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Sulfur metabolism and the sulfur cycle

The Sulfur cycle was the first of the biogeochemical cycles to be discovered. In the 1880s, while studying Beggiatoa (a bacterium living in a sulfur rich environment), Sergei Winogradsky found that it oxidized hydrogen sulfide (H2S) as an energy source, forming intracellular sulfur droplets. Winogradsky referred to this form of metabolism as inorgoxidation (oxidation of inorganic compounds). He continued to study it together with Selman Waksman till the 1950s.

Sulfur may serve as energy (chemical food) source for bacteria that use hydrogen sulfide (H2S) in the place of water as the electron donor in a primitive photosynthesis-like process in which oxygen is the electron receptor. The photosynthetic green sulfur bacteria and purple sulfur bacteria and some chemolithotrophs use elemental oxygen to carry out such oxidization of hydrogen sulfide to produce elemental sulfur (S0), oxidation state = 0. Primitive bacteria that live around deep ocean volcanic vents oxidize hydrogen sulfide in this way with oxygen; see giant tube worm for an example of large organisms that use hydrogen sulfide (via bacteria) as food to be oxidized.

The so-called sulfate-reducing bacteria, by contrast, "breathe sulfate" instead of oxygen. They use sulfur as the electron acceptor, and reduce various oxidized sulfur compounds back into sulfide, often into hydrogen sulfide. They can grow on a number of other partially oxidized sulfur compounds (e.g. thiosulfates, thionates, polysulfides, sulfites). The hydrogen sulfide produced by these bacteria is responsible for some of the smell of intestinal gases (flatus) and decomposition products.

Sulfur is absorbed by plants via the roots from soil as the sulfate and transported as a phosphate ester. Sulfate is reduced to sulfide via sulfite before it is incorporated into cysteine and other organosulfur compounds.

SO42– → SO32– → H2S → cysteine → methionine

Precautions

Picture 11. Effect of acid rain on a forest, Jizera Mountains, Czech Republic

Elemental sulfur is non-toxic, as generally are the soluble sulfate salts, such as Epsom salts. Soluble sulfate salts are poorly absorbed and laxative. However, when injected parenterally, they are freely filtered by the kidneys and eliminated with very little toxicity in multi-gram amounts.

When sulfur burns in air, it produces sulfur dioxide. In water, this gas produces sulfurous acid and sulfites, which are antioxidants that inhibit growth of aerobic bacteria and allow its use as a food additive in small amounts. However, at high concentrations these acids harm the lungs, eyes or othertissues. In organisms without lungs such as insects or plants, it otherwise prevents respiration in high concentrations. Sulfur trioxide (made by catalysis from sulfur dioxide) and sulfuric acid are similarly highly corrosive, due to the strong acids that form on contact with water.

The burning of coal and/or petroleum by industry and power plants generates sulfur dioxide (SO2), which reacts with atmospheric water and oxygen to produce sulfuric acid (H2SO4) and sulfurous acid (H2SO3). These acids are components of acid rain, which lower the pH of soil and freshwater bodies, sometimes resulting in substantial damage to the environment and chemical weathering of statues and structures. Fuel standards increasingly require that fuel producers extract sulfur from fossil fuels to prevent acid rain formation. This extracted and refined sulfur represents a large portion of sulfur production. In coal-fired power plants, flue gases are sometimes purified. More modern power plants that use synthesis gas extract the sulfur before they burn the gas.



Hydrogen sulfide is as toxic as hydrogen cyanide, and kills by the same mechanism, though hydrogen sulfide is less likely to cause surprise poisonings from small inhaled amounts, because of its disagreeable warning odor. Though pungent at first, however, hydrogen sulfide quickly deadens the sense of smell—so a victim may breathe increasing quantities and be unaware of its presence until severe symptoms occur, which can quickly lead to death. Dissolved sulfide and hydrosulfide salts are also toxic by the same mechanism.


Date: 2016-04-22; view: 170


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