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lives by Educating MATERIAL BALANCES FOR BIOGEOCHEMICAL CYCLES
for the BEST.

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CSU is committed In partial fulfilment for the requirements of the course

to transform the
Air Pollution and Control
lives of people and
communities (ChE 83)
through high
quality instruction
and innovative
research,
development,
production and
By:
extension. Acebedo, Daphne Sheerah C.
Dela Cruz, Martin Joseph L.
CSU – IGA Macalino, Virginia Isabel O.
Competence Ramirez, John Conrad P.
Social Responsibility
Unday, Jesa M.
Unifying Presence
Velasquez, Errol James S.

COE – IGA
Innovative Thinking
Synthesis
Personal Responsibility
Empathy
Research Skill
Entrepreneurial Skill

February 2020

THE SULFUR CYCLE

 The sulfur cycle is the collection of processes by which sulfur moves between rocks,
waterways and living systems. This cycle is important in geology because it affects many minerals.
Biochemical cycles are also important for life because sulfur is an essential element, being a
constituent of many proteins and cofactors, and sulfur compounds can be used as oxidants or
reductants in microbial respiration. 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 (Madigan M.T. and Martino JM., 2006).

Material Balance of Sulfur Cycle

Sulfur makes up almost 3% of the earth’s mass. Sulfur deposits are found naturally in areas
around hot springs and in volcanic regions. It is also widely found in nature as iron pyrites, galena,
gypsum, Epsom salts and many other minerals. Human activities have had a significant effect on
the sulfur cycle perhaps most particularly in the production of acid rain despite of those in natural
resources. The Earth’s surface is a source of windblown dusts, but this is influenced by grazing
activities and desertification. In mineral extraction and fuel use, enormous amounts of sulfur are
needed. Fossil fuel refining and combustion are the major human emissions to the atmosphere,
which exceed the natural sources. (Brimblecombe P., 2003)

Sulfur rises up to the atmosphere through volcanic releases, decomposition of an organism,

contact of air and sulfur from the weather of rocks, breakdown of organic matter in swamps and
tidal flats, evaporation of water, sea spray and anthropogenic activities (Jackson, Andrew R.W and
Julie M. Jackson, 1996). The following are the amount of sulfur in the different sulfur reservoirs:

 Sulfur Reservoirs (per year)

o Stratospheric: 0.04 Tg S
o Ocean: 100 Tg S
o Marine Biota: 30 Tg S
o Land Biota: 65 Tg S
o Lakes: 300 Tg S
o Sea: 80 Tg S
o Continental Atmosphere & Marine Atmosphere: 1.2 Tg S
o Anthropogenic Sulfur: 110 Tg S
o Sea Spray: 45 Tg S
o Industrial Output: 40 Tg S

Sulfur eventually settles back into the Earth or comes down through rainfall. Sulfur is
accumulated into lakes and streams and eventually oceans. (Cunningham, William P. and Barbara
Woodworth Saigo, 1999)

o Deposition: 360 Tg S per year

o Rainfall: 200 Tg S per year

Accumulation of S on Earth = Mass in of S in the atmosphere – Mass out of S in the

atmosphere

Accumulation = (0.04+100+30+65+300+80+1.2+110+45+40) – (360-200)

Accumulation of S on Earth = 771.24 – 560

Accumulation of S on Earth = 211. 24 Tg S per year

The accumulation of 211.24 Tg S per year on earth means that not all sulfur from these
reservoirs goes up in the atmosphere. Some are converted into organic forms, some are stored in
stones and some are lost to the oceans depths, combining with iron to form ferrous sulfide.

THE OXYGEN CYCLE

 The oxygen cycle is the biogeochemical transitions of oxygen atoms between the different
oxidation states in ions, oxides and molecules through redox reactions within and between the
spheres/reservoirs of the planet Earth. The word oxygen in the literature typically refers to the most
common oxygen allotrope, elemental/diatomic oxygen (O2), as it is a common product or reactant
of many biogeochemical redox reactions within the cycle. Processes within the oxygen cycle are
considered to be biological or geochemical and are evaluated as either a source (O2 production) or
sink (O2 consumption).

OXYGEN RESERVOIR

Oxygen is one of the most abundant elements on Earth and represents a large portion of each
main reservoir. By far the largest reservoir of Earth’s oxygen is within the silicate and oxide
minerals of the crust and mantle (99.5% by weight). The Earth’s atmosphere, hydrosphere, and
biosphere together hold less than 0.05% of the Earth’s total mass of oxygen. Besides O2, additional
oxygen atoms are present in various forms spread throughout the surface reservoirs in the
molecules of biomass, H2O, CO2, HNO3, NO, NO2, CO, H2O2, O3, SO2, H2SO4, MgO, CaO, AlO,
SiO2, and PO4.

 Atmosphere

The atmosphere is approximately 20.9% oxygen by volume, which equates to a

total of roughly 34 X 1018 mol of oxygen. Other oxygen-containing molecules in the
atmosphere include ozone (O3), carbon dioxide (CO2), water vapour (H2o), sulphur and
nitrogen oxides (SO2, NO, N2O, etc.).

 Biosphere

The biosphere is 22% oxygen by volume present mainly as a component of organic

molecules (CXHXNXOX) and water molecules.

 Hydrosphere

The hydrosphere is 33% oxygen by volume present mainly as a component of water

molecules with dissolved molecules including free oxygen and carbonic acids (HXCO3).

 Lithosphere
 The lithosphere is 46.6% oxygen by volume present mainly as silica minerals
(SiO2) and other oxide minerals.

OXYGEN SOURCES AND SINKS

While there are many abiotic sources and sinks for O2, the presence of the profuse
concentration of the free oxygen in the modern Earth’s atmosphere and ocean is attributed to O2
production from the biological process of oxygenic photosynthesis in conjunction with a biological
sink known as the biological pump and a geologic process of carbon burial involving plate
tectonics. Biology is the main driver of O2 flux on modern Earth, and the evolution of oxygenic
photosynthesis by bacteria, which is discussed as part of the Great Oxygenation Event, is thought
to be directly responsible for the conditions permitting the development and existence of all
complex eukaryotic metabolism.

a. Biological production

The main source of atmospheric free oxygen is photosynthesis, which produces sugars and
free oxygen from carbon dioxide and water.

6 𝐶𝑂2 + 6 𝐻2 𝑂 + 𝑒𝑛𝑒𝑟𝑔𝑦 → 𝐶6 𝐻12 𝑂6 + 6 𝑂2

Photosynthesizing organisms include the plant life of the land areas as well as the
phytoplankton of the oceans. The tiny marine cyanobacterium Prochlorococcus was
discovered in 1986 and accounts for more than half of the photosynthesis of the open ocean.

b. Abiotic production

An additional source of atmospheric free oxygen comes from photolysis, whereby high-
energy ultraviolet radiation breaks down atmospheric water and nitrous oxide into component
atoms. The free H and N atoms escape into space, leaving O2 in the atmosphere.

2 𝐻2 𝑂 + 𝑒𝑛𝑒𝑟𝑔𝑦 → 4 𝐻 + 𝑂2

2 𝑁2 𝑂 + 𝑒𝑛𝑒𝑟𝑔𝑦 → 4 𝑁 + 𝑂2

c. Biological consumption
 The main way free oxygen is lost from the atmosphere is via respiration and decay,
mechanisms in which animal life and bacteria consume oxygen and release carbon dioxide.

CAPACITIES AND FLUXES

The following tables offer estimates of oxygen cycle reservoir capacities and fluxes. These
numbers are based primarily on estimates from (Walker, J. C. G.):

Reservoir Capacity (kg O2) Flux in/out Residence time

(kg O2 per year) (years)
Atmosphere 1.4 X 1018 3 X 1014 4500
Biosphere 1.6 X 1016 3 X 1014 50
Lithosphere 2.9 X 1020 6 X 1011 500,000,000

Table 2: annual gain and loss of atmospheric oxygen (units of 1010 kg O2 per year)

Photosynthesis (land) 16,500

Photosynthesis (ocean) 13,500
Photolysis of N2O 1.3
Photolysis of N2O 0.03
Total gains 30,000 (approx.)
Losses- respiration and decay
Aerobic respiration 23,000
Microbial oxidation 5,100
Combustion of fossil fuel (anthropogenic) 1,200
Photochemical oxidation 600
Fixation of N2 by lightning 12
Fixation of N2 by industry (anthropogenic) 10
Oxidation of volcanic gases 5
Losses- weathering
Chemical weathering 50
Surface reaction of O3 12
Total losses 30,000 (approx.)
 THE CARBON CYCLE

Carbon is a chemical element that is essential to all living things because of its ability to
form multiple, stable bonds with other molecules. Without carbon, molecules such as
nucleotides, amino acids, sugars, and lipids will not exist and function in the ways that permit the
chemistry of life to occur.

The carbon moves through Earth’s various systems in a cycle called carbon cycle. This
cycle is influenced by living things, atmospheric changes, ocean chemistry, and geologic activity
are all part of this cycle. Parts of the cycle store carbon for different lengths of time, and there are
many processes that move carbon in and out of the stores. An individual atom might pass through
plants, animals and the atmosphere in a matter of days, yet stay trapped in rocks for millions of
years.

The diagram below briefly shows the carbon cycle that takes place both in terrestrial and
marine ecosystems.

Photosynthesis

Figure 1: Global carbon cycle for terrestrial ecosystems (left) and for marine ecosystems (right).
CARBON SINKS

Atmosphere
One of the major storehouses of carbon dioxide on Earth is the atmosphere. In nature, this
gas is released by volcanic activity, and by the respiration of animals who affix carbon molecules
from the food they eat to molecules of oxygen before exhaling it.
On the other hand, carbon is removed in the atmosphere by the respiration of plants through
photosynthesis and by the absorption into the ocean through bonding with water molecules to form
carbonic acid.

Biosphere
Plants remove carbon from the atmosphere and they do this because atmospheric carbon
serves as their “food” to make sugars, proteins, and other essential molecules of life. Plants also
use the energy of sunlight to build these organic compounds. The process is called photosynthesis.
In a balanced set of chemical reactions, herbivores and predators and take these synthesized
molecules apart again. Animals get their energy from the plants. In order to do that, animal cells
dissemble complex molecules such as sugars, fats, and proteins all the way down to single-carbon
units – molecules of carbon dioxide, which are produced by reacting carbon-containing food
molecules with oxygen from the air.

Oceans
The Earth’s oceans have the ability to both absorb and release carbon dioxide. When carbon
dioxide from the atmosphere comes into contact with ocean water, it can react with the water
molecules to form carbonic acid – a dissolved liquid form of carbon.
When there is more carbonic acid in the ocean compared to carbon dioxide in the
atmosphere, some carbonic acid may be released into the atmosphere as carbon dioxide. On the
other hand, when there is more carbon dioxide in the atmosphere, more carbon dioxide will be
converted to carbonic acid, and ocean acidity levels will rise.
Some scientists have raised concerns that acidity is rising in some parts of the ocean,
possibly as a result of increased carbon dioxide in the atmosphere due to human activity. Although
these changes in ocean acidity may sound small by human standards, many types of sea life depend
on chemical reactions that need a highly specific acidity level to survive. In fact, ocean
acidification is currently killing many coral reef communities.
CARBON STOCKS AND FLUXES

Figure 2: The Global Carbon Cycle. The values inside the boxes are standing stocks (in Pg C); the arrows represent
annual fluxes (Pg C/y). The black arrows and numbers show the preindustrial values of standing stocks and fluxes;
the red arrows and numbers indicate the changes due to anthropogenic activity.

Figure 2 shows the simplified global carbon cycle. The values are summarized in Gt of
carbon per year (1 Gt = 1 Pg = 1015 g). In the figure, it is shown that the ocean is the largest sink
of carbon with approximately 38, 121 Pg C/y (Lackner, 2015).
The figure also shows that the fossil fuel reserve is decreasing at 220 Pg C/y. It is one of
the essential sources of carbon on Earth yet it is continuously decreasing.
REFERENCES:
Butcher S. and Charlson R., An Introduction to Air Chemistry
Bioshpere: The Sulfur Cycle from Encyclopedia Britannica: 2006
Cunningham, William P. and Barbara Woodworth Saigo, Environmental Science: A
Global Concern, McGraw Hill: 1999
Jackson, Andrew R.W and Julie M. Jackson, Environmental Science: The Natural
Environment and Human Impact, Longman: 1996
https://enviroliteracy.org/air-climate-weather/biogeochemical-cycles/sulfur-cycle/
Lackner, Maximilian. (2015). Geoengineering for Climate Stabilization. Handbook of Climate Change
Mitigation and Adaptation. Springer Science + Business Media New York. DOI 10.1007/978-1-4614-
6431-0_72-1