Sulfur cycle - Knowledge

2108:. BIFs only form if the water is allowed to supersaturate in dissolved iron (Fe) meaning there cannot be free oxygen or sulfur in the water column because it would form Fe (rust) or pyrite and precipitate out of solution. Following this supersaturation, the water must become oxygenated in order for the ferric rich bands to precipitate it must still be sulfur poor otherwise pyrite would form instead of Fe. It has been hypothesized that BIFs formed during the initial evolution of photosynthetic organisms that had phases of population growth, causing over production of oxygen. Due to this over production they would poison themselves causing a mass die off, which would cut off the source of oxygen and produce a large amount of CO 1630: 1480: 1468: 2089:", when redox conditions on Earth's surface are thought by most workers to have shifted fundamentally from reducing to oxidizing. This shift would have led to an incredible increase in sulfate weathering which would have led to an increase in sulfate in the oceans. The large isotopic fractionations that would likely be associated with bacteria reduction are produced for the first time. Although there was a distinct rise in seawater sulfate at this time it was likely still only less than 5–15% of present-day levels. 1577:

sulfate. Such reactions are known to occur by microbial processes but it is generally accepted that TSR is responsible for the bulk of these reactions, especially in deep or hot reservoirs. Thus, TSR occurs in deep reservoirs where the temperatures are much higher. BSR is geologically instantaneous in most geologic settings, while TSR occurs at rates in the order of hundreds of thousands of years. Although much slower than BSR, even TSR appears to be a geologically fairly fast process.

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Since different sulfate sources within the ocean have distinct oxygen isotopic values it may be possible to use oxygen to trace the sulfur cycle. Biological sulfate reduction preferentially selects lighter oxygen isotopes for the same reason that lighter sulfur isotopes are preferred. By studying oxygen isotopes in ocean sediments over the last 10 million years were able to better constrain the sulfur concentrations in sea water through that same time. They found that the

122: 5446: 696: 1459:, and is the major biogenic gas emitted from the sea, where it is responsible for the distinctive “smell of the sea” along coastlines. DMS is the largest natural source of sulfur gas, but still only has a residence time of about one day in the atmosphere and a majority of it is redeposited in the oceans rather than making it to land. However, it is a significant factor in the climate system, as it is involved in the formation of clouds. 25: 148: 1905: 2010:

and thus this process determines if the organic matter is assimilated or buried. Sulfurization increases molecular weight and introduces a new moiety to the organic molecule which may inhibit its recognition by catabolic enzymes that degrade organic matter. Microbial ability for desulfurization is reflected by the presence of

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also marks the first large scale sedimentary exhalative deposits showing a link between mineralization and a likely increase in the amount of sulfate in sea water. In the Paleoproterozoic the sulfate in seawater had increased to an amount greater than in the Archean, but was still lower than present

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is met by the anaerobic methanotrophic archaea in the SMTZ which oxidize it using sulfate as an electron acceptor. More sulfate is present at the SMTZ than methane. A 4:1 ratio of sulfate: methane is observed and the excess sulfate is directed towards organic matter degradation. Syntrophic aggregates

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tube worms that grow around hydrothermal vents lack a digestive tract but contain specialized organelles called trophosomes within which autotrophic, sulfide oxidizing bacteria are housed. The tube worms provide the bacteria with sulfide and the bacteria shares the fixed carbon with the worms.

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that use sulfide or elemental sulfur to fix carbon dioxide. The oxidation pathway includes the formation of various intermediate sulfur species, including elemental sulfur and thiosulfate. Under low oxygen concentrations, microbes will oxidize to elemental sulfur. This elemental sulfur accumulates as

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exert an important control on the redox state of the metal-transporting fluids, and deposits can form from both oxidizing and reducing fluids. Metal-rich ore fluids tend to be, by necessity, comparatively sulfide deficient, so a substantial portion of the sulfide must be supplied from another source

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Sulfurization of organic matter is a significant sulfur pool, containing 35-80% of the reduced sulfur in marine sediments. These organo-sulfur molecules are also desulfurized to release oxidized sulfur species like sulfite and sulfate. This desulfurization may allow degradation of the organic matter

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deltas, and hydrothermal sediments which have intense microbial sulfate reduction because of the high concentration of dissolved sulfate in the seawater. Additionally, the high amounts of hydrogen sulfide found in oil and gas fields is thought to arise from the oxidation of petroleum hydrocarbons by

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These processes occur because there are two very different thermal regimes in which sulfate is reduced, particularly in low-temperature and high-temperature environments. BSR usually occurs at lower temperatures from 0−80 °C, while TSR happens at much higher temperatures around 100–140 °C.

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Throughout geologic history the sulfur cycle and the isotopic ratios have coevolved with the biosphere becoming overall more negative with the increases in biologically driven sulfate reduction, but also show substantial positive excursion. In general positive excursions in the sulfur isotopes mean

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generation as long as the respective transition or base metals are present or transported to a sulfate reduction site. If the system runs out of reactive hydrocarbons, economically viable elemental sulfur deposits may form. Sulfur also acts as a reducing agent in many natural gas reservoirs, and

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also act as proxies for atmospheric oxygen because sulfate is produced mostly through weathering of the continents in the presence of oxygen. The low levels in the Proterozoic simply imply that levels of atmospheric oxygen fell between the abundances of the Phanerozoic and the deficiencies of the

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of sulfur) represents the total outgassing of sulfur through geologic time. Rocks analyzed for sulfur content are generally organic-rich shales meaning they are likely controlled by biogenic sulfur reduction. Average seawater curves are generated from evaporites deposited throughout geologic time

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fueled by sulfide oxidation. Some PSB can also perform aerobic sulfide oxidation in the presence of oxygen and can even grow chemoautotrophically under low light conditions. GSB lack this metabolic potential and have compensated by developing efficient light harvesting systems. PSB can be found in

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utilizes multiple oxidants because the concentrations of the electron acceptors are depth dependent. In the upper sediment layers oxygen and nitrate are the preferred oxidants because of the high energy yield from the reaction, and in the suboxic zones iron and manganese take on the role. Sulfide

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of sulfur intermediates in the sediment. This view has changed since the 2010s that sulfate reduction can fractionate to 66 permil. As substrates for disproportionation are limited by the product of sulfate reduction, the isotopic effect of disproportionation should be less than 16 permil in most

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Temperatures for TSR are not as well defined; the lowest confirmed temperature is 127 °C and the highest temperatures occur in settings around 160−180 °C. These two different regimes appear because at higher temperatures most sulfate-reducing microbes can no longer metabolize due to the

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Over a shorter time scale (ten million years) changes in the sulfur cycle are easier to observe and can be even better constrained with oxygen isotopes. Oxygen is continually incorporated into the sulfur cycle through sulfate oxidation and then released when that sulfate is reduced once again.

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or precious metals are discovered and either burned or milled, sulfur becomes a waste product that must be dealt with properly, or it can become a pollutant. The burning of fossil fuels has greatly increased the amount of sulfur in our present-day atmosphere. Sulfur acts as a pollutant and an

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or used as electron donor or to sulfurize organic matter by microbes. Pyrite is formed through two pathways: the polysulfide and the hydrogen sulfide pathway. The polysulfide pathway is dominant until the depletion of elemental sulfur since elemental sulfur is necessary in the formation of

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high carbon burial rates increased the atmospheric oxygen level to >10% of its present-day value. In the Latest Neoproterozoic another major oxidizing event occurred on Earth's surface that resulted in an oxic deep ocean and possibly allowed for the appearance of multicellular life.

2045:(4.6–2.5 Ga) most systems appeared to be sulfate-limited. Some small Archean evaporite deposits require that at least locally elevated concentrations (possibly due to local volcanic activity) of sulfate existed in order for them to be supersaturated and precipitate out of solution. 1835:

should be the same as the overall isotope ratio in the water column at their time of precipitation. Sulfate reduction through biologic activity strongly differentiates between the two isotopes because of the more rapid enzymic reaction with S. Average present day seawater values of

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oxidation yields various sulfur intermediates such as elemental sulfur, thiosulfate, sulfite, and sulfate.The sulfur intermediates formed during sulfide oxidation are unique to this process and thus are indicative of sulfide oxidation when found in environmental samples. Sulfur

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Although the sulfur curve shows shifts between net sulfur oxidation and net sulfur reduction in the geologic past, the magnitude of the current human impact is probably unprecedented in the geologic record. Human activities greatly increase the flux of sulfur to the

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2.8 Ga marks the first evidence for oxygen production through photosynthesis. This is important because there cannot be sulfur oxidation without oxygen in the atmosphere. This exemplifies the coevolution of the oxygen and sulfur cycles as well as the biosphere.

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various environments ranging from hot sulfur springs and alkaline lakes to wastewater treatment plants. GSB populate stratified lakes with high reduced sulfur concentrations and can even grow in hydrothermal vents by using infra-red light to perform photosynthesis.

2393:, however, the average rain pH is between 4.2 and 4.4. Since pH is on a log scale dropping by 1 (the difference between normal rain water and acid rain) has a dramatic effect on the strength of the acid. In the United States, roughly two thirds of all SO 1621:

form long chains that span the length between oxic and sulfidic zones of the coastal sediments. The bacteria present in the sulfide rich zones oxidize the sulfide and transport the electrons to the bacteria present in the oxygen rich zone through multiple

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is a broad term referring to a mixture of wet and dry deposition (deposited material) from the atmosphere containing higher than normal amounts of nitric and sulfuric acids. Distilled water (water without any dissolved constituents), which contains no

2041:. All sulfur in the atmosphere would be released during volcanic eruptions. When the oceans condensed on Earth, the atmosphere was essentially swept clean of sulfur gases, owing to their high solubility in water. Throughout the majority of the 2112:

through the decomposition of their bodies, allowing for another bacterial bloom. After 1.8 Ga sulfate concentrations were sufficient to increase rates of sulfate reduction to greater than the delivery flux of iron to the oceans.

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cycles changed the area of continental shelves which then disrupted the sulfur processing, lowering the concentration of sulfate in the sea water. This was a drastic change as compared to preglacial times before 2 million years ago.

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and of geochemical importance. Of those four, two (S, light and S, heavy) comprise (99.22%) of sulfur on Earth. The vast majority (95.02%) of sulfur occurs as S with only 4.21% in S. The ratio of these two isotopes is fixed in the

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Wilbanks, Elizabeth G.; Jaekel, Ulrike; Salman, Verena; Humphrey, Parris T.; Eisen, Jonathan A.; Facciotti, Marc T.; Buckley, Daniel H.; Zinder, Stephen H.; Druschel, Gregory K.; Fike, David A.; Orphan, Victoria J. (November 2014).

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exceeded 10 present atmospheric level after the Great Oxygenation Event. Oxygen played an essential role in the global sulfur cycles after the Great Oxygenation Event, such as oxidative weathering of sulfides. The burial of

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S value according to the mass dependent fractionation law. The Great Oxidation Event represented a massive transition of global sulfur cycles. Before the Great Oxidation Event, the sulfur cycle was heavily influenced by the

1524:, elemental sulfur and metal sulfides. However, the reactive organic compounds differ for BSR and TSR because of the mutually exclusive temperature regimes. Organic acids are the main organic reactants for BSR and branched/ 2336:

has greatly increased the amount of sulfur in the atmosphere and ocean and depleted the sedimentary rock sink. Without human impact sulfur would stay tied up in rocks for millions of years until it was uplifted through

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BSR and TSR occur at different depths. BSR takes place in low-temperature environments, which are shallower settings such as oil and gas fields. BSR can also take place in modern marine sedimentary environments such as

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The primary natural source of sulfur to the atmosphere is sea spray or windblown sulfur-rich dust, neither of which is long lived in the atmosphere. In recent times, the large annual input of sulfur from the burning of

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Bjerg, Jesper T.; Boschker, Henricus T. S.; Larsen, Steffen; Berry, David; Schmid, Markus; Millo, Diego; Tataru, Paula; Meysman, Filip J. R.; Wagner, Michael; Nielsen, Lars Peter; Schramm, Andreas (2018-05-29).

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have caused large scale burning of these measures, and consequential release of sulfur to the atmosphere. This has led to substantial disruption to the climate system, and is one of the proposed causes of the

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S and S). There are two major outputs of sulfur from the oceans. The first sink is the burial of sulfate either as marine evaporites (such as gypsum) or carbonate-associated sulfate (CAS), which accounts for

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and most metal deposits because it acts as an oxidizing or reducing agent. The vast majority of the major mineral deposits on Earth contain a substantial amount of sulfur including, but not limited to

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sulfur globules, intracellularly or extracellularly, to be consumed under low sulfur concentrations. To ameliorate low oxidant concentrations (that is, to find an electron sink), sulfur oxidizers like

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Konhauser KO, Lalonde SV, Planavsky NJ, Pecoits E, Lyons TW, Mojzsis SJ, et al. (October 2011). "Aerobic bacterial pyrite oxidation and acid rock drainage during the Great Oxidation Event".

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O) to the symbiont while the symbiont generates organic carbon for sustaining the metabolic activities of the host. The produced sulfate usually combines with the leached calcium ions to form

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John EH, Wignall PB, Newton RJ, Bottrell SH (August 2010). "δ34SCAS and δ18OCAS records during the Frasnian–Famennian (Late Devonian) transition and their bearing on mass extinction models".

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at a rate that mobilizes 150 x 10 gS/yr, which is more than double the rate of 100 years ago. The result of human impact on these processes is to increase the pool of oxidized sulfur (SO

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Lyons TW, Gellatly AM, McGoldrick PJ, Kah LC (2006). "Proterozoic sedimentary exhalative (SEDEX) deposits and links to evolving global ocean chemistry". In Kesler SE, Ohmoto H (eds.).

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pathway, sulfate can be reduced either bacterially (bacterial sulfate reduction) or inorganically (thermochemical sulfate reduction). This pathway involves the reduction of sulfate by

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Newton RJ, Pevitt EL, Wignall PB, Bottrell SH (February 2004). "Large shifts in the isotopic composition of seawater sulphate across the Permo–Triassic boundary in northern Italy".

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Krouse HR, Viau CA, Eliuk LS, Ueda A, Halas S (1988). "Chemical and isotopic evidence of thermochemical sulphate reduction by light hydrocarbon gases in deep carbonate reservoirs".

2389:, has a neutral pH of 7. Rain naturally has a slightly acidic pH of 5.6, because carbon dioxide and water in the air react together to form carbonic acid, a very weak acid. Around 2349:

processes. Instead it is being drilled, pumped and burned at a steadily increasing rate. Over the most polluted areas there has been a 30-fold increase in sulfate deposition.

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states determine whether sulfides will precipitate. Most sulfide brines will remain in concentration until they reach reducing conditions, a higher pH, or lower temperatures.

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cycle involves the transformations of sulfur species through different oxidation states, which play an important role in both geological and biological processes. Steps of the

2408:, sulfur is increasingly used as a component of fertilizers. Recently sulfur deficiency has become widespread in many countries in Europe. Because of actions taken to limit 1827:

Formation of sulfur minerals through non-biogenic processes does not substantially differentiate between the light and heavy isotopes, therefore sulfur isotope ratios in

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which matches the input fluxes, implying the modern marine sulfur budget is at steady state. The residence time of sulfur in modern global oceans is 13,000,000 years.

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Pham M, Müller JF, Brasseur GP, Granier C, Mégie G (May 1996). "A 3D model study of the global sulphur cycle: Contributions of anthropogenic and biogenic sources".

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S in any deep reservoir, then it is assumed that TSR has taken over. This is due to the fact that thermal cracking of hydrocarbons doesn't provide more than 3% of H

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Wegner, Carl-Eric; Richter-Heitmann, Tim; Klindworth, Anna; Klockow, Christine; Richter, Michael; Achstetter, Tilman; Glöckner, Frank Oliver; Harder, Jens (2013).

1103:. Thus, elemental sulfur can either give or receive electrons depending on its environment. On the anoxic early Earth, most sulfur was present in minerals such as 2218:

lower than 10 of present atmospheric level (PAL). The disappearance of sulfur isotope mass-independent fractionation at ~2.45 Ga indicates that atmospheric

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because again, since they do not discriminate between the heavy and light sulfur isotopes, they should mimic the ocean composition at the time of deposition.

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are generally consistent with a seawater sulfate source, suggesting baryte formation by reaction between hydrothermal barium and sulfate in ambient seawater.

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Aharon P, Fu B (2000). "Microbial sulfate reduction rates and sulfur and oxygen isotope fractionations at oil and gas seeps in deepwater Gulf of Mexico".

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atmospheric inputs of sulfur continue to decrease, As a result, the deficit in the sulfur input is likely to increase unless sulfur fertilizers are used.

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S is affected by several factors such as, the availability of organic reactants and sulfate and the presence/availability of base and transition metals.

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Sulfide oxidation is performed by both bacteria and archaea in a variety of environmental conditions. Aerobic sulfide oxidation is usually performed by

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Sulfur has four main oxidation states in nature, which are −2, +2, +4, and +6. The common sulfur species of each oxidation state are listed as follows:

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Skennerton, Connor T.; Chourey, Karuna; Iyer, Ramsunder; Hettich, Robert L.; Tyson, Gene W.; Orphan, Victoria J. (2017-09-06). Dubilier, Nicole (ed.).

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Reheis MC, Kihl R (May 1995). "Dust deposition in southern Nevada and California, 1984–1989: Relations to climate, source area, and source lithology".

2280:. The presence or absence of sulfur is one of the limiting factors in the concentration of precious metals and their precipitation from solution. 1504:

The main products and reactants of bacterial sulfate reduction (BSR) and thermochemical sulfate reduction (TSR) are very similar. For both, various

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Brimblecombe P, Hammer C, Rodhe H, Ryaboshapko A, Boutron CF (1989). "Human Influences on the sulphur cycle.". In Brimblecombe P, Lein AY (eds.).

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Jørgensen BB, Isaksen MF, Jannasch HW (December 1992). "Bacterial Sulfate Reduction Above 100{degrees}C in Deep-Sea Hydrothermal Vent Sediments".

5088: 2193:(MIF) in the sedimentary records at around 2.45 billion years ago (Ga). The MIF of sulfur isotope (ΔS) is defined by the deviation of measured 5125: 2052:

rocks from this time still have an isotopic value of 0 because the biosphere was not developed enough (possibly at all) to fractionate sulfur.

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The marine sulfur cycle is driven by sulfate reduction because hydrogen sulfide is oxidized by microbes for energy or is oxidized abiotically.

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S is still basically 0. Shortly after, at 3.4 Ga the first evidence for minimal fractionation in evaporitic sulfate in association with

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Important sources of sulfur in ore deposits are generally deep-seated, but they can also come from local country rocks, seawater, or marine

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are primary sulfur oxidizing bacteria, and form chemosynthetic symbioses with animal hosts. The host provides metabolic substrates (e.g., CO

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and has been since its formation. The bulk Earth sulfur isotopic ratio is thought to be the same as the ratio of 22.22 measured from the

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S = +6‰) is the primary input of sulfur to the oceans. Other sources are metamorphic and volcanic degassing and hydrothermal activity (

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Sievert SM, Hügler M, Taylor CD, Wirsen CO (2008). "Sulfur Oxidation at Deep-Sea Hydrothermal Vents". In Dahl C, Friedrich CG (eds.).

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Gill BC, Lyons TW, Jenkyns HC (December 2011). "A global perturbation to the sulfur cycle during the Toarcian Oceanic Anoxic Event".

243: 236: 3222:"Biochemistry and molecular biology of lithotrophic sulfur oxidation by taxonomically and ecologically diverse bacteria and archaea" 5047: 2644:

Machel HG, Krouse HR, Sassen R (1995). "Products and distinguishing criteria of bacterial and thermochemical sulfate reduction".

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Bickle MJ, Alt JC, Teagle DA (1994). "Sulfur transport and sulphur isotope fractionations in ocean floor hydrothermal systems".

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Berner RA, Raiswell R (1983). "Burial of organic carbon and pyrite sulfur in sediments over phanerozoic time: a new theory".

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have been discovered and the underlying mechanisms observed include direct interspecies electron transfer using large multi

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with the sulfur isotope composition of ~3‰. Riverine sulfate derived from the terrestrial weathering of sulfide minerals (

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3.8–3.6 Ga marks the beginning of the exposed geologic record because this is the age of the oldest rocks on Earth.

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that oxidize hydrogen sulfide with oxygen to produce elemental sulfur or sulfate. The chemical reactions are as follows:

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episodes where the entire globe including the oceans was covered in a layer of ice cutting off oxygenation. In the late

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is established and provides a weak source of sulfate to the global ocean with sulfate concentrations incredibly low the

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with other microbes, and even animals. PSB and sulfate reducers form microbial aggregates called “pink berries” in the

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The isotopic composition of sedimentary sulfides provides primary information on the evolution of the sulfur cycle.

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Machel HG (2001). "Bacterial and thermochemical sulfate reduction in diagenetic settings — old and new insights".

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Ceccotti SP (1996). "Plant nutrient sulphur—a review of nutrient balance, environmental impact and fertilizers".

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under elevated thermal conditions, typically in extensional tectonic settings. The redox conditions of the basin

2249: 1881: 1869: 1494: 1472: 312: 4165:"Expression of sulfatases in Rhodopirellula baltica and the diversity of sulfatases in the genus Rhodopirellula" 2190: 2100:; their disappearance marks a distinct shift in the chemistry of ocean water. BIFs have alternating layers of 1890: 1873: 1848: 1844: 1573: 1353:

is assimilated by organisms, it is reduced and converted to organic sulfur, which is an essential component of

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Pellerin, André; Bui, Thi Hao; Rough, Mikaella; Mucci, Alfonso; Canfield, Donald E.; Wing, Boswell A. (2015).

75: 5490: 5449: 5111: 4348: 1918: 700: 42: 3670:"Estimating the effect of elemental sulfur disproportionation on the sulfur-isotope signatures in sediments" 3267:

Kushkevych, Ivan; Procházka, Jiří; Gajdács, Márió; Rittmann, Simon K.-M. R.; Vítězová, Monika (2021-06-15).

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Zhao F, Hawkesford M, McGrath SP (1999). "Sulphur Assimilation and Effects on Yield and Quality of Wheat".

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derived sulfides can be seen in the rock record. This fractionation shows possible evidence for anoxygenic

1390: 380: 372: 358: 285: 5431: 4658:"Sulfur isotopes track the global extent and dynamics of euxinia during Cretaceous Oceanic Anoxic Event 2" 1926:

of these intermediates and other sulfur species has been a useful tool in the study of sulfide oxidation.

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Yücel, Mustafa; Konovalov, Sergey K.; Moore, Tommy S.; Janzen, Christopher P.; Luther, George W. (2010).

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that there is an excess of pyrite deposition rather than oxidation of sulfide minerals exposed on land.

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Farquhar J, Bao H, Thiemens M (August 2000). "Atmospheric influence of Earth's earliest sulfur cycle".

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Jørgensen BB (1982). "Mineralization of organic matter in the sea bed—the role of sulphate reduction".

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2.3 Ga sulfate increases to more than 1 mM; this increase in sulfate is coincident with the "

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of Massachusetts within which sulfur cycling occurs through the direct exchange of sulfur species. The

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through reactions with water in the atmosphere. Once the acid is completely dissociated in water the

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Pedersen RB, Rapp HT, Thorseth IH, Lilley MD, Barriga FJ, Baumberger T, et al. (November 2010).

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can drop to 4.3 or lower causing damage to both man-made and natural systems. According to the EPA,

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Holmer M, Storkholm P (2001). "Sulphate reduction and sulphur cycling in lake sediments: a review".

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generally, ore-forming fluids have a close relationship with ancient hydrocarbon seeps or vents.

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750 million years ago (Ma) there is a renewed deposition of BIF which marks a significant change in

5389: 5384: 2357:, some of which is transported globally. Humans are mining coal and extracting petroleum from the 448: 443: 199: 4213:

Johnston DT (2011). "Multiple sulfur isotopes and the evolution of Earth's surface sulfur cycle".

1629: 772:, and sulfur compounds can be used as oxidants or reductants in microbial respiration. The global 5480: 5323: 4164: 3822: 3669: 2304:

S-containing) water column is a necessary source of that sulfide. When present, the δS values of

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at the site of mineralization. Bacterial reduction of seawater sulfate or a euxinic (anoxic and H

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Sulfide produced by sulfate reduction can be oxidized by iron minerals to make iron sulfides and

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Owens JD, Gill BC, Jenkyns HC, Bates SM, Severmann S, Kuypers MM, et al. (November 2013).

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Evolution of Early Earth's Atmosphere, Hydrosphere, and Biosphere—Constraints from Ore Deposits

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Muyzer G, Stams AJ (June 2008). "The ecology and biotechnology of sulphate-reducing bacteria".

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are key processes in the oceanic sulfur cycle. Approximately, 10% (of the total gas) of H

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up to 46 permil and fractionation larger than 46 permil recorded in sediments must be due to

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S, oxidation state = –2). An analogous process for organic nitrogen compounds is deamination.

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of proteins or deactivation of enzymes, so TSR takes over. However, in hot sediments around

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are the main organic reactants for TSR. The inorganic reaction products in BSR and TSR are H

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to have a depleted δ S which provide the first compelling evidence for sulfate reduction.

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and dissolved sulfate are the reactants, and the products or by-products are as follows:

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Incorporation of sulfide into organic compounds (including metal-containing derivatives).

623: 433: 324: 4972: 4877: 4842: 4791: 4740: 4673: 4610: 4470: 4419: 4364: 4268: 4226: 4180: 4115: 4057: 4016: 3976: 3967: 3951: 3877: 3838: 3724: 3622: 3488: 3430: 3170: 3043: 2992: 2898: 2820: 2701: 2657: 2613: 2548: 2509: 5019: 4984: 4811: 4760: 4692: 4657: 4638: 4439: 4384: 4292:"Isotopic inferences of ancient biochemistries-Carbon, sulfur, hydrogen, and nitrogen." 4140: 4099: 4077: 3981: 3919: 3907: 3798: 3765: 3689: 3650: 3523: 3472: 3447: 3414: 3390: 3363: 3303: 3268: 3197: 3154: 3116: 3081: 3012: 2961: 2918: 2867: 2789: 2713: 1983: 1930: 1876:(AOM) both of which produce carbon dioxide. At depths where sulfate is depleted, 1852: 1789: 1386: 835: 562: 5037: 4513: 3707:

Egger, Matthias; Riedinger, Natascha; Mogollón, José M.; Jørgensen, Bo Barker (2018).

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Oxygen isotopes in marine sulfate and the sulfur cycle over the last 140 million years

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Paytan, A. (1998-11-20). "Sulfur Isotopic Composition of Cenozoic Seawater Sulfate".

4431: 4376: 4327: 4192: 4145: 4127: 4069: 3985: 3923: 3889: 3803: 3785: 3746: 3693: 3642: 3634: 3585: 3528: 3510: 3452: 3415:"Discovery of a black smoker vent field and vent fauna at the Arctic Mid-Ocean Ridge" 3395: 3342: 3308: 3290: 3249: 3241: 3237: 3202: 3184: 3121: 3103: 3055: 3051: 3004: 2953: 2910: 2859: 2793: 2781: 2746: 2736: 2665: 2562: 2476: 2431: 2421: 2292: 1661: 1561: 1004: 757: 592: 438: 290: 226: 5023: 4988: 4764: 4642: 4388: 4234: 3708: 2965: 2871: 2401:

come from electric power generation that relies on burning fossil fuels, like coal.

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Ore fluids are generally linked to metal-rich waters that have been heated within a

2037:

S value of 0. Since there was no biologic activity on early Earth there would be no

1361:

does not act as a major sink for sulfur, instead the majority of sulfur is found in

5330: 5318: 5249: 5219: 5011: 4976: 4933: 4881: 4846: 4795: 4744: 4687: 4677: 4614: 4597:

Paytan, A. (2004-06-11). "Seawater Sulfur Isotope Fluctuations in the Cretaceous".

4571: 4544: 4509: 4474: 4443: 4423: 4368: 4272: 4230: 4184: 4135: 4119: 4081: 4061: 4020: 3971: 3915: 3881: 3842: 3793: 3777: 3736: 3728: 3681: 3654: 3626: 3518: 3500: 3492: 3442: 3434: 3385: 3375: 3334: 3298: 3280: 3233: 3192: 3174: 3111: 3093: 3047: 3016: 2996: 2945: 2922: 2902: 2851: 2824: 2773: 2717: 2705: 2661: 2617: 2552: 2513: 2390: 2269: 2162: 2117: 2097: 2079: 1509: 1505: 1498: 1366: 980: 972: 904: 855: 797: 789: 609: 597: 307: 170: 4951:

Blake-Kalff MM (2000). "Diagnosing sulfur deficiency in field-grown oilseed rape (

4575: 4478: 4372: 3846: 3685: 2777: 1467: 5485: 5350: 5308: 4748: 4291: 4188: 3578: 3338: 3269:"Molecular Physiology of Anaerobic Phototrophic Purple and Green Sulfur Bacteria" 2517: 2405: 2358: 2324:

Human activities have a major effect on the global sulfur cycle. The burning of

2257: 2130: 1444: 1212: 1136: 1120: 1082: 1061: 1013: 930: 587: 542: 406: 389: 2842:

Goldstein TP, Aizenshtat Z (1994). "Thermochemical sulfate reduction a review".

1809:. That ratio is accepted as the international standard and is therefore set at 1569: 5229: 5202: 5197: 5177: 5172: 4662:

Proceedings of the National Academy of Sciences of the United States of America

4548: 3668:

Tsang, Man-Yin; Böttcher, Michael Ernst; Wortmann, Ulrich Georg (August 2023).

2386: 2138: 2134: 2056: 1877: 1793: 1618: 992: 922: 614: 557: 512: 502: 497: 472: 411: 394: 270: 265: 257: 4980: 3885: 3732: 1982:

S = +21‰). The second sulfur sink is pyrite burial in shelf sediments or deep

1929:

The sulfur cycle in marine environments has been well-studied via the tool of

5464: 5406: 5192: 5187: 4626: 4403: 4131: 4042:"Low marine sulphate and protracted oxygenation of the Proterozoic biosphere" 3893: 3789: 3750: 3638: 3514: 3380: 3294: 3245: 3188: 3107: 3098: 3059: 3008: 2914: 2863: 2373: 2153:

S, with an average value close to that of today. Notably changes in seawater

1462: 1452: 1433: 1425: 1050: 547: 537: 492: 487: 477: 425: 348: 280: 5098: 4682: 4618: 4402:

Gill BC, Lyons TW, Young SA, Kump LR, Knoll AH, Saltzman MR (January 2011).

4276: 4123: 4100:"The life sulfuric: microbial ecology of sulfur cycling in marine sediments" 3861: 3630: 3496: 3179: 2750: 2557: 2532: 2025:

The total inventory of sulfur compounds on the surface of the Earth (nearly

1404:

sulfate reduction and sulfide re-oxidation on continental shelves and slopes

903:

in which organic molecules containing sulfur can be desulfurized, producing

5234: 5207: 5150: 4937: 4807: 4756: 4701: 4634: 4435: 4196: 4149: 4073: 4025: 4000: 3807: 3646: 3532: 3456: 3399: 3312: 3253: 3206: 3125: 2957: 2785: 2566: 2312: 2181:

The Great Oxidation Event and sulfur isotope mass-independent fractionation

1894: 1798: 1773: 522: 507: 353: 302: 194: 186: 5089:

Sulfur Oxidation from Soil Microbiology course at Virginia Tech University

4583: 4380: 3781: 1761:, which can form widespread deposits on near mid-ocean spreading centers. 5355: 5345: 5340: 5244: 4404:"Geochemical evidence for widespread euxinia in the later Cambrian ocean" 4326:. Geological Society of America Memoir. Vol. 198. pp. 169–184. 3285: 2333: 2329: 2244: 2207: 2170: 2122: 1456: 1417: 1276: 1260: 1228: 934: 847: 482: 399: 231: 221: 165: 157: 121: 5103: 4799: 4427: 4065: 3607:"Large Sulfur Isotope Fractionation Does Not Require Disproportionation" 2949: 5224: 5182: 5015: 4162: 3741: 3438: 3155:"Long-distance electron transport in individual, living cable bacteria" 2855: 2533:"Reducing food's environmental impacts through producers and consumers" 2354: 2346: 2265: 2101: 2068: 1885: 1769: 1642: 1638: 1592:

S is produced in TSR settings. If there is more than a few percent of H

1116: 894: 567: 532: 527: 517: 340: 2621: 752:

moves between rocks, waterways and living systems. It is important in

5372: 5277: 4255:

Canfield DE, Raiswell R (1999). "The evolution of the sulfur cycle".

3505: 3000: 2906: 2409: 2381: 2296: 2277: 2011: 1806: 1765: 1623: 1613: 1581: 1521: 1378: 1374: 1358: 1292: 1144: 1112: 1111:). Over Earth history, the amount of mobile sulfur increased through 803: 660: 628: 1123:

in an oxygenated atmosphere. Earth's main sulfur sink is the oceans

24: 2338: 2166: 2157:

S occurred during extinction and climatic events during this time.

1362: 926: 147: 4898: 3266: 3080:

Jørgensen, Bo Barker; Findlay, Alyssa J.; Pellerin, André (2019).

2033:

4.6 billion years ago (Ga) the Earth formed and had a theoretical

1917:

polysulfides, then the hydrogen sulfide pathway takes over.

897:. The oxidation states of sulfur are +6 in sulfate and –2 in R–SH. 2342: 2173: 2042: 1821: 1429: 1394: 1354: 1244: 1100: 1086: 1020: 851: 843: 811: 807: 765: 753: 4777: 1814: 4347:

Hoffman PF, Kaufman AJ, Halverson GP, Schrag DP (August 1998).

4098:

Wasmund, Kenneth; Mußmann, Marc; Loy, Alexander (August 2017).

3706: 2446: 2305: 2261: 2228: 1913: 1832: 1828: 1758: 1529: 1382: 1180: 1104: 998: 839: 773: 761: 749: 2231:

in sediments in turn contributes to the accumulation of free O

2189:(GOE) is characterized by the disappearance of sulfur isotope 2096:(BIF) are common sedimentary rocks throughout the Archean and 1908:

Oxidant concentrations at different depths in marine sediments

5282: 4346: 2441: 2285: 2105: 2064: 1501:

to produce hydrogen sulfide, which occurs in both processes.

1370: 949:

in which elemental sulfur can be reduced to hydrogen sulfide.

890: 886: 756:

as it affects many minerals and in life because sulfur is an

669: 3763: 3469: 1813: = 0.00. Deviation from 0.00 is expressed as the 1147:(air pollution) of different foods per 100 grams of protein 5287: 4491: 2325: 1898: 1413: 1324: 1308: 1196: 1164: 674: 4321: 3412: 1872:

is driven by the degradation of buried organic matter and

1664:

emit hydrogen sulfide that support the carbon fixation of

1463:

Biologically and thermochemically driven sulfate reduction

4863: 4456: 3820: 3328: 3709:"Global diffusive fluxes of methane in marine sediments" 3547:"Understanding the symbiosis between the giant tubeworm 3151: 3079: 2763: 1965:

S = 0‰), which release reduced sulfur species (such as H

1764:

Sulfur metabolizing microbes are often engaged in close

3914:. Vol. 10. Amsterdam: Elsevier. pp. 559–591. 3584:(2nd ed.). San Diego, California: Academic Press. 2377: 2281: 5083: 4289: 1397:

in the oceans is controlled by three major processes:

4923: 4655: 4001:"The evolution of the Earth surface sulfur reservoir" 3859: 3667: 3605:

Sim, Min Sub; Bosak, Tanja; Ono, Shuhei (July 2011).

3082:"The Biogeochemical Sulfur Cycle of Marine Sediments" 5070:. Sulphurinstitute.org. Retrieved on 16 August 2012. 4901:

Evolution of the Global Biogeochemical Sulphur Cycle

4298:. Princeton, New Jersey: Princeton University Press. 3823:"Sulfur speciation in the upper Black Sea sediments" 3142:(6th ed). CRC Press. pp. 479-516. ISBN 9781466592414 2116:

Along with the disappearance of BIF, the end of the

1407:

burial of anhydrite and pyrite in the oceanic crust.

921:), oxidation state = 0. This reaction occurs in the 4726: 2884: 2841: 2243:Sulfur is intimately involved in the production of 1998:S = −20‰). The total marine sulfur output flux is 1937:S. The modern global oceans have sulfur storage of 1588:

S is produced in BSR settings, whereas 90% of the H

49:. Unsourced material may be challenged and removed. 4401: 3577: 2643: 1564:BSR can happen at temperatures up to 110 °C. 4097: 3361: 1884:(SMTZ), the upwelling of methane produced by the 1637:Anaerobic sulfide oxidation is performed by both 5462: 4722: 4720: 4526: 4254: 4250: 4248: 4246: 4244: 4208: 4206: 3333:. Springer Berlin Heidelberg. pp. 238–258. 2017: 3949: 3324: 3322: 3220:Ghosh, Wriddhiman; Dam, Bomba (November 2009). 3159:Proceedings of the National Academy of Sciences 3029: 2495: 1633:Biogeochemical sulfur cycle of marine sediments 4828: 3571: 3569: 3567: 3565: 3563: 3551:and chemoautotrophic sulfur-oxidizing bacteria 2524: 2470: 2149:has generally varied between +10‰ and +30‰ in 2145:During the last 600 million years, seawater SO 5119: 5030: 4717: 4317: 4315: 4313: 4311: 4309: 4307: 4305: 4241: 4203: 4039: 3956:Annual Review of Earth and Planetary Sciences 2683: 2681: 2679: 2677: 2675: 2639: 2637: 2635: 2633: 2631: 1607: 721: 3945: 3943: 3941: 3939: 3906: 3580:Biogeochemistry an analysis of global change 3319: 2602:Journal of Geophysical Research: Atmospheres 2530: 1949:S value of +21‰. The overall input flux is 1580:BSR in shallow environments and TSR in deep 4950: 4290:Schidlowski M, Hayes JM, Kaplan IR (1983). 4040:Kah LC, Lyons TW, Frank TD (October 2004). 3604: 3575: 3560: 3273:International Journal of Molecular Sciences 2935: 1076: 933:. Often the elemental sulfur is stored as 5126: 5112: 5094:Sulfur Cycle at Carnegie Mellon University 4302: 2672: 2628: 2599: 728: 714: 5133: 4691: 4681: 4139: 4024: 3975: 3936: 3797: 3740: 3522: 3504: 3446: 3389: 3379: 3302: 3284: 3196: 3178: 3115: 3097: 2978: 2578: 2576: 2556: 2372:is emitted as an air pollutant, it forms 2078:2.7–2.5 Ga is the age of the oldest 963: 109:Learn how and when to remove this message 5001: 4212: 3998: 3219: 2806: 1903: 1628: 1478: 1466: 120: 3362:Klotz MG, Bryant DA, Hanson TE (2011). 2582: 2475:(11th ed.). Pearson. p. 136. 2466: 2464: 2462: 2254:Carbonate-hosted lead-zinc ore deposits 2121:day values. The sulfate levels in the 1945:, mainly occurring as sulfate with the 1473:Dissimilatory sulfate reduction pathway 959:generate hydrogen sulfide from sulfate. 5463: 5050:from the original on December 13, 2011 4596: 4561: 3138:Fike, Bradley, Leavitt (Jan 1, 2015). 2730: 2687: 2573: 2238: 1863: 1488:(key intermediate in the sulfur cycle) 5107: 4093: 4091: 3952:"Rethinking the Ancient Sulfur Cycle" 3950:Fike DA, Bradley AS, Rose CV (2015). 3075: 3073: 3071: 3069: 1626:strings where the oxygen is reduced. 1485:3′-phosphoadenosine-5′-phosphosulfate 943:by sulfur oxidizers produces sulfate. 4903:. New York: Wiley. pp. 77–121. 2459: 2316:economic resource at the same time. 1843:Prior to 2010s, it was thought that 1447:is produced by the decomposition of 1420:has added a substantial amount of SO 47:adding citations to reliable sources 18: 4714:Tychyn et al. (2004) incomplete ref 4529:Earth and Planetary Science Letters 4494:Earth and Planetary Science Letters 3977:10.1146/annurev-earth-060313-054802 3910:(2014). "The global sulfur cycle". 2589:(PhD). Harvard University. 3174055. 2256:(Mississippi Valley-Type MVT), and 2201:S value inferred from the measured 862:These are often termed as follows: 636:Biogeochemical planetary boundaries 13: 5397:Human impact on the nitrogen cycle 4104:Environmental Microbiology Reports 4088: 3920:10.1016/B978-0-08-095975-7.00814-7 3066: 2210:(UV) radiation and the associated 1572:inland seas, continental shelves, 14: 5502: 5077: 4349:"A neoproterozoic snowball earth" 2341:events and then released through 1439:Permian–Triassic extinction event 796:S), elemental sulfur, as well as 5445: 5444: 3238:10.1111/j.1574-6976.2009.00187.x 3052:10.1046/j.1365-2427.2001.00687.x 2531:Poore J, Nemecek T (June 2018). 2235:in Earth's surface environment. 1387:calcium and magnesium carbonates 829:Reduction of sulfate to sulfide. 695: 694: 146: 23: 5061: 4995: 4944: 4917: 4892: 4857: 4831:Geochimica et Cosmochimica Acta 4822: 4771: 4708: 4649: 4590: 4555: 4520: 4485: 4450: 4395: 4340: 4283: 4235:10.1016/j.earscirev.2011.02.003 4156: 4033: 3992: 3900: 3866:Geochimica et Cosmochimica Acta 3853: 3814: 3757: 3700: 3661: 3598: 3539: 3463: 3406: 3355: 3260: 3213: 3145: 3132: 3023: 2972: 2929: 2878: 2835: 2809:Geochimica et Cosmochimica Acta 2800: 2473:Brock Biology of Microorganisms 2471:Madigan MT, Martino JM (2006). 2437:Sulfate-reducing microorganisms 2319: 2250:sedimentary exhalative deposits 1882:sulfate-methane transition zone 1870:Dissimilatory sulfate reduction 1495:dissimilatory sulfate reduction 953:Dissimilative sulfate reduction 838:of sulfur compounds (elemental 764:), being a constituent of many 34:needs additional citations for 2757: 2724: 2593: 2583:Turchyn, Alexandra V. (2005). 2489: 2191:mass-independent fractionation 1874:anaerobic oxidation of methane 1840:S are on the order of +21‰. 947:Dissimilative sulfur reduction 867:Assimilative sulfate reduction 810:, and elemental sulfur (S) to 788:into inorganic forms, such as 16:Biogeochemical cycle of sulfur 1: 4576:10.1126/science.282.5393.1459 4514:10.1016/S0012-821X(03)00676-9 4479:10.1016/j.chemgeo.2010.05.012 4373:10.1126/science.281.5381.1342 3847:10.1016/j.chemgeo.2009.10.010 3686:10.1016/j.chemgeo.2023.121533 2829:10.1016/S0016-7037(99)00292-6 2778:10.1126/science.258.5089.1756 2710:10.1016/S0037-0738(00)00176-7 2452: 2284:, temperature and especially 2018:Evolution of the sulfur cycle 1820:which is a ratio in per mill 941:Oxidation in elemental sulfur 915:Oxidation of hydrogen sulfide 5402:Lichens and nitrogen cycling 5257:Marine biogeochemical cycles 4886:10.1016/1352-2310(95)00390-8 4851:10.1016/0016-7037(83)90151-5 4749:10.1126/science.289.5480.756 4189:10.1016/j.margen.2012.12.001 3364:"The microbial sulfur cycle" 3339:10.1007/978-3-540-72682-1_19 2938:Nature Reviews. Microbiology 2666:10.1016/0883-2927(95)00008-8 2518:10.1180/minmag.1994.58A.1.49 2268:will form as by-products of 1788:Although there are 25 known 1391:carbonate-associated sulfate 917:produces elemental sulfur (S 381:Marine biogeochemical cycles 7: 4257:American Journal of Science 4005:American Journal of Science 3331:Microbial Sulfur Metabolism 2844:Journal of Thermal Analysis 2415: 10: 5507: 4549:10.1016/j.epsl.2011.10.030 4296:Earth's Earliest Biosphere 3477:Environmental Microbiology 2735:. New York: Plenum Press. 2260:deposits. Iron sulfides, 2133:. This was likely due to 1931:sulfur isotope systematics 1919:Microbial sulfur oxidation 1666:chemolithotrophic bacteria 1608:Microbial sulfur oxidation 1449:dimethylsulfoniopropionate 1155:Acidifying Emissions (g SO 5440: 5301: 5265: 5141: 4926:Journal of Cereal Science 3886:10.1016/j.gca.2014.11.007 3733:10.1038/s41561-018-0122-8 3368:Frontiers in Microbiology 3226:FEMS Microbiology Reviews 3140:Ehrlich's Geomicrobiology 3086:Frontiers in Microbiology 2733:Sulfate-reducing bacteria 1655:anoxygenic photosynthesis 1323: 1307: 1291: 1275: 1259: 1243: 1227: 1211: 1195: 1179: 1163: 1154: 1151: 997:S: native, or elemental, 5390:Arctic methane emissions 5385:clathrate gun hypothesis 5156:carbonate–silicate cycle 3912:Treatise on Geochemistry 3545:de Vries, Pablo. (2013) 3381:10.3389/fmicb.2011.00241 3099:10.3389/fmicb.2019.00849 2397:and one fourth of all NO 2055:3.5 Ga anoxyogenic 1856:sedimentary settings. 1428:. In the geologic past, 1135:, where it is the major 1077:Sulfur sources and sinks 925:green and purple sulfur 449:Arctic methane emissions 444:clathrate gun hypothesis 359:Carbonate–silicate cycle 5422:Phosphorus assimilation 5324:environmental chemistry 4981:10.1023/A:1026503812267 4866:Atmospheric Environment 4683:10.1073/pnas.1305304110 4619:10.1126/science.1095258 4541:2011E&PSL.312..484G 4506:2004E&PSL.218..331N 4277:10.2475/ajs.299.7-9.697 4124:10.1111/1758-2229.12538 3631:10.1126/science.1205103 3576:Schlesinger WH (1997). 3555:University of Groningen 3497:10.1111/1462-2920.12388 3180:10.1073/pnas.1800367115 2558:10.1126/science.aaq0216 2212:photochemical reactions 2187:Great Oxygenation Event 2087:Great Oxygenation Event 1780: 1766:symbiotic relationships 1369:including: pyrite rich 603:environmental chemistry 126:Sulfur cycle in general 5068:Sulfur as a fertilizer 5044:NASA Earth Observatory 4938:10.1006/jcrs.1998.0241 4294:. In Schopf JW (ed.). 4026:10.2475/ajs.304.10.839 2498:Mineralogical Magazine 2404:As it is an important 2094:Banded iron formations 2039:isotopic fractionation 1909: 1803:Canyon Diablo troilite 1651:purple sulfur bacteria 1634: 1490: 1476: 1159:eq per 100 g protein) 964:Sulfur oxidation state 742:important sulfur cycle 128: 5417:Nitrogen assimilation 5135:Biogeochemical cycles 4215:Earth-Science Reviews 3782:10.1128/mBio.00530-17 3419:Nature Communications 1924:isotope fractionation 1907: 1880:is prevalent. At the 1647:Green sulfur bacteria 1632: 1482: 1470: 1455:cells in the ocean's 806:of hydrogen sulfide, 140:Biogeochemical cycles 124: 5491:Biogeochemical cycle 5432:Planetary boundaries 5336:carbon sequestration 5166:oceanic carbon cycle 4872:(10–11): 1815–1822. 3999:Canfield DE (2004). 3286:10.3390/ijms22126398 2646:Applied Geochemistry 2427:Microbial metabolism 1145:acidifying emissions 873:) in which sulfate ( 746:biogeochemical cycle 286:nitrogen and lichens 43:improve this article 5427:Sulfur assimilation 5368:Ocean acidification 5004:Fertilizer Research 4973:2000PlSoi.225...95B 4878:1996AtmEn..30.1815P 4843:1983GeCoA..47..855B 4800:10.1038/nature10511 4792:2011Natur.478..369K 4741:2000Sci...289..756F 4674:2013PNAS..11018407O 4668:(46): 18407–18412. 4611:2004Sci...304.1663P 4605:(5677): 1663–1665. 4570:(5393): 1459–1462. 4471:2010ChGeo.275..221J 4428:10.1038/nature09700 4420:2011Natur.469...80G 4365:1998Sci...281.1342H 4359:(5381): 1342–1346. 4269:1999AmJS..299..697C 4227:2011ESRv..106..161J 4181:2013MarGn...9...51W 4116:2017EnvMR...9..323W 4066:10.1038/nature02974 4058:2004Natur.431..834K 4017:2004AmJS..304..839C 3968:2015AREPS..43..593F 3878:2015GeCoA.149..152P 3839:2010ChGeo.269..364Y 3725:2018NatGe..11..421E 3623:2011Sci...333...74S 3489:2014EnvMi..16.3398W 3431:2010NatCo...1..126P 3171:2018PNAS..115.5786B 3044:2001FrBio..46..431H 2993:1982Natur.296..643J 2950:10.1038/nrmicro1892 2899:1988Natur.333..415K 2821:2000GeCoA..64..233A 2772:(5089): 1756–1757. 2702:2001SedG..140..143M 2690:Sedimentary Geology 2658:1995ApGC...10..373M 2614:1995JGR...100.8893R 2549:2018Sci...360..987P 2510:1994MinM...58...88B 2406:nutrient for plants 2239:Economic importance 1864:Marine sulfur cycle 1148: 1085:ranging from +6 in 1081:Sulfur is found in 871:sulfur assimilation 624:Ocean acidification 434:Atmospheric methane 134:Part of a series on 5016:10.1007/BF00747690 3439:10.1038/ncomms1124 3032:Freshwater Biology 2856:10.1007/BF02547004 1984:seafloor sediments 1910: 1853:disproportionation 1847:could fractionate 1790:isotopes of sulfur 1733:In modern oceans, 1662:Hydrothermal vents 1635: 1600:S. The amount of H 1562:hydrothermal vents 1491: 1477: 1451:(DMSP) from dying 1393:). The amount of 1229:Farmed Crustaceans 1142: 836:Disproportionation 784:Mineralization of 129: 5458: 5457: 5412:Nitrogen fixation 5380:Methane clathrate 5361:mycorrhizal fungi 5314:geochemical cycle 5161:deep carbon cycle 5042:, United States: 4957:Triticum aestivum 4910:978-0-471-92251-3 4786:(7369): 369–373. 4735:(5480): 756–759. 4333:978-0-8137-1198-0 4052:(7010): 834–838. 3713:Nature Geoscience 3549:Riftia pachyptila 3483:(11): 3398–3415. 3348:978-3-540-72679-1 3165:(22): 5786–5791. 2987:(5858): 643–645. 2893:(6172): 415–419. 2731:Barton L (1995). 2622:10.1029/94JD03245 2608:(D5): 8893–8918. 2543:(6392): 987–992. 2482:978-0-13-196893-6 2432:Sulfide intrusion 2422:Sulfur metabolism 2293:sedimentary basin 2197:S value from the 2163:sea level changes 2080:sedimentary rocks 1845:sulfate reduction 1506:organic compounds 1499:organic compounds 1424:which acts as an 1401:input from rivers 1367:sedimentary rocks 1339: 1338: 1113:volcanic activity 758:essential element 738: 737: 593:geochemical cycle 439:Methane clathrate 237:mycorrhizal fungi 227:deep carbon cycle 119: 118: 111: 93: 5498: 5448: 5447: 5331:Biosequestration 5319:chemical cycling 5250:deep water cycle 5220:Phosphorus cycle 5128: 5121: 5114: 5105: 5104: 5071: 5065: 5059: 5058: 5057: 5055: 5034: 5028: 5027: 5010:(1–3): 117–125. 4999: 4993: 4992: 4948: 4942: 4941: 4921: 4915: 4914: 4896: 4890: 4889: 4861: 4855: 4854: 4826: 4820: 4819: 4775: 4769: 4768: 4724: 4715: 4712: 4706: 4705: 4695: 4685: 4653: 4647: 4646: 4594: 4588: 4587: 4559: 4553: 4552: 4535:(3–4): 484–496. 4524: 4518: 4517: 4500:(3–4): 331–345. 4489: 4483: 4482: 4465:(3–4): 221–234. 4459:Chemical Geology 4454: 4448: 4447: 4399: 4393: 4392: 4344: 4338: 4337: 4319: 4300: 4299: 4287: 4281: 4280: 4263:(7–9): 697–723. 4252: 4239: 4238: 4221:(1–2): 161–183. 4210: 4201: 4200: 4160: 4154: 4153: 4143: 4095: 4086: 4085: 4037: 4031: 4030: 4028: 3996: 3990: 3989: 3979: 3947: 3934: 3933: 3904: 3898: 3897: 3857: 3851: 3850: 3833:(3–4): 364–375. 3827:Chemical Geology 3818: 3812: 3811: 3801: 3761: 3755: 3754: 3744: 3704: 3698: 3697: 3674:Chemical Geology 3665: 3659: 3658: 3602: 3596: 3595: 3583: 3573: 3558: 3543: 3537: 3536: 3526: 3508: 3467: 3461: 3460: 3450: 3410: 3404: 3403: 3393: 3383: 3359: 3353: 3352: 3326: 3317: 3316: 3306: 3288: 3264: 3258: 3257: 3217: 3211: 3210: 3200: 3182: 3149: 3143: 3136: 3130: 3129: 3119: 3101: 3077: 3064: 3063: 3027: 3021: 3020: 3001:10.1038/296643a0 2976: 2970: 2969: 2933: 2927: 2926: 2907:10.1038/333415a0 2882: 2876: 2875: 2839: 2833: 2832: 2804: 2798: 2797: 2761: 2755: 2754: 2728: 2722: 2721: 2696:(1–2): 143–175. 2685: 2670: 2669: 2641: 2626: 2625: 2597: 2591: 2590: 2580: 2571: 2570: 2560: 2528: 2522: 2521: 2493: 2487: 2486: 2468: 2391:Washington, D.C. 2270:hydrogen sulfide 2118:Paleoproterozoic 2098:Paleoproterozoic 2092:At 1.8 Ga, 2028: 2005: 2003: 1993: 1991: 1977: 1975: 1956: 1954: 1944: 1942: 1891:sulfate reducers 1792:, only four are 1739:Halothiobacillus 1728: 1727: 1726: 1547: 1546: 1545: 1432:intrusions into 1352: 1351: 1350: 1334: 1333: 1318: 1317: 1302: 1301: 1286: 1285: 1270: 1269: 1254: 1253: 1238: 1237: 1222: 1221: 1206: 1205: 1190: 1189: 1174: 1173: 1149: 1141: 1134: 1133: 1132: 1097: 1096: 1095: 1083:oxidation states 1048: 1047: 1046: 1032: 1031: 1030: 957:sulfate reducers 931:chemolithotrophs 905:hydrogen sulfide 885:) is reduced by 884: 883: 882: 856:hydrogen sulfide 825: 824: 823: 798:sulfide minerals 790:hydrogen sulfide 730: 723: 716: 703: 698: 697: 610:Biosequestration 598:chemical cycling 308:Phosphorus cycle 171:deep water cycle 150: 131: 130: 114: 107: 103: 100: 94: 92: 51: 27: 19: 5506: 5505: 5501: 5500: 5499: 5497: 5496: 5495: 5461: 5460: 5459: 5454: 5436: 5351:biological pump 5309:Biogeochemistry 5297: 5266:Research groups 5261: 5137: 5132: 5080: 5075: 5074: 5066: 5062: 5053: 5051: 5036: 5035: 5031: 5000: 4996: 4967:(1−2): 95–107. 4955:L.) and wheat ( 4949: 4945: 4922: 4918: 4911: 4897: 4893: 4862: 4858: 4827: 4823: 4776: 4772: 4725: 4718: 4713: 4709: 4654: 4650: 4595: 4591: 4560: 4556: 4525: 4521: 4490: 4486: 4455: 4451: 4414:(7328): 80–83. 4400: 4396: 4345: 4341: 4334: 4320: 4303: 4288: 4284: 4253: 4242: 4211: 4204: 4169:Marine Genomics 4161: 4157: 4096: 4089: 4038: 4034: 4011:(10): 839–861. 3997: 3993: 3948: 3937: 3930: 3905: 3901: 3858: 3854: 3819: 3815: 3762: 3758: 3705: 3701: 3666: 3662: 3617:(6038): 74–77. 3603: 3599: 3592: 3574: 3561: 3544: 3540: 3468: 3464: 3411: 3407: 3360: 3356: 3349: 3327: 3320: 3265: 3261: 3232:(6): 999–1043. 3218: 3214: 3150: 3146: 3137: 3133: 3078: 3067: 3028: 3024: 2977: 2973: 2934: 2930: 2883: 2879: 2840: 2836: 2805: 2801: 2762: 2758: 2743: 2729: 2725: 2686: 2673: 2642: 2629: 2598: 2594: 2581: 2574: 2529: 2525: 2494: 2490: 2483: 2469: 2460: 2455: 2418: 2400: 2396: 2371: 2364: 2322: 2303: 2258:porphyry copper 2241: 2234: 2225: 2217: 2183: 2148: 2131:ocean chemistry 2111: 2050:Metasedimentary 2026: 2020: 2001: 1999: 1989: 1987: 1973: 1971: 1968: 1952: 1950: 1940: 1938: 1866: 1849:sulfur isotopes 1786: 1774:Vestimentiferan 1756: 1752: 1748: 1725: 1722: 1721: 1720: 1718: 1716: 1712: 1708: 1704: 1700: 1691: 1687: 1683: 1679: 1675: 1610: 1603: 1599: 1595: 1591: 1587: 1551: 1544: 1541: 1540: 1539: 1537: 1535: 1519: 1513: 1489: 1487: 1475: 1465: 1445:Dimethylsulfide 1423: 1357:. However, the 1349: 1346: 1345: 1344: 1342: 1335: 1331: 1330: 1319: 1315: 1314: 1303: 1299: 1298: 1287: 1283: 1282: 1271: 1267: 1266: 1255: 1251: 1250: 1239: 1235: 1234: 1223: 1219: 1218: 1213:Lamb and Mutton 1207: 1203: 1202: 1191: 1187: 1186: 1175: 1171: 1170: 1158: 1137:oxidizing agent 1131: 1128: 1127: 1126: 1124: 1110: 1094: 1091: 1090: 1089: 1087: 1079: 1072: 1065: 1058: 1054: 1045: 1042: 1041: 1040: 1038: 1029: 1026: 1025: 1024: 1022: 1017: 1008: 988: 984: 976: 966: 920: 910: 901:Desulfurization 881: 878: 877: 876: 874: 822: 819: 818: 817: 815: 795: 734: 693: 686: 685: 684: 665: 650: 649:Research groups 642: 641: 640: 619: 588:Biogeochemistry 582: 574: 573: 572: 467: 457: 456: 455: 428: 418: 417: 416: 407:Calcareous ooze 390:Biological pump 385: 375: 365: 364: 363: 343: 333: 332: 331: 260: 250: 249: 248: 189: 179: 178: 177: 160: 127: 115: 104: 98: 95: 52: 50: 40: 28: 17: 12: 11: 5: 5504: 5494: 5493: 5488: 5483: 5481:Soil chemistry 5478: 5473: 5456: 5455: 5453: 5452: 5441: 5438: 5437: 5435: 5434: 5429: 5424: 5419: 5414: 5409: 5404: 5399: 5394: 5393: 5392: 5387: 5377: 5376: 5375: 5365: 5364: 5363: 5358: 5353: 5348: 5343: 5338: 5328: 5327: 5326: 5321: 5316: 5305: 5303: 5302:Related topics 5299: 5298: 5296: 5295: 5290: 5285: 5280: 5275: 5269: 5267: 5263: 5262: 5260: 5259: 5254: 5253: 5252: 5242: 5237: 5232: 5230:Selenium cycle 5227: 5222: 5217: 5216: 5215: 5205: 5203:Nutrient cycle 5200: 5198:Nitrogen cycle 5195: 5190: 5185: 5180: 5178:Hydrogen cycle 5175: 5173:Chlorine cycle 5170: 5169: 5168: 5163: 5158: 5147: 5145: 5139: 5138: 5131: 5130: 5123: 5116: 5108: 5102: 5101: 5096: 5091: 5086: 5079: 5078:External links 5076: 5073: 5072: 5060: 5029: 4994: 4961:Plant and Soil 4953:Brassica napus 4943: 4916: 4909: 4891: 4856: 4837:(5): 855–862. 4821: 4770: 4716: 4707: 4648: 4589: 4554: 4519: 4484: 4449: 4394: 4339: 4332: 4301: 4282: 4240: 4202: 4155: 4110:(4): 323–344. 4087: 4032: 3991: 3962:(1): 593–622. 3935: 3928: 3908:Brimblecombe P 3899: 3852: 3813: 3756: 3719:(6): 421–425. 3699: 3660: 3597: 3590: 3559: 3538: 3462: 3405: 3354: 3347: 3318: 3259: 3212: 3144: 3131: 3065: 3038:(4): 431–451. 3022: 2971: 2944:(6): 441–454. 2928: 2877: 2850:(1): 241–290. 2834: 2815:(2): 233–246. 2799: 2756: 2741: 2723: 2671: 2652:(4): 373–389. 2627: 2592: 2572: 2523: 2488: 2481: 2457: 2456: 2454: 2451: 2450: 2449: 2444: 2439: 2434: 2429: 2424: 2417: 2414: 2398: 2394: 2387:carbon dioxide 2369: 2362: 2321: 2318: 2301: 2240: 2237: 2232: 2223: 2215: 2182: 2179: 2146: 2139:Neoproterozoic 2135:snowball Earth 2109: 2057:photosynthesis 2019: 2016: 1966: 1878:methanogenesis 1865: 1862: 1785: 1779: 1754: 1750: 1746: 1735:Thiomicrospira 1731: 1730: 1723: 1714: 1710: 1706: 1702: 1698: 1694: 1693: 1689: 1685: 1681: 1677: 1673: 1653:(PSB) perform 1619:cable bacteria 1609: 1606: 1601: 1597: 1593: 1589: 1585: 1549: 1542: 1533: 1517: 1511: 1483: 1471: 1464: 1461: 1421: 1409: 1408: 1405: 1402: 1347: 1337: 1336: 1329: 1327: 1321: 1320: 1313: 1311: 1305: 1304: 1297: 1295: 1289: 1288: 1281: 1279: 1273: 1272: 1265: 1263: 1257: 1256: 1249: 1247: 1241: 1240: 1233: 1231: 1225: 1224: 1217: 1215: 1209: 1208: 1201: 1199: 1193: 1192: 1185: 1183: 1177: 1176: 1169: 1167: 1161: 1160: 1156: 1153: 1129: 1108: 1092: 1078: 1075: 1070: 1063: 1056: 1052: 1043: 1027: 1015: 1006: 986: 982: 974: 965: 962: 961: 960: 950: 944: 938: 923:photosynthetic 918: 912: 908: 898: 879: 860: 859: 833: 830: 827: 820: 801: 793: 786:organic sulfur 736: 735: 733: 732: 725: 718: 710: 707: 706: 705: 704: 688: 687: 683: 682: 677: 672: 666: 664: 663: 658: 652: 651: 648: 647: 644: 643: 639: 638: 633: 632: 631: 620: 618: 617: 615:Deep biosphere 612: 607: 606: 605: 600: 595: 584: 583: 581:Related topics 580: 579: 576: 575: 571: 570: 565: 560: 555: 550: 545: 540: 535: 530: 525: 520: 515: 510: 505: 500: 495: 490: 485: 480: 475: 469: 468: 463: 462: 459: 458: 454: 453: 452: 451: 446: 436: 430: 429: 424: 423: 420: 419: 415: 414: 412:Siliceous ooze 409: 404: 403: 402: 397: 395:microbial loop 386: 384: 383: 377: 376: 371: 370: 367: 366: 362: 361: 356: 351: 345: 344: 339: 338: 335: 334: 330: 329: 328: 327: 317: 316: 315: 305: 300: 299: 298: 293: 288: 283: 278: 271:Nitrogen cycle 268: 266:Hydrogen cycle 262: 261: 258:Nutrient cycle 256: 255: 252: 251: 247: 246: 244:Boreal forests 241: 240: 239: 234: 229: 224: 214: 213: 212: 207: 202: 191: 190: 185: 184: 181: 180: 176: 175: 174: 173: 162: 161: 156: 155: 152: 151: 143: 142: 136: 135: 125: 117: 116: 58:"Sulfur cycle" 31: 29: 22: 15: 9: 6: 4: 3: 2: 5503: 5492: 5489: 5487: 5484: 5482: 5479: 5477: 5474: 5472: 5469: 5468: 5466: 5451: 5443: 5442: 5439: 5433: 5430: 5428: 5425: 5423: 5420: 5418: 5415: 5413: 5410: 5408: 5407:Nitrification 5405: 5403: 5400: 5398: 5395: 5391: 5388: 5386: 5383: 5382: 5381: 5378: 5374: 5371: 5370: 5369: 5366: 5362: 5359: 5357: 5354: 5352: 5349: 5347: 5344: 5342: 5339: 5337: 5334: 5333: 5332: 5329: 5325: 5322: 5320: 5317: 5315: 5312: 5311: 5310: 5307: 5306: 5304: 5300: 5294: 5291: 5289: 5286: 5284: 5281: 5279: 5276: 5274: 5271: 5270: 5268: 5264: 5258: 5255: 5251: 5248: 5247: 5246: 5243: 5241: 5238: 5236: 5233: 5231: 5228: 5226: 5223: 5221: 5218: 5214: 5211: 5210: 5209: 5206: 5204: 5201: 5199: 5196: 5194: 5193:Mineral cycle 5191: 5189: 5188:Mercury cycle 5186: 5184: 5181: 5179: 5176: 5174: 5171: 5167: 5164: 5162: 5159: 5157: 5154: 5153: 5152: 5149: 5148: 5146: 5144: 5140: 5136: 5129: 5124: 5122: 5117: 5115: 5110: 5109: 5106: 5100: 5097: 5095: 5092: 5090: 5087: 5085: 5082: 5081: 5069: 5064: 5049: 5046:, acid rain, 5045: 5041: 5040: 5033: 5025: 5021: 5017: 5013: 5009: 5005: 4998: 4990: 4986: 4982: 4978: 4974: 4970: 4966: 4962: 4958: 4954: 4947: 4939: 4935: 4931: 4927: 4920: 4912: 4906: 4902: 4895: 4887: 4883: 4879: 4875: 4871: 4867: 4860: 4852: 4848: 4844: 4840: 4836: 4832: 4825: 4817: 4813: 4809: 4805: 4801: 4797: 4793: 4789: 4785: 4781: 4774: 4766: 4762: 4758: 4754: 4750: 4746: 4742: 4738: 4734: 4730: 4723: 4721: 4711: 4703: 4699: 4694: 4689: 4684: 4679: 4675: 4671: 4667: 4663: 4659: 4652: 4644: 4640: 4636: 4632: 4628: 4624: 4620: 4616: 4612: 4608: 4604: 4600: 4593: 4585: 4581: 4577: 4573: 4569: 4565: 4558: 4550: 4546: 4542: 4538: 4534: 4530: 4523: 4515: 4511: 4507: 4503: 4499: 4495: 4488: 4480: 4476: 4472: 4468: 4464: 4460: 4453: 4445: 4441: 4437: 4433: 4429: 4425: 4421: 4417: 4413: 4409: 4405: 4398: 4390: 4386: 4382: 4378: 4374: 4370: 4366: 4362: 4358: 4354: 4350: 4343: 4335: 4329: 4325: 4318: 4316: 4314: 4312: 4310: 4308: 4306: 4297: 4293: 4286: 4278: 4274: 4270: 4266: 4262: 4258: 4251: 4249: 4247: 4245: 4236: 4232: 4228: 4224: 4220: 4216: 4209: 4207: 4198: 4194: 4190: 4186: 4182: 4178: 4174: 4170: 4166: 4159: 4151: 4147: 4142: 4137: 4133: 4129: 4125: 4121: 4117: 4113: 4109: 4105: 4101: 4094: 4092: 4083: 4079: 4075: 4071: 4067: 4063: 4059: 4055: 4051: 4047: 4043: 4036: 4027: 4022: 4018: 4014: 4010: 4006: 4002: 3995: 3987: 3983: 3978: 3973: 3969: 3965: 3961: 3957: 3953: 3946: 3944: 3942: 3940: 3931: 3929:9780080983004 3925: 3921: 3917: 3913: 3909: 3903: 3895: 3891: 3887: 3883: 3879: 3875: 3871: 3867: 3863: 3856: 3848: 3844: 3840: 3836: 3832: 3828: 3824: 3817: 3809: 3805: 3800: 3795: 3791: 3787: 3783: 3779: 3775: 3771: 3767: 3760: 3752: 3748: 3743: 3738: 3734: 3730: 3726: 3722: 3718: 3714: 3710: 3703: 3695: 3691: 3687: 3683: 3679: 3675: 3671: 3664: 3656: 3652: 3648: 3644: 3640: 3636: 3632: 3628: 3624: 3620: 3616: 3612: 3608: 3601: 3593: 3591:9780126251555 3587: 3582: 3581: 3572: 3570: 3568: 3566: 3564: 3556: 3552: 3550: 3542: 3534: 3530: 3525: 3520: 3516: 3512: 3507: 3502: 3498: 3494: 3490: 3486: 3482: 3478: 3474: 3466: 3458: 3454: 3449: 3444: 3440: 3436: 3432: 3428: 3424: 3420: 3416: 3409: 3401: 3397: 3392: 3387: 3382: 3377: 3373: 3369: 3365: 3358: 3350: 3344: 3340: 3336: 3332: 3325: 3323: 3314: 3310: 3305: 3300: 3296: 3292: 3287: 3282: 3278: 3274: 3270: 3263: 3255: 3251: 3247: 3243: 3239: 3235: 3231: 3227: 3223: 3216: 3208: 3204: 3199: 3194: 3190: 3186: 3181: 3176: 3172: 3168: 3164: 3160: 3156: 3148: 3141: 3135: 3127: 3123: 3118: 3113: 3109: 3105: 3100: 3095: 3091: 3087: 3083: 3076: 3074: 3072: 3070: 3061: 3057: 3053: 3049: 3045: 3041: 3037: 3033: 3026: 3018: 3014: 3010: 3006: 3002: 2998: 2994: 2990: 2986: 2982: 2975: 2967: 2963: 2959: 2955: 2951: 2947: 2943: 2939: 2932: 2924: 2920: 2916: 2912: 2908: 2904: 2900: 2896: 2892: 2888: 2881: 2873: 2869: 2865: 2861: 2857: 2853: 2849: 2845: 2838: 2830: 2826: 2822: 2818: 2814: 2810: 2803: 2795: 2791: 2787: 2783: 2779: 2775: 2771: 2767: 2760: 2752: 2748: 2744: 2742:0-306-44857-2 2738: 2734: 2727: 2719: 2715: 2711: 2707: 2703: 2699: 2695: 2691: 2684: 2682: 2680: 2678: 2676: 2667: 2663: 2659: 2655: 2651: 2647: 2640: 2638: 2636: 2634: 2632: 2623: 2619: 2615: 2611: 2607: 2603: 2596: 2588: 2587: 2579: 2577: 2568: 2564: 2559: 2554: 2550: 2546: 2542: 2538: 2534: 2527: 2519: 2515: 2511: 2507: 2503: 2499: 2492: 2484: 2478: 2474: 2467: 2465: 2463: 2458: 2448: 2445: 2443: 2440: 2438: 2435: 2433: 2430: 2428: 2425: 2423: 2420: 2419: 2413: 2411: 2407: 2402: 2392: 2388: 2383: 2379: 2375: 2374:sulfuric acid 2366: 2360: 2359:Earth's crust 2356: 2350: 2348: 2344: 2340: 2335: 2331: 2327: 2317: 2314: 2309: 2307: 2298: 2294: 2289: 2287: 2283: 2279: 2274: 2271: 2267: 2263: 2259: 2255: 2251: 2246: 2236: 2230: 2221: 2213: 2209: 2204: 2200: 2196: 2192: 2188: 2178: 2175: 2172: 2168: 2164: 2158: 2156: 2152: 2143: 2140: 2136: 2132: 2127: 2124: 2119: 2114: 2107: 2103: 2099: 2095: 2090: 2088: 2083: 2081: 2076: 2072: 2070: 2066: 2062: 2058: 2053: 2051: 2046: 2044: 2040: 2036: 2031: 2023: 2015: 2013: 2007: 1997: 1985: 1981: 1964: 1960: 1948: 1936: 1933:expressed as 1932: 1927: 1925: 1920: 1915: 1906: 1902: 1900: 1896: 1895:methanotrophs 1892: 1887: 1883: 1879: 1875: 1871: 1861: 1857: 1854: 1850: 1846: 1841: 1839: 1834: 1830: 1825: 1823: 1819: 1817: 1812: 1808: 1804: 1800: 1795: 1791: 1783: 1778: 1775: 1771: 1767: 1762: 1760: 1744: 1740: 1736: 1696: 1695: 1688:O + 4 S + 3 H 1671: 1670: 1669: 1667: 1663: 1659: 1656: 1652: 1648: 1644: 1640: 1631: 1627: 1625: 1620: 1615: 1605: 1583: 1578: 1575: 1571: 1565: 1563: 1559: 1553: 1531: 1527: 1523: 1515: 1507: 1502: 1500: 1496: 1486: 1481: 1474: 1469: 1460: 1458: 1454: 1453:phytoplankton 1450: 1446: 1442: 1440: 1435: 1434:coal measures 1431: 1427: 1426:air pollutant 1419: 1415: 1406: 1403: 1400: 1399: 1398: 1396: 1392: 1388: 1384: 1380: 1376: 1372: 1368: 1364: 1360: 1356: 1328: 1326: 1322: 1312: 1310: 1306: 1296: 1294: 1290: 1280: 1278: 1274: 1264: 1262: 1258: 1248: 1246: 1242: 1232: 1230: 1226: 1216: 1214: 1210: 1200: 1198: 1194: 1184: 1182: 1178: 1168: 1166: 1162: 1150: 1146: 1140: 1138: 1122: 1118: 1114: 1106: 1102: 1098: 1084: 1074: 1073: 1066: 1059: 1035: 1034: 1018: 1010: 1009: 1001: 1000: 995: 994: 990: 978: 969: 958: 954: 951: 948: 945: 942: 939: 936: 932: 928: 924: 916: 913: 906: 902: 899: 896: 892: 888: 872: 868: 865: 864: 863: 857: 853: 849: 845: 841: 837: 834: 831: 828: 813: 809: 805: 802: 799: 791: 787: 783: 782: 781: 779: 775: 771: 767: 763: 759: 755: 751: 748:in which the 747: 743: 731: 726: 724: 719: 717: 712: 711: 709: 708: 702: 692: 691: 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