SULFUR CYCLE

Sulfur is found on Earth as sulfates in rocks or as free sulfur. Sulfur occurs in the
combination with several metals such as lead and mercury. In the Periodic Table, sulfur is
denoted as S with the molecular weight of 32.065 g/mol and atomic number of 16. Sulfur was
mined in the form of yellow element and used for gunpowder and fireworks. Sulfur also become
an important element of biological molecules in small quantities. Sulfur and its compounds had
become an important element in the industrial processes.

In the paper and textile industries, sulfur dioxide (SO 2) is used as a bleaching agent to
bleach wood pulp for paper and fiber for various textiles. Sulfur dioxide is a colorless gas that
give a choking sensation when breathed. It able to kill molds and bacteria and is used for the
preservations of dry fruits such as apples and to clean out vats that is used to prepare fermented
food such as cheese. Sulfuric acid (H2SO4) is a chemical that is widely used and it has a very
strong affinity for water. It absorbs water and is used in various industrial processes as a
dehydrating agent.[ http://environ.andrew.cmu.edu/m3/s4/cycleSulfur.shtml]

The concentration of sulfur by sulfur oxides (SOx) at the atmosphere is found due to two
type of source; natural and anthropogenic sources. For the anthropogenic sources such as
electricity generation, factories and motor vehicles, the gases emitted can be carried hundreds of
kilometers in the atmosphere before they are converted to acids and deposited. This would cause
the ecological damage being widely spread. Natural sources such as volcanic eruptions would
release large quantities of sulfur dioxide into the air. Each time the eruptions occur is enough to
cause the change of global climate. Not only volcanic eruptions, the biological decaying process
become the source of sulfur dioxide production. The biological decaying process will release
hydrogen sulfide and then reacted with oxygen to produce sulfur dioxide.[
http://www.ehow.com/info_10011402_major-sources-sulfur-dioxide.html]

In Malaysia, the environmental issues was monitored by Department of Environment

(DOE). DOE will follow the Environment Quality Act (EQA) enacted by the Malaysian
Parliament. For sulfur emission, it lies under the Environment Quality (Clean Air) Regulations
2014. For each activities and industry, there are limitations that need to be followed in order to
conserve and preserve the environment. The limitations for sulfur emission according to EQA is
as follows:

a) For control of fuel burning equipment, incinerators and crematoria:

Fuel type Fuel Fuel quality parameter

Liquid All Sulfur content < 500 ppm (per weight)
Solid Coal Sulfur content < 1% (per weight)

b) For heat and power generations (boiler):

Fuel type Pollutant Capacity Limit value

Solid and liquid Sum of SO2 and > 10 MWe 500 mg/m3
fuels SO3, expressed as
SO2

c) For production and processing of ferrous metals (iron and steel mills):

Source Pollutant Limit value

Sinter plants (waste gas from Sum of SO2 and SO3, 500 mg/m3
the sintering belt) expressed as SO2

d) For ferrous metal foundries with a capacity > 1 ton molten metal per day:

Source Pollutant Limit value

Cupola furnace Sum of SO2 and SO3, 500 mg/m3
expressed as SO2

e) For production and processing of non-ferrous metals with a capacity > 0.5 tons per
day for lead or cadmium or > 2 tons per day for other metals:

Source Pollutant Limit value

Sinter plants (waste gas from Sum of SO2 and SO3, 500 mg/m3
the sintering belt) expressed as SO2

f) For oil and gas industries : refineries (all sizes);natural gas processing and storage;
storage and handling of petroleum products:

Source Pollutant Limit value

Claus plant Sulphur Recovery > 95%
g) For non-metallic (mineral) industry:

Source Pollutant Limit value

Glass furnace Sum of SO2 and SO3, 800 mg/m3
Ceramic furnace
expressed as SO2

h) For pulp and paper industry including paper recycling facilities in all sizes:

Source Pollutant Limit value

Lime kilns Hydrogen sulfide (H2S) 15 mg/m3
Sulfite mills Total sulfur 1.5 kg/t Air Dried Pulp
(ADP)
Kraft and others 1.0 kg/t Air Dried Pulp
(ADP)

i) For chemical and petrochemical industry in all sizes:

Pollutant Limit value

3
Sum of SO2 and SO3, expressed as SO2 100 mg/m
Hydrogen sulfide (H2S) 7.5 mg/m3

j) For waste incinerators in all sizes:

Pollutant Limit value

Sum of SO2 and SO3, expressed as SO2 50 mg/m3
[http://ensearch.org/wp-content/uploads/2014/10/Peraturan-
peraturan_kualiti_alam_sekeliling_udara_bersih_2014-1.pdf]
 Figure 1 : The sulfur cycle
(SOURCE: https://global.britannica.com/science/sulfur-cycle)

The sulfur cycles is the collection of sulfur movement processes to and from minerals and
living systems. The sulfur cycles exist between the oceans, lands and atmosphere. There are four
steps in sulfur cycle which are;

1) Mineralization of organic sulfur into inorganic forms, such as hydrogen sulfide (H 2S),
elemental sulfur, as well as sulfide minerals.
2) Oxidation of hydrogen sulfide, sulfide and elemental sulfur (S) to sulfate (SO42-)
3) Reduction of sulfate to sulfide.
4) Incorporation of sulfide into organic compounds including metal-containing derivatives.
[https://en.wikipedia.org/wiki/Sulfur_cycle]

On the land, there are four major ways for the sulfur deposition which are precipitation,
direct fallout from the atmosphere, rock weathering and decomposition of organic materials. At
the atmosphere, the sulfur is found in the form of sulfur dioxide (SO2) from the smelting and
burning of fossil fuel and volcanic eruptions. As the rain falls, the sulfur dioxide is oxidized by
reaction with the hydroxyl radical via a intermolecular reaction:

SO2 + OH. -----> HOSO2.

which is followed by :

HOSO2. + O2 ----> HO2. + SO3

In the presence of water sulfur trioxide (SO3) is converted rapidly to sulfuric acid:

SO3(g) + H2O(l) ----> H2SO4 (l)

The weak sulfuric acid that fall down to the Earth is known as acid rain phenomena. Sulfur also
can fall directly from the atmosphere in a fallout process.

The weathering of sulfur-containing rocks will release sulfur into the soil. These kind of
rocks were originated from ocean sediments that are moved to land by geologic unlift. their soil
sulfates (SO42-) will be used by terrestrial ecosystems. On the death and decomposition of
organisms, the sulfur will be released back into the atmosphere as hydrogen sulfide (H 2S) gas
and through geothermal vents. The sulfur will enters the ocean by the runoff from land, fallout
and underwater geothermal vents. Sulfur, in the forms of sulfates becomes a biological energy
sources for chemoautotrophs that is important for some marine ecosystems.

[https://www.boundless.com/biology/textbooks/boundless-biology-textbook/ecosystems-
46/biogeochemical-cycles-258/the-sulfur-cycle-961-12220/]

Even so, this cycle will cause some effect to environment and human. In the water aspect,
the result of acid rain can cause damage to fish and other marine animals due to lower pH and
higher aluminum concentrations in surface water. At pH lower than5, most of the fish egg will no
hatch and kill the adult fish. As the acidity of the water increase, the biodiversity will reduced.
 Figure 2: Effect of acid rain to marine life

(SOURCE : http://acidraintoxicity.weebly.com/effects-of-acid-rain.html)

Not only that, the soil biology can be serious damaged due to acid rain. There are some of
the tropical microbes can consume acids but other microbes are unable to withstand the acidity.
The enzymes of the microbes will be denatured. The hydronium ions in the acid rain will
mobilize toxins and leach away the essential nutrient and minerals. Acid rain will slow down the
growth of vulnerable forests such as high altitude forests and cause leaves and needles to turn
brown and fall off. They are surrounded by clouds and fog which are more acidic than rain. In
order to maintain the stability of the pH, a limestone is added to the soil.
 Figure 3: Effect of acid rain to plants

(SOURCE : http://imgarcade.com/1/acid-rain-damage-to-plants/)

Since nowadays the awareness about environment become a serious issues, most of the
companies had install a system that is able to reduce the emission of the sulfur to the atmosphere.
One of it is Flue gas desulfurization (FGD). FGD is mainly used in the coal-fired power plants in
order to remove the sulfur content in their flue gas emission. The FGD tower is equipped with a
fan that extracts hot smoke stack gasses from the power plant into the tower. Since SO 2 is an
acidic gas, the sorbent slurries or other material that is suitable to remove SO 2 gas is alkaline
.Lime or limestone in slurry form will be injected into the tower to mix with the flue gasses and
combine with the sulfur dioxide present. The calcium carbonate of the limestone will produces
pH-neutral calcium sulfate that is physically removed from the scrubber. The reaction can be
expressed as :

CaCO3 (s) + SO2 (g) ----> CaSO3 (s) + CO2 (g)

When wet scrubbing with a lime slurry, the reaction will also produces CaSO3 :

Ca(OH)2 (s) + SO2 (g) ----> CaSO3 (s) + H2O (l)

It is also possible to use magnesium hydroxide to replace lime slurry :

Mg(OH)2 (s) + SO2 (g) ----> MgSO3 (s) + H2O (l)

Figure 4 : The flow of flue gas in FGD

(SOURCE : Meng Cao, Introduction to Sea Water FGD (SWFGD) Alstom presentation for TNB
Janamanjung)