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The sulfur cycle: not what you thought

In an article published in the journal Science, Dr. Itai Halevi from the Department of Environmental Sciences and Energy Research in the Faculty of Chemistry at the Weizmann Institute, together with Dr. Shannon Peters from the University of Wisconsin and Dr. and Edward Fisher from the California Institute of Technology, sought to understand the global sulfur cycle over the past 550 million years

Pyrite - fool's gold. From Wikipedia
Pyrite - fool's gold. From Wikipedia

The sulfur cycle in nature moves through the Earth's atmosphere, seas and continents. While moving, the sulfur undergoes chemical changes, and these are sometimes related to the chemistry of other elements, such as carbon and oxygen. So, for example, some single-celled organisms use sulfur compounds to digest their food, similar to how other organisms use oxygen. This activity does affect the concentration of free oxygen in the air, but sulfur is generally considered a secondary factor in the process of controlling oxygen levels in the atmosphere, while carbon is always considered the "main player". New findings recently published in the scientific journal Science indicate that the role of sulfur is greater than we thought.

Dr. Itai Halevi from the Department of Environmental Sciences and Energy Research in the Faculty of Chemistry at the Weizmann Institute, together with Dr. Shanan Peters from the University of Wisconsin and Dr. Edward Fisher from the California Institute of Technology, sought to understand the global sulfur cycle over the past 550 million years - during which the oxygen levels in the atmosphere were close to those found in it today - about 20%. For this purpose, they used a database called "Macrostrat", developed by Dr. Peters. The database contains detailed information on the geometry, age and mineralogical properties of thousands of rock units in North America and abroad.

The researchers used the database to trace one of the ways in which sulfur dissolved in ocean water forms sediments at the bottom and thus leaves the oceans: through the formation of minerals called sulfur evaporites. These sulphur-bearing minerals, such as, for example, natural gypsum, sink to the bottom of shallow seas as a result of the evaporation of seawater. The team found that the rates of production and deposition of sulfuric evaporites changed relatively frequently over the past 550 million years. These changes are related to changes in the area of ​​the shallow seas, the geographic latitudes where the ancient continents were found, and the sea level. But the discovery that surprised Dr. Halevi and his colleagues was that only a relatively small percentage of the sulfur that reaches the ocean waters leaves them in this way. Their findings pointed to a much more important way to precipitate sulfur - through another mineral, called pyrite.

Pyrite (also known as "fools' gold") is a compound of iron and sulfur, which is formed when single-celled creatures living in sediments at the bottom of the sea use sulfur dissolved in seawater to digest organic matter. These creatures absorb sulfur in the form of sulfate (that is, bound to four oxygen atoms) and release it as sulfide (without oxygen). During the process, four oxygen atoms are released, so it is considered a source of oxygen in the air. However, this part of the sulfur cycle is always considered secondary - in relation to the deposition of sulfur evaporites (which does not involve the release of oxygen), and therefore its effect on the oxygen levels in the air is considered negligible.

By checking theoretical models of different sulfur cycles against the information in the database, the team realized that the production and deposition of pyrite is actually much more significant than it is common to think: over 80% of the sulfur dissolved in the ocean water comes out of them this way (compared to previous estimates of 30-40%) Compared to the high variability in evaporite deposition throughout the period, pyrite deposition maintained relative stability. The analysis also showed that the source of most of the sulfur entering the sea is the weathering of pyrite from the land. In other words, it was discovered that there is a balance between the production and deposition of pyrite - in the process that releases oxygen, and the weathering of pyrite from the land , while consuming oxygen. The findings point to the great importance of the sulfur cycle in controlling the concentration of oxygen in the atmosphere.

Dr. Fisher: "The most surprising result is the fact that the weathering and deposition of the pyrite were, apparently, very important processes, throughout the history of the earth. The carbon cycle is known as a central player, which controls the chemistry of oxygen. However, according to our findings, a similar number of electrons move through the sulfur circuit."

Dr. Halevi: These findings not only shed new light on the role of sulfur in controlling oxygen levels in the atmosphere, but are an important step in developing a quantitative understanding of the processes that control the global sulfur cycle."

for the scientific article

3 תגובות

  1. To Avihai - in fact every oxidation reaction is also a redox reaction (and therefore vice versa).
    Creating or burning fuel is just a question of what is oxidized or recycled, when you are right that it is mostly carbon compounds that undergo oxidation (respiration) or reduction (fixation).
    For the purpose of breathing, we mainly know the exothermic which is a very strong oxidizer, therefore the energy gain from aerobic respiration (of oxygen) is the highest known in nature, but this is not the only mechanism, there are bacteria that are able to breathe (oxygenate) using for example: nitrate (NO3) trivalent iron and sulfate as described In the article, if I understood correctly, the meaning is that the effect of the process in question on the oxygen is actually that it is an organic substance that is breathed using sulfate instead of oxygen and not that the process releases oxygen directly as a gas.
    In any case, this process is carried out wherever there is organic matter available for decomposition but no oxygen available - in the sea, mainly in the sand a few centimeters below the surface. This can be seen by the color of the sand which is black - the color is obtained from the same pyrite (fools gold). The sand may also smell like a rotten egg in cases where not all of the sulfur reacted to form pyrite and some remained in the form of sulfide (H2S).
    By the way, the same sulfide can be used as a source of energy in the environments of the same hydrothermal vents you mentioned and entire ecosystems in the deep sea are based on it. It gets even more complicated but the scene is short...

  2. Just a fascinating article! Really, we talk about the carbon cycle all the time, due to global warming, but almost never about sulfur... it's refreshing and rejuvenating to read about it.

  3. There are also bacteria that use sulfur as a "fuel" source. In the end, the entire cycle of energy in living things is a collection of redox reactions. Redox = creation of "fuel" (organic matter that can be oxidized or "burned" and thus obtain a lot of energy). Oxidation = utilization of fuel to produce energy (glycolysis and cellular "breathing" in our case). In the animals it is redox/oxidation of carbon compounds. In some bacteria (I think mainly in the hydrothermal origins of various kinds) it is oxidation/reduction of sulfur compounds.

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