BNL-112491-2016-BC

Sulfur Cycle The Modern Natural Global Sulfur Cycle

Martin A. Schoonen The modern natural global sulfur cycle is dominated by

Brookhaven National Laboratory, Upton, NY, USA processes involving transfer of sulfur in and out of the oceans
Department of Geosciences, Stony Brook University, Stony (Sievert et al., 2007). A significant amount of sulfur is lofted
Brook, NY, USA into the air in the form of small sulfate-containing salt crys-
tals; see Figure 1. Most of the particles settle rapidly back into
the ocean, but some are transported over land and are
Definition removed from the air mass through precipitation or by set-
tlings as dry deposition. Removal of sulfate through microbial
The global sulfur cycle refers to the transfer of sulfur between reduction in marine sediments to sulfide, followed by the
the upper lithosphere, hydrosphere, pedosphere, biosphere, formation of pyrite, is a major process that removes sulfate
and atmosphere as a result of geological, biological, and from the ocean (Schoonen, 2004). Some sulfate is also
anthropogenic processes. Sulfur passing through the cycle is removed from the oceans in the form of evaporate minerals
subject to redox reactions with oxygen, carbon, and iron as and as a trace constituent of sedimentary carbonates (Staudt
major reactants, which lead to a tight coupling of the global and Schoonen, 1995). Microbial conversion of sulfate into
cycles for these elements. volatile organo-sulfur compounds in marine environments
also contributes to a transfer of sulfur from the ocean reservoir
through the biosphere into the atmosphere (Sievert et al.,
The Major Sulfur Reservoirs on Earth 2007).
Inputs to the ocean reservoir in the natural sulfur cycle are
Most sulfur on Earth involved in the global sulfur cycle is dominated by weathering of sulfate-containing evaporative
retained in the upper lithosphere and marine sediments deposits and weathering of pyrite-containing sediments.
(Table 1). A large unknown amount of sulfur residing in the Removal of volcanogenic sulfur emissions via precipitation
Earth’s core and mantle is effectively sequestered and or dry deposition into the oceans constitutes a small input,
excluded from the global sulfur cycle. The oceans contain although the magnitude of this flux varies with volcanic
most of the sulfur residing in the hydrosphere, dwarfing the activity (Jones et al., 2016).
amount of sulfur in lakes and rivers (Table 1). The amount of The magnitudes of all the fluxes in the modern natural
sulfur contained in soils and biomass is roughly four orders of global sulfur cycle are difficult to reconstruct because contri-
magnitude smaller than the amount of sulfur in the oceans, butions from human activity are difficult to separate from
while the atmosphere represents the smallest reservoir of natural contributions. New approaches relying on the study
sulfur on Earth (Table 1). Table 1 not only summarizes esti- of multiple S isotope systematics are promising (Tostevin
mates of the amount of sulfur contained in the major reser- et al., 2014), but it remains difficult to close the natural sulfur
voirs; it also indicates the most abundant forms of sulfur in budget.
each reservoir.

# Springer International Publishing Switzerland 2016

W.M. White (ed.), Encyclopedia of Geochemistry,
DOI 10.1007/978-3-319-39193-9_73-1
2 Sulfur Cycle

Sulfur Cycle, Table 1 Major sulfur reservoirs on Eartha

Reservoir Major forms of sulfur Mass (Tg S)b
Atmosphere Gas: H2S, SO2, DMS, OCS 4.8
Aerosols: H2SO4, (NH4)2SO4
Pedosphere and biosphere Sulfates, organic S, pyrite 3  105
Rivers and lakes SO42 300
Oceans SO42 1.3  109
Marine sediments Pyrite, gypsum, anhydrite 3  108
Lithosphere Gypsum, anhydrite, metal sulfides, sulfur 2  1010
a
Based on Brimblecombe (2014) and Jones et al., (2016)
b
Tg is 1012 g

Sulfur Cycle,
Figure 1 Simplified
modern natural sulfur cycle.
The weight of the arrow
indicates the relative
importance of a given flux.
There is considerable
cycling of sulfur that
involves uptake and release
of sulfur within the overlaps
of hydrosphere, lithosphere,
and biosphere as indicated
by the curved arrows.
Anthropogenic activities
have a significant effect on
the natural sulfur cycle; see
Figure 2, which makes it
difficult to determine the
absolute magnitude of the
modern natural fluxes.
#
CAS carbonate associated
sulfur.

Sulfur Cycle Through the Earth’s History sequestration of sulfate as metal sulfide as ocean water
interacted with the crust at elevated temperatures.
As the Earth evolved, so did the sulfur cycle (Rickard, 2012; The emergence of life triggered significant changes in the
Brimblecombe, 2014). Microbial processes play a significant sulfur cycle (Rickard, 2012). The most profound change to
role in the modern natural sulfur cycle (Figure 1). Hence, on a the sulfur cycle occurred at the time of the transition from an
prebiotic Earth, the sulfur cycle would have been dominated anoxic atmosphere to an oxic atmosphere around 2.3 Ga as a
by emissions of volcanic sulfur gases – predominantly SO2, result of the emergence of photosynthetic bacteria producing
with minor H2S – into the atmosphere and removal of sulfur oxygen as a waste product. Detailed studies exploiting multi-
from the atmosphere through photochemical reactions. There S-isotope systematics point to a sulfur cycle that is largely
was likely very little subaerial crust, all but eliminating gyp- dominated by inorganic processes up to this point in the
sum deposition and dissolution as major processes at this Earth’s history (Johnston, 2011). Once the atmosphere
early time. Dissolved reduced iron (Fe(II)), leached from contained molecular oxygen, volcanogenic sulfur emitted
crustal rock interacting with ocean waters, would have limited into the atmosphere was readily oxidized to sulfate. Besides
the amount of hydrogen sulfide in solution through iron the accumulation of oxygen in the atmosphere, the growth of
sulfide precipitation. A higher heat flow on the early Earth continents enabled chemical weathering of sulfide-containing
would have promoted widespread hydrothermal circulation of rocks through oxidation, resulting in the enhanced transport
ocean water through the crust. The net effect would have been of sulfate to the ocean. This sets the stage for sulfate-reducing
bacteria – possibly long present in the ocean but limited by the
Sulfur Cycle 3

Sulfur Cycle,
Figure 2 Annual fluxes of
sulfur (Tg/a). Fluxes based
on Brimblecombe (2014)
and Berner and Berner
(1996) The flux associated
with wildfires is estimated
to be a factor of ten smaller
than biomass burning
associated with crop waste
burning and land-clearing
activities.

availability of sulfate – to flourish and produce sedimentary the sea. Roasting of metal sulfide ores, a necessary step to
pyrite in abundance. The emergence of continents also pro- provide society with metals such as zinc and copper, releases
vided settings for the formation of evaporite deposits that a significant amount of SO2. International shipping, which
removed sulfate from the oceans in the form of gypsum and relies on burning of S-rich bunker fuel, amounts to about
barite. 10 % of the global anthropogenic SO2 emissions (Klimont
With microbial life established and continents forming and et al., 2013).
reforming, the sulfur cycle saw additional perturbation as a The magnitude of the anthropogenic perturbation of the
result of changes in the rate of primary production, evaporite sulfur cycle is illustrated in Figure 2. For example, it is
deposition, and weathering (Brimblecombe, 2014). Geologi- estimated that more than half of the sulfur transported to the
cal, geochemical, and isotopic studies have allowed for oceans by rivers and 75 % of the sulfur emissions to the
detailed reconstructions of these excursions. However, one atmosphere are anthropogenic in origin (Berner and Berner,
of the single largest excursions in the sulfur cycle has been 1996).
induced by human activity over the last two centuries. On a global scale, the emissions of SO2 have dropped
recently (Klimont et al., 2013). Changes in economic activity
have a profound effect on the demand for fossil fuel, metals,
Anthropogenic Influence on the Sulfur Cycle and transportation of goods via international shipping, and the
recent (2005–2011) drop likely reflects the impact of a global
Anthropogenic activities transfer a significant amount of recession. However, it is projected that economic growth in
additional sulfur into the atmosphere and hydrosphere. Most India, an expansion of international shipping, and growth of
pronounced is the burning of S-containing fossil fuel, such as emerging economies in Africa will add to the atmospheric
coal. Sulfur in coal is predominantly present as small pyrite SO2 burden. At the same time, stricter environmental regula-
crystals (FeS2), which converts to gaseous SO2 upon burning tions are expected to lead to a broader application of technol-
and contributes to acidification of rain. Modern scrubbing ogies to scrub SO2 from flue gas in China, Europe, and North
technologies remove much of the SO2 from flue gas, but the America. While this will lead to a long-term, sustained
technology is not widely implemented in China and India, decrease in SO2 emissions, it only addresses one of the
which have emerged as major contributors to the atmospheric anthropogenic processes that contributes to the imbalance of
SO2 burden (Klimont et al., 2013). In addition, mining of coal the global sulfur cycle (Klimont et al., 2013; Brimblecombe,
or metal sulfides creates sulfur-containing dust as well as 2014).
sulfide-containing mine waste that often reacts with water
and air to form acid mine drainage. Oxidation of mine waste
contributes significantly to the riverine flux of sulfate out to
4 Sulfur Cycle

Conclusions Brimblecombe, P., 2014. 10.14 – The global sulfur cycle A2. In Holland,
H. D., and Turekian, K. K. (eds.), Treatise on Geochemistry, 2nd edn.
Oxford: Elsevier, pp. 559–591.
The modern global sulfur cycle is out of balance as a result of Johnston, D. T., 2011. Multiple sulfur isotopes and the evolution of
anthropogenic activity. The sulfur cycle has changed as the Earth’s surface sulfur cycle. Earth-Science Reviews, 106, 161–183.
Earth evolved. On the prebiotic Earth, volcanic emissions Jones, M. T., Jerram, D. A., Svensen, H. H., and Grove, C., 2016. The
played a key role in the sulfur cycle. This cycle may have effects of large igneous provinces on the global carbon and sulphur
cycles. Palaeogeography Palaeoclimatology Palaeoecology, 441,
remained largely unchanged, until free oxygen accumulated 4–21.
in the atmosphere as photosynthetic microbes emerged. The Klimont, Z., Smith, S. J., and Cofala, J., 2013. The last decade of global
presence of oxygen and the growth of continents fundamen- anthropogenic sulfur dioxide. Environmental Research Letters, 8.
tally changed the sulfur cycle, with evaporate deposition, Rickard, D., 2012. The Evolution of the Sedimentary Sulfur Cycle,
Sulfidic Sediments and Sedimentary Rocks. Amsterdam: Elsevier,
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It is thought that the flux of sulfate removal from the ocean Sievert, S. M., Kiene, R. P., and Schulz-Vogt, H. N., 2007. The sulfur
through microbial sulfate reduction has grown with the cycle. Oceanography, 20, 117–123.
increased atmospheric sulfur deposited in the ocean as a result Staudt, W. J., and Schoonen, M. A. A., 1995. Sulfate incorporation into
of human activity. Adoption of new mitigation technologies is sedimentary carbonates. In Vairavamurthy, M. A., and Schoonen,
M. A. A. (eds.), Geochemical Transformations of Sedimentary Sul-
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