Biogeochemical cycles ± sulfur cycles

Sulfur Cycle The cycling of sulfur between biotic and abiotic systems is called sulfur cycle. Sulfur is an important component of proteins and amino acids. Sulfur exists in a number of states. Of these, three are important. They are elemental sulfur, sulfides and sulfates. Sulfur is present in rocks. It is made available for plants in the form of inorganic sulfate by weathering and erosion. Sulfur passes into the animals through food chain. As with nitrogen, these organic sulfur compounds are returned to the land or water after the plants die or are consumed by animals. By the time these plants and animals die, the decomposers bring the sulfur to the soil for the use of plants. Decomposers such as the bacteria Escherichia coli release sulfur in dead bodies into the air as hydrogen sulfide (H2S) under anaerobic combustion. Similarly incomplete combustion of fossil fuel release sulfur dioxide (SO2). The H2S are then oxidize to sulfate which can be used by plants. In the oceans, certain phytoplankton can produce a chemical that transforms to SO2 that resides in the atmosphere. These gases can re-enter the atmosphere, water, and soil, and continue the cycle. In its reduced oxidation state, the nutrient sulfur plays an important part in the structure and function of proteins. In its fully oxidized state, sulfur exists as sulfate and is the major cause of acidity in both natural and polluted rainwater. This link to acidity makes sulfur important to geochemical, atmospheric, and biological processes such as the natural weathering of rocks, acid precipitation, and rates of denitrification. Sulfur is also one of the main elemental cycles most heavily perturbed by human activity. Estimates suggest that emissions of sulfur to the atmosphere from human activity are at least equal or probably larger in magnitude than those from natural processes. Like nitrogen, sulfur can exist in many forms: as gases or sulfuric acid particles. Sulfuric acid particles contribute to the polluting smog that engulfs some industrial centers and cities where many sulfur containing fuels are burned. Such particles floating in air (known as sulfate aerosols) can cause respiratory diseases or cool the climate by reflecting some extra sunlight to space. The lifetime of most sulfur compounds in the air is relatively short (e.g. days). Superimposed on these fast cycles of sulfur are the extremely slow sedimentary-cycle processes or erosion, sedimentation, and uplift of rocks containing sulfur. In addition, sulfur compounds from volcanoes are intermittently injected into the atmosphere, and a continual stream of these compounds is produced from industrial activities. These compounds mix with water vapor and form sulfuric acid smog. In addition to contributing to acid rain, the sulfuric acid droplets of smog form a haze layer that reflects solar radiation and can cause a cooling of the earth's surface. While many questions remain concerning specifics, the sulfur cycle in general, and acid rain and smog issues in particular are becoming major physical, biological, and social problems.

Role of microorganisms in sulfur cycles:

Sulfur is a component of a couple of vitamins and essential metabolites and it occurs in two amino acids, cysteine and methionine. In spite of its paucity in cells, it is an absolutely essential element for living systems. Like nitrogen and carbon, the microbes can transform sulfur from its most oxidized form (sulfate or SO4) to its most reduced state (sulfide or H2S). The sulfur cycle, in particular, involves some unique groups of procaryotes and procaryotic processes. Two unrelated groups of procaryotes oxidize H2S to S and S to SO4. The first is the anoxygenic photosynthetic purple and green sulfur bacteria that oxidize H2S as a source of electrons for cyclic photophosphorylation. The second is the "colorless sulfur bacteria" (now a misnomer because the group contains many Archaea) which oxidize H2S and S as sources of energy. In either case, the organisms can usually mediate the complete oxidation of H2S to SO4. H2S----------------> S ----------------> SO4 litho or phototrophic sulfur oxidation Sulfur-oxidizing procaryotes are frequently thermophiles found in hot (volcanic) springs and near deep sea thermal vents that are rich in H2S. They may be acidophiles, as well, since they acidify their own environment by the production of sulfuric acid. Since SO4 and S may be used as electron acceptors for respiration, sulfate reducing bacteria produce H2S during a process of anaerobic respiration analogous to denitrification. The use of SO4 as an electron acceptor is an obligatory process that takes place only in anaerobic environments. The process results in the distinctive odor of H2S in anaerobic bogs, soils and sediments where it occurs. Sulfur is assimilated by bacteria and plants as SO4 for use and reduction to sulfide. Animals and bacteria can remove the sulfide group from proteins as a source of S during decomposition. These processes complete the sulfur cycle. Sulfide Oxidation Hydrogen sulfide is normally toxic to aerobic plant and animal tissue; the exception is ruminant animals. Whenever sulfide is generated, a specialized microflora usually develops that is capable of oxidizing the sulfide to elemental sulfur. Sulfide may be oxidized to elemental sulfur aerobically by species of Thiothrix and Beggiatoa (morphologically conspicuous sulfur oxidizers), and anaerobically by the purple sulfur bacteria. Both of these groups are primarily aquatic microbes. In soil, the predominant microbes involved in the oxidation of sulfide to elemental sulfur belong to the genus Thiobacillus. However, many thiobacilli are aquatic as well, especially in acidic mine waters. For the following two "generic" reactions, the first is typical of oxidation of sulfide to sulfur, and the second of oxidation of sulfide to sulfate. As shown in the diagram to the left, the rate-limiting step is mediated by the enzyme sulfite oxidase (cofactors for the enzyme are Mo and Fe).

CO2 + 2H2S -----> CH2O + 2S + H2O 2CO2 + H2S + 2H2O -------> 2(CH2O) + H2SO4

Purple sulfur bacteria

Published by Globe Pequot The purple sulfur bacteria are divided into two families, the Chromatiaceae and Ectothiorhodospiraceae, which respectively produce internal and external sulfur granules, and show differences in the structure of their internal membranes. They make up the order Chromatiales, included in the gamma subdivision of the Proteobacteria. The genus Halothiobacillus is also included in the Chromatiales, in its own family, but it is not photosynthetic. Purple sulfur bacteria are generally found in illuminated anoxic zones of lakes and other aquatic habitats where hydrogen sulfide accumulates and also in "sulfur springs" where geochemically or biologically produced hydrogen sulfide can trigger the formation of blooms of purple sulfur bacteria. Anoxic conditions are required for photosynthesis; these bacteria cannot thrive in oxygenated environments. The most favorable lakes for the development of purple sulfur bacteria are meromictic (permanently stratified) lakes. Meromictic lakes stratify because they have denser (usually saline) water in the bottom and less dense (usually freshwater) nearer the surface. If sufficient sulfate is present to support sulfate reduction, the sulfide, produced in the sediments, diffuses

upward into the anoxic bottom waters, and here purple sulfur bacteria can form dense cell masses, called blooms, usually in association with green phototrophic bacteria

A bloom of purple sulfur bacteria
The Colorless Sulfur-Oxidizing Bacteria

Beggiatoa (beg-ee-a-toe-a) is a colourless sulphur bacterium which occurs as filaments of various widths. Beggiatoa is found in sediments above the reduced zone. It oxidizes hydrogen sulphide, producing Image

copyright: D. J. Patterson, L. Amaral-Zettler and V. Edgcomb elemental sulphur which is deposited within the bacterial cell as sulphur granules and give this filament its opaque appearance.

The colorless sulfur bacteria comprise a very heterogeneous group of organisms which share the ability to oxidize reduced or partially oxidized inorganic sulfur compounds. Both obligate and facultative chemoautotrophs occur, as well as chemohoheterotrophs. A few organisms classified as colorless sulfur bacteria (e.g., some Beggiatoa spp.) may not be true chemoheterotrophs, as they do not gain energy from the oxidation of sulfur compounds. They do, however, profit from the oxidation in other ways. Colorless sulfur bacteria can be found wherever reduced sulfur compounds are available (e.g., in sediments, soil, at aerobic/anaerobic interfaces in water, and at volcanic sources such as the hydrothermal vents). Natural enrichments with sometimes 108 cells/mL or more may be found at sulfide/oxygen interfaces and where sulfur compounds and oxygen mix. The presence of colorless sulfur bacteria may often be evident to the naked eye by the appearance of copious white deposits of sulfur, streamers, veils, rosettes, or films. Samples taken from sites exposed to light may also contain (at least below 55oC) photoautotrophic (purple) sulfur-oxidizing bacteria, many of which can also be grown as chemoautotrophs.

The Sulfur Cycle

Other Micro-organism Reactions in the Sulphur Cycle Sulphate ion is taken up from soil by plants, which incorporate it into protein, and plant protein is consumed by animals that convert plant protein to animal protein. Death of plants and animals allows bacterial decomposition of protein in remains to produce hydrogen sulphide and other products , in processes involving many fungi, actinomycetes and bacteria such as the heterotroph Proteus vulgaris. Some bacteria can function in the transition zone between aerobic and anaerobic environments,. Hydrogen sulphide may be oxidized to sulphur by such bacteria which deposit elemental sulphur in their cells while using oxygen as the terminal electron acceptor. Hydrogen sulphide may also be oxidized to sulphate photosynthetically by the bacteria, Chromtiacceae and Chlorobiaceae.