Sulfur Cycle

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Sulfur cycle

The sulfur cycle is a biogeochemical cycle


in which the sulfur moves between rocks,
waterways and living systems. It is
important in geology as it affects many
minerals and in life because sulfur is an
essential element (CHNOPS), being a
constituent of many proteins and cofactors,
and sulfur compounds can be used as
oxidants or reductants in microbial
respiration.[1] The global sulfur 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 sulfur cycle are:
Sulfur cycle in general
Mineralization of organic sulfur into
inorganic forms, such as hydrogen
sulfide (H2S), elemental sulfur, as well as sulfide minerals.
Oxidation of hydrogen sulfide, sulfide, and elemental sulfur (S) to sulfate (SO2−
4 ).
Reduction of sulfate to sulfide.
Incorporation of sulfide into organic compounds (including metal-containing derivatives).
Disproportionation of sulfur compounds (elemental sulfur, sulfite, thiosulfate) into sulfate and
hydrogen sulfide.

These are often termed as follows:

Assimilative sulfate reduction (see also sulfur assimilation) in which sulfate (SO2−
4 ) is
reduced by plants, fungi and various prokaryotes. The oxidation states of sulfur are +6 in
sulfate and –2 in R–SH.
Desulfurization in which organic molecules containing sulfur can be desulfurized,
producing hydrogen sulfide gas (H2S, oxidation state = –2). An analogous process for
organic nitrogen compounds is deamination.
Oxidation of hydrogen sulfide produces elemental sulfur (S8), oxidation state = 0. This
reaction occurs in the photosynthetic green and purple sulfur bacteria and some
chemolithotrophs. Often the elemental sulfur is stored as polysulfides.
Oxidation in elemental sulfur by sulfur oxidizers produces sulfate.
Dissimilative sulfur reduction in which elemental sulfur can be reduced to hydrogen
sulfide.
Dissimilative sulfate reduction in which sulfate reducers generate hydrogen sulfide from
sulfate.

Sulfur oxidation state


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:

S2−: H2 S; (CH3 )2 S; BaS

S0 : native, or elemental, sulfur

S2+: SCl2

S4+: SO2 ; sulfite (SO2−


3 )

S6+: SO2−
4 (H 2 SO 4 , CaSO 4 ); SF6

Sulfur sources and sinks


Sulfur is found in oxidation states ranging from +6 in SO2− 4 to −2 in sulfides. 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 pyrite (FeS2 ). Over Earth history, the amount of mobile sulfur increased through
volcanic activity as well as weathering of the crust in an oxygenated atmosphere.[1] Earth's main sulfur sink
is the oceans SO2−
4 , where it is the major oxidizing agent.
[2]

Mean acidifying emissions (air pollution) of different foods per 100


grams of protein[3]
Food Types Acidifying Emissions (g SO2eq per 100 g protein)
Beef 343.6
Cheese 165.5
Pork 142.7
Lamb and Mutton 139.0
Farmed Crustaceans 133.1
Poultry 102.4
Farmed Fish 65.9
Eggs 53.7
Groundnuts 22.6
Peas 8.5
Tofu 6.7

When SO2− 4 is assimilated by organisms, it is reduced and converted to organic sulfur, which is an essential
component of proteins. However, the biosphere does not act as a major sink for sulfur, instead the majority
of sulfur is found in seawater or sedimentary rocks including: pyrite rich shales, evaporite rocks (anhydrite
and baryte), and calcium and magnesium carbonates (i.e. carbonate-associated sulfate). The amount of
sulfate in the oceans is controlled by three major processes:[4]

1. input from rivers


2. sulfate reduction and sulfide re-oxidation on continental shelves and slopes
3. burial of anhydrite and pyrite in the oceanic crust.
The primary natural source of sulfur to the atmosphere is sea spray or windblown sulfur-rich dust,[5] neither
of which is long lived in the atmosphere. In recent times, the large annual input of sulfur from the burning
of coal and other fossil fuels has added a substantial amount of SO2 which acts as an air pollutant. In the
geologic past, igneous intrusions into coal measures 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 Permian–Triassic extinction event.

Dimethylsulfide [(CH3 )2 S or DMS] is produced by the decomposition of dimethylsulfoniopropionate


(DMSP) from dying phytoplankton cells in the ocean's photic zone, and is the major biogenic gas emitted
from the sea, where it is responsible for the distinctive “smell of the sea” along coastlines.[1] 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.

Biologically and thermochemically driven sulfate reduction

Dissimilatory sulfate reduction pathway

Through the dissimilatory sulfate reduction pathway, sulfate


can be reduced either bacterially (bacterial sulfate reduction)
or inorganically (thermochemical sulfate reduction). This
pathway involves the reduction of sulfate by organic
compounds to produce hydrogen sulfide, which occurs in
both processes.

The main products and reactants of bacterial sulfate reduction


(BSR) and thermochemical sulfate reduction (TSR) are very
similar. For both, various organic compounds and dissolved
sulfate are the reactants, and the products or by-products are
as follows: H2 S, CO2 , carbonates, elemental sulfur and metal
sulfides.[6] However, the reactive organic compounds differ 3′-phosphoadenosine-5′-phosphosulfate
for BSR and TSR because of the mutually exclusive (key intermediate in the sulfur cycle)
temperature regimes. Organic acids are the main organic
reactants for BSR and branched/n-alkanes are the main
organic reactants for TSR. The inorganic reaction products in BSR and TSR are H2 S (HS−) and HCO−3
(CO2 ).[7]

These processes occur because there are two very different thermal regimes in which sulfate is reduced,
particularly in low-temperature and high-temperature environments.[6] BSR usually occurs at lower
temperatures from 0−80 °C, while TSR happens at much higher temperatures around 100–140 °C.[7]
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.[7] These two different regimes appear because at higher
temperatures most sulfate-reducing microbes can no longer metabolize due to the denaturation of proteins
or deactivation of enzymes,[8] so TSR takes over. However, in hot sediments around hydrothermal vents
BSR can happen at temperatures up to 110 °C.[9]

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 stratified inland seas, continental shelves, organic-rich deltas, and hydrothermal
sediments which have intense microbial sulfate reduction because of the high concentration of dissolved
sulfate in the seawater.[10] Additionally, the high amounts of hydrogen sulfide found in oil and gas fields is
thought to arise from the oxidation of petroleum hydrocarbons by sulfate.[11] 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.[12] 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.[13][6] Although much slower than BSR, even
TSR appears to be a geologically fairly fast process.

BSR in shallow environments and TSR in deep reservoirs are key processes in the oceanic sulfur
cycle.[14][6] Approximately, 10% (of the total gas) of H2 S is produced in BSR settings, whereas 90% of
the H2 S is produced in TSR settings.[7] If there is more than a few percent of H2 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 a couple percent of H2 S. The amount of H2 S is affected by several factors such
as, the availability of organic reactants and sulfate and the presence/availability of base and transition
metals.[15]

Sulfur-oxidizing bacteria in hydrothermal vents


Hydrothermal vents emit hydrogen sulfide that support the carbon fixation of chemolithotrophic bacteria
that oxidize hydrogen sulfide with oxygen to produce elemental sulfur or sulfate.[16] The chemical
reactions are as follows:

CO2 + 4 H2S + O2 → CH2O + 4 S0 + 3 H2O

CO2 + H2S + O2 + H2O → CH2O + SO2–


4 +2H
+

In modern oceans, Thiomicrospira, Halothiobacillus, and Beggiatoa are primary sulfur oxidizing
bacteria,[16] and form chemosynthetic symbioses with animal hosts.[17] The host provides metabolic
substrates (e.g., CO2 , O2 , H2 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 gypsum, which can form widespread deposits on near mid-ocean spreading centers.[18]

δ34S
Although there are 25 known isotopes of sulfur, only four are stable and of geochemical importance. Of
those four, two (32 S, light and 34 S, heavy) comprise (99.22%) of sulfur on Earth. The vast majority
(95.02%) of sulfur occurs as 32 S with only 4.21% in 34 S. The ratio of these two isotopes is fixed in the
Solar System 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 Canyon Diablo troilite (CDT), a meteorite.[19] That ratio is
accepted as the international standard and is therefore set at δ = 0.00. Deviation from 0.00 is expressed as
the δ34 S which is a ratio in per mill ( ‰ ). Positive values correlate to increased levels of 34 S, whereas
negative values correlate with greater 32 S in a sample.

Formation of sulfur minerals through non-biogenic processes does not substantially differentiate between
the light and heavy isotopes, therefore sulfur isotope ratios in gypsum or barite 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
32 S.[19] Average present day seawater values of δ34 S are on the order of +21‰.

Prior to 2010s, it was thought that sulfate reduction could fractionate sulfur isotopes up to 46 permil and
fractionation larger than 46 permil recorded in sediments must be due to disproportionation of sulfur
intermediates in the sediment. This view has changed since the 2010s that sulfate reduction can fractionate
to 66 permil.[20] 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 sedimentary settings.[21]

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 that there is an
excess of pyrite deposition rather than oxidation of sulfide minerals exposed on land.[19]

Marine sulfur cycle


The sulfur cycle in marine environments has been well-studied via the tool of sulfur isotope systematics
expressed as δ34 S. The modern global oceans have sulfur storage of 1.3 × 1018 kg,[22] mainly occurring as
sulfate with the δ34 S value of +21‰.[23] The overall input flux is 1.0 × 1011 kg/a with the sulfur isotope
composition of ~3‰.[23] Riverine sulfate derived from the terrestrial weathering of sulfide minerals (δ34 S =
+6‰) is the primary input of sulfur to the oceans. Other sources are metamorphic and volcanic degassing
and hydrothermal activity (δ34 S = 0‰), which release reduced sulfur species (such as H2 S and S0 ). 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 6 × 1010 kg/a (δ34 S
= +21 ‰ ). The second sulfur sink is pyrite burial in shelf sediments or deep seafloor sediments
(4 × 1010 kg/a; δ34 S = −20‰).[24] The total marine sulfur output flux is 1.0 × 1011 kg/a which matches the
input fluxes, implying the modern marine sulfur budget is at steady state.[23] The residence time of sulfur in
modern global oceans is 13,000,000 years.[25]

Evolution of the sulfur cycle


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

The total inventory of sulfur compounds on the surface of the Earth (nearly 1019 kg of sulfur) represents
the total outgassing of sulfur through geologic time.[26][19] 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 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.
4.6 billion years ago (Ga) the Earth formed and had a theoretical δ34 S value of 0. Since there was no
biologic activity on early Earth there would be no isotopic fractionation.[23] 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 Archean (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.[27]

3.8–3.6 Ga marks the beginning of the exposed geologic record because this is the age of the oldest rocks
on Earth. Metasedimentary rocks from this time still have an isotopic value of 0 because the biosphere was
not developed enough (possibly at all) to fractionate sulfur.[28]

3.5 Ga anoxyogenic photosynthesis is established and provides a weak source of sulfate to the global ocean
with sulfate concentrations incredibly low the δ34 S is still basically 0.[27] Shortly after, at 3.4 Ga the first
evidence for minimal fractionation in evaporitic sulfate in association with magmatically derived sulfides
can be seen in the rock record. This fractionation shows possible evidence for anoxygenic phototrophic
bacteria.

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.

2.7–2.5 Ga is the age of the oldest sedimentary rocks to have a depleted δ 34 S which provide the first
compelling evidence for sulfate reduction.[27]

2.3 Ga sulfate increases to more than 1 mM; this increase in sulfate is coincident with the "Great
Oxygenation Event", when redox conditions on Earth's surface are thought by most workers to have
shifted fundamentally from reducing to oxidizing.[29] 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.[29]

At 1.8 Ga, Banded iron formations (BIF) are common sedimentary rocks throughout the Archean and
Paleoproterozoic; their disappearance marks a distinct shift in the chemistry of ocean water. BIFs have
alternating layers of iron oxides and chert. BIFs only form if the water is allowed to supersaturate in
dissolved iron (Fe2+) meaning there cannot be free oxygen or sulfur in the water column because it would
form Fe3+ (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 Fe3+. 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 CO2 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.[27]

Along with the disappearance of BIF, the end of the Paleoproterozoic 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 day values.[29] The sulfate levels in the Proterozoic
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 Archean.

750 million years ago (Ma) there is a renewed deposition of BIF which marks a significant change in ocean
chemistry. This was likely due to snowball Earth episodes where the entire globe including the oceans was
covered in a layer of ice cutting off oxygenation.[30] In the late Neoproterozoic 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.[29]

During the last 600 million years, seawater SO4 has generally varied between +10‰ and +30‰ in δ34 S,
with an average value close to that of today. Notably changes in seawater δ34 S occurred during extinction
and climatic events during this time.[31][32][33][34][35][36][37]

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.[4] 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[38] were able to better constrain the sulfur concentrations in sea water through that
same time. They found that the sea level changes due to Pliocene and Pleistocene glacial 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.

The Great Oxidation Event and sulfur isotope mass-independent


fractionation
The Great Oxygenation Event (GOE) is characterized by the disappearance of sulfur isotope mass-
independent fractionation (MIF) in the sedimentary records at around 2.45 billion years ago (Ga).[39] The
MIF of sulfur isotope (Δ33 S) is defined by the deviation of measured δ33 S value from the δ33 S value
inferred from the measured δ34 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 ultraviolet (UV) radiation and the associated photochemical
reactions, which induced the sulfur isotope mass-independent fractionation (Δ33 S ≠ 0). The preservation of
sulfur isotope mass-independent fractionation signals requires the atmospheric O2 lower than 10−5 of
present atmospheric level (PAL).[26] The disappearance of sulfur isotope mass-independent fractionation at
~2.45 Ga indicates that atmospheric pO2 exceeded 10−5 present atmospheric level after the Great
Oxygenation Event.[39] Oxygen played an essential role in the global sulfur cycles after the Great
Oxygenation Event, such as oxidative weathering of sulfides.[40] The burial of pyrite in sediments in turn
contributes to the accumulation of free O2 in Earth's surface environment.[41]

Economic importance
Sulfur is intimately involved in production of fossil fuels and a majority of metal deposits because of its
ability to act 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: sedimentary exhalative deposits
(SEDEX), Carbonate-hosted lead-zinc ore deposits (Mississippi Valley-Type MVT) and porphyry copper
deposits. Iron sulfides, galena and sphalerite will form as by-products of hydrogen sulfide generation, as
long as the respective transition or base metals are present or transported to a sulfate reduction site.[7] 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 generally ore forming fluids have a close
relationship with ancient hydrocarbon seeps or vents.[29]

Important sources of sulfur in ore deposits are generally deep-seated, but they can also come from local
country rocks, sea water, or marine evaporites. The presence or absence of sulfur is one of the limiting
factors on both the concentration of precious metals and its precipitation from solution. pH, temperature and
especially redox states determine whether sulfides will precipitate. Most sulfide brines will remain in
concentration until they reach reducing conditions, a higher pH or lower temperatures.

Ore fluids are generally linked to metal rich waters that have been heated within a sedimentary basin under
the elevated thermal conditions typically in extensional tectonic settings. The redox conditions of the basin
lithologies exert an important control on the redox state of the metal-transporting fluids and deposits can
form from both oxidizing and reducing fluids.[29] 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
at the site of mineralization. Bacterial reduction of seawater sulfate or a euxinic (anoxic and H2 S-
containing) water column is a necessary source of that sulfide. When present, the δ34 S values of barite are
generally consistent with a seawater sulfate source, suggesting baryte formation by reaction between
hydrothermal barium and sulfate in ambient seawater.[29]

Once fossil fuels or precious metals are discovered and either burned or milled, the sulfur become a waste
product which must be dealt with properly or it can become a pollutant. There has been a great increase in
the amount of sulfur in our present day atmosphere because of the burning of fossil fuels. Sulfur acts as a
pollutant and an economic resource at the same time.

Human impact
Human activities have a major effect on the global sulfur cycle. The burning of coal, natural gas, and other
fossil fuels 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 tectonic events and then released through erosion and weathering 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.[42]

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 atmosphere, some of which is transported globally.
Humans are mining coal and extracting petroleum from the Earth's crust at a rate that mobilizes 150 x 1012
gS/yr, which is more than double the rate of 100 years ago.[43] The result of human impact on these
processes is to increase the pool of oxidized sulfur (SO4 ) in the global cycle, at the expense of the storage
of reduced sulfur in the Earth's crust. Therefore, human activities do not cause a major change in the global
pools of sulfur, but they do produce massive changes in the annual flux of sulfur through the
atmosphere.[19]

When SO2 is emitted as an air pollutant, it forms sulfuric acid through reactions with water in the
atmosphere. Once the acid is completely dissociated in water the pH can drop to 4.3 or lower causing
damage to both man-made and natural systems. According to the EPA, acid rain 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 carbon dioxide, 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
Washington, D.C., 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 SO2 and one fourth of all NO3 come from
electric power generation that relies on burning fossil fuels, like coal.

As it is an important nutrient for plants, sulfur is increasingly used as a component of fertilizers. Recently
sulfur deficiency has become widespread in many countries in Europe.[44][45][46] Because of actions taken
to limit acid rains 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.[47][48]

See also
Sulfur metabolism
Microbial metabolism
Sulfide intrusion
Sulfate-reducing microorganisms
Redox
Sulfur

References
1. Madigan MT, Martino JM (2006). Brock Biology of Microorganisms (11th ed.). Pearson.
p. 136. ISBN 978-0-13-196893-6.
2. Bickle MJ, Alt JC, Teagle DA (1994). "Sulfur transport and sulphur isotope fractionations in
ocean floor hydrothermal systems". Mineralogical Magazine. 58A (1): 88–89.
Bibcode:1994MinM...58...88B (https://ui.adsabs.harvard.edu/abs/1994MinM...58...88B).
doi:10.1180/minmag.1994.58A.1.49 (https://doi.org/10.1180%2Fminmag.1994.58A.1.49).
3. Poore J, Nemecek T (June 2018). "Reducing food's environmental impacts through
producers and consumers" (https://doi.org/10.1126%2Fscience.aaq0216). Science. 360
(6392): 987–992. Bibcode:2018Sci...360..987P (https://ui.adsabs.harvard.edu/abs/2018Sci...
360..987P). doi:10.1126/science.aaq0216 (https://doi.org/10.1126%2Fscience.aaq0216).
PMID 29853680 (https://pubmed.ncbi.nlm.nih.gov/29853680).
4. Turchyn, Alexandra V. (2005). Oxygen isotopes in marine sulfate and the sulfur cycle over
the last 140 million years (https://www.proquest.com/openview/0e5ae0050b1db9b3db0c292
d95bb42b6/1) (PhD). Harvard University. 3174055.
5. Reheis MC, Kihl R (May 1995). "Dust deposition in southern Nevada and California, 1984–
1989: Relations to climate, source area, and source lithology". Journal of Geophysical
Research: Atmospheres. 100 (D5): 8893–8918. Bibcode:1995JGR...100.8893R (https://ui.ad
sabs.harvard.edu/abs/1995JGR...100.8893R). doi:10.1029/94JD03245 (https://doi.org/10.10
29%2F94JD03245).
6. Machel HG, Krouse HR, Sassen R (1995). "Products and distinguishing criteria of bacterial
and thermochemical sulfate reduction". Applied Geochemistry. 10 (4): 373–389.
Bibcode:1995ApGC...10..373M (https://ui.adsabs.harvard.edu/abs/1995ApGC...10..373M).
doi:10.1016/0883-2927(95)00008-8 (https://doi.org/10.1016%2F0883-2927%2895%290000
8-8).
7. Machel HG (2001). "Bacterial and thermochemical sulfate reduction in diagenetic settings —
old and new insights". Sedimentary Geology. 140 (1–2): 143–175.
Bibcode:2001SedG..140..143M (https://ui.adsabs.harvard.edu/abs/2001SedG..140..143M).
doi:10.1016/S0037-0738(00)00176-7 (https://doi.org/10.1016%2FS0037-0738%2800%2900
176-7). S2CID 4606551 (https://api.semanticscholar.org/CorpusID:4606551).
8. Barton L (1995). Sulfate-reducing bacteria. New York: Plenum Press. ISBN 0-306-44857-2.
OCLC 32311676 (https://www.worldcat.org/oclc/32311676).
9. Jørgensen BB, Isaksen MF, Jannasch HW (December 1992). "Bacterial Sulfate Reduction
Above 100{degrees}C in Deep-Sea Hydrothermal Vent Sediments". Science. 258 (5089):
1756–1757. doi:10.1126/science.258.5089.1756 (https://doi.org/10.1126%2Fscience.258.50
89.1756). PMID 17831655 (https://pubmed.ncbi.nlm.nih.gov/17831655). S2CID 129371120
(https://api.semanticscholar.org/CorpusID:129371120).
10. 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". Geochimica et
Cosmochimica Acta. 64 (2): 233–246. Bibcode:2000GeCoA..64..233A (https://ui.adsabs.harv
ard.edu/abs/2000GeCoA..64..233A). doi:10.1016/S0016-7037(99)00292-6 (https://doi.org/1
0.1016%2FS0016-7037%2899%2900292-6).
11. Goldstein TP, Aizenshtat Z (1994). "Thermochemical sulfate reduction a review". Journal of
Thermal Analysis. 42 (1): 241–290. doi:10.1007/BF02547004 (https://doi.org/10.1007%2FB
F02547004). ISSN 0368-4466 (https://www.worldcat.org/issn/0368-4466). S2CID 95526523
(https://api.semanticscholar.org/CorpusID:95526523).
12. 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". Nature. 333 (6172): 415–419. Bibcode:1988Natur.333..415K (https://ui.adsabs.h
arvard.edu/abs/1988Natur.333..415K). doi:10.1038/333415a0 (https://doi.org/10.1038%2F33
3415a0). ISSN 0028-0836 (https://www.worldcat.org/issn/0028-0836). S2CID 4354648 (http
s://api.semanticscholar.org/CorpusID:4354648).
13. Muyzer G, Stams AJ (June 2008). "The ecology and biotechnology of sulphate-reducing
bacteria". Nature Reviews. Microbiology. 6 (6): 441–454. doi:10.1038/nrmicro1892 (https://d
oi.org/10.1038%2Fnrmicro1892). PMID 18461075 (https://pubmed.ncbi.nlm.nih.gov/184610
75). S2CID 22775967 (https://api.semanticscholar.org/CorpusID:22775967).
14. Jørgensen BB (1982). "Mineralization of organic matter in the sea bed—the role of sulphate
reduction". Nature. 296 (5858): 643–645. Bibcode:1982Natur.296..643J (https://ui.adsabs.ha
rvard.edu/abs/1982Natur.296..643J). doi:10.1038/296643a0 (https://doi.org/10.1038%2F296
643a0). ISSN 0028-0836 (https://www.worldcat.org/issn/0028-0836). S2CID 4308770 (http
s://api.semanticscholar.org/CorpusID:4308770).
15. Holmer M, Storkholm P (2001). "Sulphate reduction and sulphur cycling in lake sediments: a
review". Freshwater Biology. 46 (4): 431–451. doi:10.1046/j.1365-2427.2001.00687.x (http
s://doi.org/10.1046%2Fj.1365-2427.2001.00687.x). ISSN 0046-5070 (https://www.worldcat.o
rg/issn/0046-5070).
16. Sievert SM, Hügler M, Taylor CD, Wirsen CO (2008). Dahl C, Friedrich CG (eds.). "Sulfur
Oxidation at Deep-Sea Hydrothermal Vents". Microbial Sulfur Metabolism. Springer Berlin
Heidelberg: 238–258. doi:10.1007/978-3-540-72682-1_19 (https://doi.org/10.1007%2F978-3
-540-72682-1_19). ISBN 978-3-540-72679-1.
17. Klotz MG, Bryant DA, Hanson TE (2011). "The microbial sulfur cycle" (https://www.ncbi.nlm.
nih.gov/pmc/articles/PMC3228992). Frontiers in Microbiology. 2: 241.
doi:10.3389/fmicb.2011.00241 (https://doi.org/10.3389%2Ffmicb.2011.00241).
PMC 3228992 (https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3228992). PMID 22144979
(https://pubmed.ncbi.nlm.nih.gov/22144979).
18. Pedersen RB, Rapp HT, Thorseth IH, Lilley MD, Barriga FJ, Baumberger T, et al. (November
2010). "Discovery of a black smoker vent field and vent fauna at the Arctic Mid-Ocean
Ridge" (https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3060606). Nature Communications.
1 (8): 126. Bibcode:2010NatCo...1..126P (https://ui.adsabs.harvard.edu/abs/2010NatCo...1..
126P). doi:10.1038/ncomms1124 (https://doi.org/10.1038%2Fncomms1124). PMC 3060606
(https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3060606). PMID 21119639 (https://pubmed.
ncbi.nlm.nih.gov/21119639).
19. Schlesinger WH (1997). Biogeochemistry an analysis of global change (https://archive.org/d
etails/isbn_9780126251555) (2nd ed.). San Diego, California: Academic Press.
ISBN 9780126251555.
20. Sim, Min Sub; Bosak, Tanja; Ono, Shuhei (July 2011). "Large Sulfur Isotope Fractionation
Does Not Require Disproportionation" (https://www.science.org/doi/10.1126/science.120510
3). Science. 333 (6038): 74–77. doi:10.1126/science.1205103 (https://doi.org/10.1126%2Fsc
ience.1205103). ISSN 0036-8075 (https://www.worldcat.org/issn/0036-8075).
21. Tsang, Man-Yin; Böttcher, Michael Ernst; Wortmann, Ulrich Georg (August 2023).
"Estimating the effect of elemental sulfur disproportionation on the sulfur-isotope signatures
in sediments" (https://linkinghub.elsevier.com/retrieve/pii/S0009254123002334). Chemical
Geology. 632: 121533. doi:10.1016/j.chemgeo.2023.121533 (https://doi.org/10.1016%2Fj.ch
emgeo.2023.121533).
22. Brimblecombe P (2014). "The global sulfur cycle". Treatise on Geochemistry. Vol. 10.
Amsterdam: Elsevier. pp. 559–591. doi:10.1016/B978-0-08-095975-7.00814-7 (https://doi.or
g/10.1016%2FB978-0-08-095975-7.00814-7). ISBN 9780080983004.
23. Fike DA, Bradley AS, Rose CV (2015). "Rethinking the Ancient Sulfur Cycle". Annual
Review of Earth and Planetary Sciences. 43 (1): 593–622. Bibcode:2015AREPS..43..593F
(https://ui.adsabs.harvard.edu/abs/2015AREPS..43..593F). doi:10.1146/annurev-earth-
060313-054802 (https://doi.org/10.1146%2Fannurev-earth-060313-054802).
S2CID 140644882 (https://api.semanticscholar.org/CorpusID:140644882).
24. Canfield DE (2004). "The evolution of the Earth surface sulfur reservoir" (https://doi.org/10.2
475%2Fajs.304.10.839). American Journal of Science. 304 (10): 839–861.
Bibcode:2004AmJS..304..839C (https://ui.adsabs.harvard.edu/abs/2004AmJS..304..839C).
doi:10.2475/ajs.304.10.839 (https://doi.org/10.2475%2Fajs.304.10.839).
25. Kah LC, Lyons TW, Frank TD (October 2004). "Low marine sulphate and protracted
oxygenation of the Proterozoic biosphere" (https://digitalcommons.unl.edu/cgi/viewcontent.c
gi?article=1098&context=geosciencefacpub). Nature. 431 (7010): 834–838.
Bibcode:2004Natur.431..834K (https://ui.adsabs.harvard.edu/abs/2004Natur.431..834K).
doi:10.1038/nature02974 (https://doi.org/10.1038%2Fnature02974). PMID 15483609 (https://
pubmed.ncbi.nlm.nih.gov/15483609). S2CID 4404486 (https://api.semanticscholar.org/Corp
usID:4404486).
26. Johnston DT (2011). "Multiple sulfur isotopes and the evolution of Earth's surface sulfur
cycle". Earth-Science Reviews. 106 (1–2): 161–183. Bibcode:2011ESRv..106..161J (https://
ui.adsabs.harvard.edu/abs/2011ESRv..106..161J). doi:10.1016/j.earscirev.2011.02.003 (http
s://doi.org/10.1016%2Fj.earscirev.2011.02.003).
27. Canfield DE, Raiswell R (1999). "The evolution of the sulfur cycle". American Journal of
Science. 299 (7–9): 697–723. Bibcode:1999AmJS..299..697C (https://ui.adsabs.harvard.ed
u/abs/1999AmJS..299..697C). doi:10.2475/ajs.299.7-9.697 (https://doi.org/10.2475%2Fajs.2
99.7-9.697).
28. Schidlowski M, Hayes JM, Kaplan IR (1983). "Isotopic inferences of ancient biochemistries-
Carbon, sulfur, hydrogen, and nitrogen." (https://ntrs.nasa.gov/search.jsp?R=19840060271).
In Schopf JW (ed.). Earth's Earliest Biosphere. Princeton, New Jersey: Princeton University
Press.
29. 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.). Evolution of Early Earth's Atmosphere, Hydrosphere, and Biosphere—Constraints
from Ore Deposits. Geological Society of America Memoir. Vol. 198. pp. 169–184. ISBN 978-
0-8137-1198-0.
30. Hoffman PF, Kaufman AJ, Halverson GP, Schrag DP (August 1998). "A neoproterozoic
snowball earth" (https://semanticscholar.org/paper/37b1ffb6aadc8b436c029fb8a3311c0b26
e30d4e). Science. 281 (5381): 1342–1346. Bibcode:1998Sci...281.1342H (https://ui.adsabs.
harvard.edu/abs/1998Sci...281.1342H). doi:10.1126/science.281.5381.1342 (https://doi.org/
10.1126%2Fscience.281.5381.1342). PMID 9721097 (https://pubmed.ncbi.nlm.nih.gov/9721
097). S2CID 13046760 (https://api.semanticscholar.org/CorpusID:13046760).
31. Gill BC, Lyons TW, Young SA, Kump LR, Knoll AH, Saltzman MR (January 2011).
"Geochemical evidence for widespread euxinia in the later Cambrian ocean" (http://www.nat
ure.com/articles/nature09700). Nature. 469 (7328): 80–83. Bibcode:2011Natur.469...80G (htt
ps://ui.adsabs.harvard.edu/abs/2011Natur.469...80G). doi:10.1038/nature09700 (https://doi.o
rg/10.1038%2Fnature09700). PMID 21209662 (https://pubmed.ncbi.nlm.nih.gov/21209662).
S2CID 4319979 (https://api.semanticscholar.org/CorpusID:4319979).
32. 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". Chemical Geology. 275 (3–4): 221–234.
Bibcode:2010ChGeo.275..221J (https://ui.adsabs.harvard.edu/abs/2010ChGeo.275..221J).
doi:10.1016/j.chemgeo.2010.05.012 (https://doi.org/10.1016%2Fj.chemgeo.2010.05.012).
33. 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".
Earth and Planetary Science Letters. 218 (3–4): 331–345. Bibcode:2004E&PSL.218..331N
(https://ui.adsabs.harvard.edu/abs/2004E&PSL.218..331N). doi:10.1016/S0012-
821X(03)00676-9 (https://doi.org/10.1016%2FS0012-821X%2803%2900676-9).
34. Gill BC, Lyons TW, Jenkyns HC (December 2011). "A global perturbation to the sulfur cycle
during the Toarcian Oceanic Anoxic Event". Earth and Planetary Science Letters. 312 (3–4):
484–496. Bibcode:2011E&PSL.312..484G (https://ui.adsabs.harvard.edu/abs/2011E&PSL.3
12..484G). doi:10.1016/j.epsl.2011.10.030 (https://doi.org/10.1016%2Fj.epsl.2011.10.030).
35. Paytan, A. (1998-11-20). "Sulfur Isotopic Composition of Cenozoic Seawater Sulfate".
Science. 282 (5393): 1459–1462. doi:10.1126/science.282.5393.1459 (https://doi.org/10.112
6%2Fscience.282.5393.1459). PMID 9822370 (https://pubmed.ncbi.nlm.nih.gov/9822370).
36. Paytan, A. (2004-06-11). "Seawater Sulfur Isotope Fluctuations in the Cretaceous". Science.
304 (5677): 1663–1665. Bibcode:2004Sci...304.1663P (https://ui.adsabs.harvard.edu/abs/20
04Sci...304.1663P). doi:10.1126/science.1095258 (https://doi.org/10.1126%2Fscience.1095
258). ISSN 0036-8075 (https://www.worldcat.org/issn/0036-8075). PMID 15192227 (https://p
ubmed.ncbi.nlm.nih.gov/15192227). S2CID 10539452 (https://api.semanticscholar.org/Corp
usID:10539452).
37. Owens JD, Gill BC, Jenkyns HC, Bates SM, Severmann S, Kuypers MM, et al. (November
2013). "Sulfur isotopes track the global extent and dynamics of euxinia during Cretaceous
Oceanic Anoxic Event 2" (https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3831968).
Proceedings of the National Academy of Sciences of the United States of America. 110 (46):
18407–18412. Bibcode:2013PNAS..11018407O (https://ui.adsabs.harvard.edu/abs/2013PN
AS..11018407O). doi:10.1073/pnas.1305304110 (https://doi.org/10.1073%2Fpnas.1305304
110). PMC 3831968 (https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3831968).
PMID 24170863 (https://pubmed.ncbi.nlm.nih.gov/24170863).
38. Tychyn et al. (2004) incomplete ref
39. Farquhar J, Bao H, Thiemens M (August 2000). "Atmospheric influence of Earth's earliest
sulfur cycle". Science. 289 (5480): 756–759. Bibcode:2000Sci...289..756F (https://ui.adsabs.
harvard.edu/abs/2000Sci...289..756F). doi:10.1126/science.289.5480.756 (https://doi.org/10.
1126%2Fscience.289.5480.756). PMID 10926533 (https://pubmed.ncbi.nlm.nih.gov/109265
33). S2CID 12287304 (https://api.semanticscholar.org/CorpusID:12287304).
40. 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". Nature. 478 (7369): 369–373. Bibcode:2011Natur.478..369K (https://ui.adsabs.harva
rd.edu/abs/2011Natur.478..369K). doi:10.1038/nature10511 (https://doi.org/10.1038%2Fnatu
re10511). PMID 22012395 (https://pubmed.ncbi.nlm.nih.gov/22012395). S2CID 205226545
(https://api.semanticscholar.org/CorpusID:205226545).
41. Berner RA, Raiswell R (1983). "Burial of organic carbon and pyrite sulfur in sediments over
phanerozoic time: a new theory". Geochimica et Cosmochimica Acta. 47 (5): 855–862.
Bibcode:1983GeCoA..47..855B (https://ui.adsabs.harvard.edu/abs/1983GeCoA..47..855B).
doi:10.1016/0016-7037(83)90151-5 (https://doi.org/10.1016%2F0016-7037%2883%299015
1-5).
42. 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". Atmospheric
Environment. 30 (10–11): 1815–1822. Bibcode:1996AtmEn..30.1815P (https://ui.adsabs.har
vard.edu/abs/1996AtmEn..30.1815P). doi:10.1016/1352-2310(95)00390-8 (https://doi.org/1
0.1016%2F1352-2310%2895%2900390-8).
43. Brimblecombe P, Hammer C, Rodhe H, Ryaboshapko A, Boutron CF (1989). "Human
Influences on the sulphur cycle.". In Brimblecombe P, Lein AY (eds.). Evolution of the Global
Biogeochemical Sulphur Cycle. New York: Wiley. pp. 77–121. ISBN 978-0-471-92251-3.
44. Zhao F, Hawkesford M, McGrath SP (1999). "Sulphur Assimilation and Effects on Yield and
Quality of Wheat". Journal of Cereal Science. 30 (1): 1–17. doi:10.1006/jcrs.1998.0241 (http
s://doi.org/10.1006%2Fjcrs.1998.0241).
45. Blake-Kalff MM (2000). "Diagnosing sulfur deficiency in field-grown oilseed rape (Brassica
napus L.) and wheat (Triticum aestivum L.)". Plant and Soil. 225 (1−2): 95–107.
doi:10.1023/A:1026503812267 (https://doi.org/10.1023%2FA%3A1026503812267).
S2CID 44208638 (https://api.semanticscholar.org/CorpusID:44208638).
46. Ceccotti SP (1996). "Plant nutrient sulphur—a review of nutrient balance, environmental
impact and fertilizers". Fertilizer Research. 43 (1–3): 117–125. doi:10.1007/BF00747690 (htt
ps://doi.org/10.1007%2FBF00747690). S2CID 42207099 (https://api.semanticscholar.org/Co
rpusID:42207099).
47. Glossary (http://earthobservatory.nasa.gov/Glossary/?mode=all), United States: NASA Earth
Observatory, acid rain, archived (https://web.archive.org/web/20111213175357/http://earthob
servatory.nasa.gov/Glossary/?mode=all) from the original on December 13, 2011, retrieved
February 15, 2013
48. Sulfur as a fertilizer (https://www.sulphurinstitute.org/learnmore/faq.cfm#plants).
Sulphurinstitute.org. Retrieved on 16 August 2012.

External links
EPA (http://www.epa.gov/)
Sulfur Oxidation from Soil Microbiology course at Virginia Tech University (https://web.archiv
e.org/web/20090226194932/http://filebox.vt.edu/users/chagedor/biol_4684/Cycles/Soxidat.h
tml)
Sulfur Cycle at Carnegie Mellon University (https://web.archive.org/web/20030525021101/ht
tp://telstar.ote.cmu.edu/environ/m3/s4/cycleSulfur.shtml)
Lenntech (http://www.lenntech.com/sulphur-cycle.htm)

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