1.

Biogeochemical Cycles
It is the natural circulation pathways of the essential elements of living matter. These elements flow from the abiotic to biotic components of the biosphere and back to the abiotic component again. For the survival of living components of a major ecosystem like forest, all the chemical elements that make up living cells need to be recycled continuously.
1.1

Sulfur Cycle

The essential steps of the sulfur cycle are

Mineralization of organic sulfur to the inorganic form, hydrogen sulfide, H2S. Oxidation of sulfide and elemental sulfur (S) and related compounds to sulfate, SO42. Reduction of sulfate to sulfide. Microbial immobilization of the sulfur compounds and subsequent incorporation into

the organic form of sulfur

Figure 1: Processes of Sulfur Cycle

1.2
Seral No.

Key Processes and Prokaryotes in the Sulfur Cycle

Process Sulfide/ Sulfur oxidation (H2SS0 SO42-) Organisms

1.

Aerobic Anaerobic

Sulfur chemolithotrophs (Thiobacillus, Beggiatoa etc) Purple and green phototrophic bacteria, some chemolithotrophs Desulfovibrio, Desulfobacter Desulfuromonas, many hyperthermophilic Archea Desulfovibrio etc Many organisms can do this Many organisms can do this

2. 3. 4. 5. 6.

Sulfate reduction (anaerobic) (SO42-H2S) Sulfur reduction (anaerobic) (S0H2S) Sulfur disproportionation (S2O32-H2S+SO42-) Organic sulfur compound oxidation or reduction (CH3SHCO2+H2S) Desulfurylation (organic SH2S)

1.3

Major Sulfur Reservoirs

Reservoir Atmosphere Troposphere Sulfate in aerosols Sulfur dioxide Carbonyl sulfide Other reduced sulfur gases Stratosphere Hydrosphere Lithosphere Ocean Water Continental and subcontinental Sedimentary Granite Basalt Oceanic Sedimentary Tholeitic and olivine basalt Layer 3 Pedosphere Soil Soil organic matter Land Plants

TgS

0.7 0.5 2.3 0.8 0.5 1.3 109

5.2 109 7.8109 8.8 109

0.3 109 0.6 109 1.6 109 2.6 105 1.1 104 760

1.4

Forms of Sulfur present in different Reservoirs

Atmosphere (gas) Sulfur dioxide, DMS, other biogenic products Atmosphere (particulates) Sulfates/bisulfates/sulfuric acid, MSA Hydrosphere (oceans, waterways, soil) Sulfates/bisulfates, hydrogen sulfide Lithosphere (earths crust) Sulfur, metal sulfides, sulfates Biosphere Amino acids, proteins etc.
1.5

Sources of Sulfur in Environment

Soil, water and rocks containing sulfates, sulfides and organic sulfur, and also body of living organisms.

Oxides of sulfur in the atmosphere due to the burning of fossil fuels and volcanic emissions.

Sulfur occurs as elemental sulfur also. The largest physical reservoir is the Earth's crust where sulfur is found in gypsum (CaSO4) and pyrite (FeS2).

The largest reservoir of biologically useful sulfur is found in the ocean as sulfate anions (2.6g/L), dissolved hydrogen sulfide gas, and elemental sulfur.

Freshwater contains sulfate, hydrogen sulfide and elemental sulfur Land contains sulfate Atmosphere contains sulfur oxide (SO2) and methane sulfonic acid (CH3SO3-) Volcanic activity releases some hydrogen sulfide into the air.
1.6

Production of Sulfur in Environment

Decomposers like Aspergillus (aerobic fungi), Neurospora (aerobic fungi) and Escherichia (anaerobic bacteria) act on the dead and decaying organic matter of plants and animals, releasing hydrogen sulfide (H2S) to the environment.

Heterotrophic bacteria like Desulfsavibrio and Acetobacter reduce sulfates to elemental sulfur or sulfides under anaerobic conditions. Though sulfides are harmful to most organisms, sulfur bacteria oxidize them to sulfate and bring back the element to cycle.

Oxides of sulfur (SO2 and H2S) in the atmosphere, gets dissolved in rain water and return to soil as sulfates and sulfuric acid.

From the reservoir pool in deep sediments in the sea, sulfur reaches the land through food chains, sea sprays and geological upheavals.

Hydrogen sulfide is released into atmosphere from lakes, marshes and water logged soils, which is oxidized to sulfur dioxide in the atmosphere.

About 70 Tg(S) per year in the form of SO2 comes from fossil fuel combustion and industry, 2.8 Tg(S) from wildfires and 8 Tg(S) per year from volcanoes.

1.7

Human Intervention in Sulfur Cycle

Since the Industrial Revolution, human activities have contributed to the amount of sulfur that enters the atmosphere, primarily through the burning of fossil fuels and the processing of metals. Humans are influencing sulfur cycle by

Burning sulfur-containing coal and oil to produce electric power. Refining sulfur-containing petroleum to make gasoline, heating oil, and other useful

products.

Converting sulfur-containing metallic mineral ores into free metals such as copper,

lead, and zinc.

Mining which cause erosion that results in exposure of mineral sulfides.

Emissions from these sources react with other chemicals in the atmosphere which results in acid rain and sulfate salt production which not only damage the natural environment (affects both plants and animals) as well as man-made environments i.e. weathering/corrosion of buildings.

1.8

Change in pH Level

Humans are responsible for 1/3 of the sulfur that reaches the atmosphere, and once there, this sulfur mixes with water, oxygen, and other chemicals in the atmosphere to create acid rain. Acid rain then negatively affects the various ecosystems on the Earth including the soil one due to changes in environments pH level. The pH of the environment is very important because the correct balance of positively charged hydrogen ions and negatively charged hydroxide ions is vital to any of the chemical processes of life, and pH is the measurement of the concentration of the hydrogen ions in a liquid. Having the correct amount of positively charged hydrogen ions and negatively charged hydroxide ions determines the correct structure of proteins in living things and too many or too few positively charged hydrogen ions or hydroxide ions can damage this structure. A strong change in pH, therefore, will affect the functions of the many proteins so critical to the chemical processes in living things. Enzymes in particular are susceptible to a

change in pH, and since enzymes control all chemical reactions within the fundamental life of the cell, any change in an enzymes structure will prevent any of the chemical reactions that take place in the cell from occurring, including the four essential tasks of cells: respiration, reproduction, transformation, and synthesis. If all chemical reactions cannot occur in a cell, then it would lead to death of the organism. Normally the best pH range for most organisms is between 6 and 8, with acidic rain, the pH in an environment can drop to a range of 1 to 4, meaning acid rain can create acidic soil which can kill the organisms that live there.

1.9

Impacts on Microorganisms

Microbes are the unsung heroes of soil. They are responsible for changing inorganic and organic matter from one form to another, and they do so through external digestion which provides the correct chemicals for consumption of other organisms such as plants. Bacteria are able to digest many different forms of organic and inorganic matter because of the many enzymes in their digestive metabolic pathways. The chemicals produced from the pathways are nutrient rich and keeps the soil healthy for plant growth. The digestive enzymes of bacteria are made of amino acids which are found in sulfur. Without the correct amount of sulfur in the soil there would not be bacterias digestive enzymes which would not allow them to have metabolic pathways, and without them bacteria could not produce nutrients and chemicals for the organisms in the soil. It is important to have healthy bacteria in the soil. When there are large amounts of acid in the soil from acid rain, the soil has an acidic pH level, which is unhealthy for the bacteria. Therefore when sulfur is released in the atmosphere creating acid rain which then creates low pH levels, this untimely harms the bacteria which harms the organisms that bacteria support. All of these processes contribute to bad soil and bad ecosystems.

1.10

Deposition of Atmospheric Sulfur

Two types of depositions of atmospheric sulfur occur

a) Dry Deposition
Gaseous sulfur dioxide component of the sulfur cycle and the nitrogen oxides of the nitrogen cycle mix in the atmosphere. Some of this mixture returns to the Earth as particulate matter and airborne gases, known as dry deposition

Effects

For humans, it irritates the respiratory tract, from the nose then moves into the lungs

and attacks sensitive tissues. High concentrations have caused a number of air-pollution disasters characterized by higher than expected death rates and increased incidences of bronchial asthma.

b) Wet Deposition

Major portion of atmospheric sulfur is transported away from the source in a direction

influenced by the atmospheric circulation. During their transport, sulfur dioxide and their oxidative products participate in complex reactions involving hydrogen chloride and other compounds, oxygen and water vapor. These reactions dilute solutions of strong acid (sulfuric acid). Eventually they come to earth in acidic rain, snow and fog.

Sulfur dioxide combines with atmospheric moisture to form sulfuric acid which falls

on land and water and forms significant part of acid rain which causes major damage to vegetation in areas surrounding the source of emission and injures or kills exposed plants

Acidic aerosols present during periods of fog, light rain and high relative humidity

together with moderate temperatures do the injury. External surfaces of the leaves absorb the aerosols. When dry, leaves and needles take up sulfur dioxide through the stomata. In the leaf, the sulfur dioxide rapidly reacts with moisture forming sulfuric acid.

1.11

Acid Rain

In the gas phase sulfur dioxide is oxidized by reaction with the hydroxyl radical via a intermolecular reaction: SO2+ OH HOSO2 Which is followed by: HOSO2 + O2 HO2 + SO3 In the presence of water sulfur trioxide (SO the presence of water sulfur trioxide (SO)3 is converted rapidly to sulfuric acid: SO3 (g) + H2O (l) H2SO4 (l)
1.11.1

Impact of Acid Rain on Hydrosphere

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 pH 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 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. However, there there has been some debate on the extent to which acid rain has been some debate on the extent to which acid rain contributes to lake acidity (i.e., that many acid lakes may result primarily from characteristics of the surrounding watershed, and not the rain itself). The EPA's website states: "Of the lakes and streams surveyed, acid rain caused acidity in 75 percent of the acidic lakes and about 50 percent of the acidic streams".
1.11.2

Impact of Acid Rain on Lithosphere

Soil biology can be seriously damaged by acid rain. Some tropical microbes can quickly consume acids 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.
1.11.3

Impact of Acid Rain on Vegetation

Acid rain can slow the growth of vulnerable forests and and cause leaves and needles to turn brown and fall off cause leaves and needles to turn brown and fall off. 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.
1.11.4

Technical Solutions

In the United States, many coal-burning power plants use Flue Flue gas desulfurization (FGD) to remove sulfur gas desulfurization (FGD) to remove sulfur-containing 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 limestone produces pH produces pH-neutral neutral calcium sulfate that is physically 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 to chemical companies as gypsum when the purity of calcium sulfate is high. In others, they are placed in landfill
1.11.5

Scrubbing with base solution

SO2 is an acid gas and thus the typical sorbent slurries or other materials used to remove the SO2 from the flue gases are alkaline. The reaction taking place in wet scrubbing using a CaCO3(limestone) slurry produces CaSO3 (calcium sulfite) and can be expressed as: CaCO3 (solid) + SO2 (gas) CaSO3 (solid) + CO2 (gas) When wet scrubbing with a Ca(OH)2 (lime) slurry, the reaction also produces CaSO3 (calcium sulfite): Ca(OH)2 (solid) + SO2 (gas) CaSO3 (solid) + H2O (liquid) A similar process is possible with magnesium hydroxide: Mg(OH)2 (solid) + SO2 (gas) + MgSO3(solid) + H2O (liquid) Some FGD systems go a step further and oxidize the CaSO3 (calcium sulfite) to produce marketable CaSO4 2H2O (gypsum) CaSO3 (solid) + O2 (gas) + 2H2O (liquid) CaSO4 2H2O (solid)

References
Environmental Protection Agency. (2008). Acid Rain. Retrieved October 19, 2012 from http://www.epa.gov/acidrain/effects/surface_water.html.

The Environmental Literacy Council. (2002). Biogeochemical Cycles. The Environmental Literacy Council. Retrieved October 18, 2012 from http://www.enviroliteracy.org/subcategory.php/198.html. Turner, B. L., Clark, W. C., Kates, R. W., Richards, J. F., Mathews, J. T. & Meyer, W. B. (1991). The Earth as Transformed by Human Action:. USA: Published by CUP Archive. Sulfur Cycle. (n.d.). Retrieved October 18, 2012, http://www.tutorvista.com/content/biology/biology-iv/ecosystem/sulfur-cycle.php from