the main sources of sulfur dioxide is the burning of coal, which represents more than 70% of energy in China..

There are some technological alternatives that can help reduce emissions. For example, in industry the so-called “fluidized beds” incorporate absorbents (limestone or dolomite) that retain SO2. In the case of motor vehicles and combustion engines in general, catalytic converters comply also help to reduce SO2 emissions.

On the other hand, some countries have been implementing specific acid rain reduction programs. For example, the United States developed the National Acid Precipitation Assessment Program (NAPAP). Among some of the measures contemplated by the NAPAP is the implementation of the use of low sulfur fuels.

Another possible measure is the replacement of the vehicle fleet by electric cars to reduce both acid rain and global warming. However, although the technology exists to achieve this, pressure from the automotive and oil industries has delayed decisions in this regard. Other factors that influence are cultural elements related to the speed that a vehicle is expected to reach..

Apply acidity correction measures

In some cases, the pH of soils and waters can be increased by adding alkalis, for example by incorporating large amounts of lime. However, this practice is not feasible in very large areas of land..

Surface protection

Stone

There are various methods to protect or at least reduce the deterioration of the stone under the effect of acid rain. One of these methods is to wash it with steam or hot water..

Chemical agents such as hydrofluoric acid or ammonium bifluoride can also be used. Once washed, the stone can be sealed by applying special products that clog pores, such as barium hydroxide.

Metal

Corroded metal surfaces can be protected by coating with a non-corrosive metal such as zinc..

For this, electrodeposition can be applied, or the metal structure to be protected can be immersed in the protective metal in liquid state..

References

  1. Espada L and A. Sánchez (1995). Influence of acid rain on the corrosion of metals. pp. 145-171. In: Sastre de Vicente M. (Coord.) Electrochemistry and environment on the threshold of the XXI century. University of La Coruña. Publications Service. La Coruña, Spain.
  2. García-Ruiz G (2018). Protection of building structures in corrosive atmospheres. End of Degree Project in Engineering in Industrial Technologies. Polytechnic University of Cartagena. Higher Technical School of Industrial Engineering. Cartagena, Spain. 75 p.
  3. Granados-Sánchez D, GF López-Ríos and MA Hernández-García (2010). Acid rain and forest ecosystems… Chapingo Magazine Forestry and Environmental Sciences Series 16: 187-206.
  4. Likens GE, CT Driscoll and DC Buso (1996). Long-Term Effects of Acid Rain: Response and Recovery of a Forest Ecosystem. Science, 272; 244-246.
    Likens GE and FH Bormann (1974). Acid Rain: A Serious Regional Environmental Problem. Science, 184: 1176-1179.
  5. Schindler DW (1988). Effects of Acid Rain on Freshwater Ecosystems. Science, 239: 149-157.
  6. Vélez-Upegui JJ, MC Valencia-Giraldo, A Londoño-Carvajal, CM González-Duque, JP Mariscal-Moreno (2010). Air pollution and acid rain. Diagnosis of the phenomenon in the city of Manizales. Faculty of Engineering and Architecture. National university of Colombia. Manizales headquarters. Editorial Blanecolor Ltda. First edition. Manizales, Colombia. 150 p.

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