The sulfate-methane transition zone (SMTZ) is a zone in oceans, lakes, and rivers typically found below the sediment surface in which sulfate and methane coexist. The formation of a SMTZ is driven by the diffusion of sulfate down the sediment column and the diffusion of methane up the sediments. At the SMTZ, their diffusion profiles meet and sulfate and methane react with one another, which allows the SMTZ to harbor a unique microbial community whose main form of metabolism is anaerobic oxidation of methane (AOM). The presence of AOM marks the transition from dissimilatory sulfate reduction to methanogenesis as the main metabolism utilized by organisms. The SMTZ is a global feature that can occur at depths that range anywhere from a few millimeters to hundreds of meters below the sediment surface. It tends to span several centimeters, but can also reach widths up to a whole meter. It is characterized by low concentrations of sulfate and methane because the anaerobic oxidation of methane consumes both molecules.
History It was previously believed that methane and sulfate could not coexist due to the established hierarchy of metabolisms in sediments. In well-oxygenated sediments, oxygen is the main electron acceptor in aerobic respiration. Once all of the oxygen is consumed, organisms begin using substrates like nitrate, manganese oxides, and iron oxides as the electron acceptor in anaerobic respiration. However, these substrates tend to be low in concentrations throughout sediments. Sulfate, on the other hand, is relatively high in abundance in comparison, so sulfate reduction is the main form of respiration after oxygen is consumed. Methanogenesis is the next form of metabolism after sulfate reduction, but was thought to begin only when all the sulfate in the sediments was reduced. However, it was discovered that sulfate reduction and methanogenesis could occur simultaneously in marine sediment in 1977 by Ronald S. Oremland and Barrie F. Taylor. Following this discovery, non-zero concentration of sulfate and methane were found in the same zone in ocean setting, leading Niels Iverson and Bo Barker Jorgenson to investigate the methane oxidation rates in the so-called "sulfate-methane transition" in 1985. Since then, many studies have been conducted to trace the sulfate and methane profiles above, in, and below the SMTZ.
Metabolic processes All organisms need a metabolic pathway in order to generate energy. In a sediment column, the dominant metabolism used by organisms changes with depth, as the availability of different electron acceptors changes.
Above SMTZ After oxygen, nitrate, manganeses, and iron are depleted, sulfate is the main electron acceptor used in anaerobic respiration. The metabolism associated with this is dissimilatory sulfate reduction (DSR) and is carried out by sulfur-reducing bacteria, which are widely distributed in anoxic environments. DSR oxidizes organic carbon using sulfate, and is described by the following equation:
SO 4 2 − + 2 CH 2 O ⟶ H 2 S + 2 HCO 3 − {\displaystyle {\ce {SO4^2- +2CH2O -> H2S +2HCO3^-}}} .
Within SMTZ The main metabolism is anaerobic oxidation of methane (AOM). AOM uses sulfate to oxidize methane into bicarbonate and forms hydrogen sulfide as a byproduct, and is described by the following equation:
SO 4 2 − + CH 4 ⟶ HS − + HCO 3 − + H 2 O {\displaystyle {\ce {SO4^2- + CH4 -> HS^- +HCO3^- +H2O}}} . The rate of AOM is pretty slow, with turnover times for the coexisting sulfate and methane in the oceans ranging from weeks to years. This inefficiency can be a result of the small change in free energy associated with the reaction. Highest rates of AOM usually over methane gas seeps. The maximum rates of AOM generally overlap with the maximum rates of sulfate reduction. It has also been proposed that methanogens can also oxidize methane into acetate or carbon dioxide, and not just bicarbonate.
Below SMTZ Below the SMTZ, methanogenesis is the main metabolism after AOM. Methanogens are organisms who produce methane and take a carbon source, either carbon dioxide or organic matter, and reduce it to methane through the following reaction:
4 H 2 + CO 2 ⟶ CH 4 + 2 H 2 O {\displaystyle {\ce {4H2 +CO2->CH4 +2H2O}}} . It is this reaction that leads to the sharp increase in methane concentrations below the SMTZ.
Geochemistry
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