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Republic of the Philippines

Cagayan State University

COLLEGE OF ENGINEERING
Carig Sur, Tuguegarao City

DEPARTMENT OF CHEMICAL ENGINEERING

ChE Technical Elective 3 (Air Pollution and Control)
(ChE 83)
Second Semester 2019 – 2020

Course Activity: Mass Balances of Biogeochemical Cycles

Name of Students: Casibang, Jariss Red F.

Dela Cruz, Amazing Grace U.
Edillo, Nikie S.
Hababag, Maricar L.
Jimenez, Emmanuel V.
Mathis, Rodrigo D.
Omnes, Preciously U.

Program: BSChE
Year Level: V

Date Submitted: February 28, 2020

Instructor: Engr. Theresa Lean B. Tuliao

MASS BALANCES OF BIOGEOCHEMICAL CYCLES

Biogeochemical cycling of most abundant elements of the Earth like oxygen, iron, silicon,
hydrogen, nitrogen, carbon and sulfur and other elements, determines the composition of the
Earth’s atmosphere and the life evolution . It’s a need to understand biogeochemical cycles
since they play a key role in the functioning of the climate system and are responsible for the supply
of products such as food and fiber for human use (McGuire & Lukina). They also provide regulating,
supplying, and supporting services, as well as the role of biodiversity (genetic and functional
diversity, abundance and activity of organisms) in supporting these services (Smith P., et. al,2015).

Human activities including fossil fuel burning, agriculture, deforestation and industrial
emissions, have substantially altered the composition of Earth’s atmosphere, the land surface and
ocean (Sarmiento and Gruber, 2002). The impact of these activities to the biosphere and
biogeochemical cycles results into climate change that has negative implications for ecosystems,
society and the climate system (Reichstein et al., 2013).

Because of the ability of man to alter significant biogeochemical cycles, interactive effects
may overshadow the measured effects in terms of individual elements. Changes in the availability
of one element could impact not only biological productivity but also the availability and
requirements of the other element and also the structure and functioning of ecosystems over the
longer term (Gruber and Galloway, 2008).

OXYGEN CYCLE

About 21% of our air is composed of oxygen. It is essential to all living organisms and the main
component in respiration. It is the most crucial component of atmosphere which is maintained not
only by the process of photosynthesis by green plants and algae but also by the processes that
consume oxygen such as respiration, combustion and decomposition. Industries and modern
civilization has developed rapidly over the past few decades that resulted to declining of
concentration of atmospheric oxygen.

The four main reservoirs of oxygen cycle are terrestrial biosphere (green), marine biosphere (blue),
lithosphere (brown), and atmosphere (grey). The reservoir capacities and fluxes are shown below.
Table 1: The following tables offer estimates of oxygen cycle reservoir capacities and fluxes. These
numbers are based primarily on estimates from (Walker, J. C. G.)

Capacity Flux in/out Residence time

Reservoir
(kg O2) (kg O2 per year) (years)

Atmosphere 1.4×1018 3×1014 4500

Biosphere 1.6×1016 3×1014 50

Lithosphere 2.9×1020 6×1011 500000000

 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 H2O 0.03

Total gains ~ 30,000

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

The annual averaged global O2 budget from year 1990 to 2005, with the mass of O2 in
gigatonnes (Gt) are listed below. The inputs of O2 to the atmosphere by land and outgassing from
oceans are quantified as 16.01 and 1.74 Gt/a, respectively. Fossil fuel combustion, which accounts
for the largest consumption of O2 of the three main processes, consumed 25.16 Gt/a. Fire burning
consumed 5.87 Gt/a O2. The O2 consumed by human and livestock respiration comprises 3.09 and
2.24 Gt/a, respectively. The residual term, which includes the systematic bias, is about 2.69 Gt. In
total, the O2 depletion in the atmosphere is 21.23 Gt/a, which is mainly associated with the growth
rate of atmospheric CO2 concentration.
 Fig. 4. The annual averaged global O2 budget from 1990 to 2005. The green arrows denote the
production from land vegetation and outgassing from oceans. The red arrows represent
consumption by fossil fuel combustion , human and livestock respiration, fire and residual.

Mass Balance:

Mass In= Mass Out

LP+ OO+AD=FFC +FIRE+ HR+LR+ R

(16.01+1.74+21.23) Gt/yr = (25.02 +5.87+ 3.09+ 2.24+2.69) Gt/yr

38.98 Gt/yr = 38.91 Gt/yr

SULFUR CYCLE

Sulfur is one of the macronutrients required by plants and is obtained by them from the soil
and from the atmosphere. It is present in proteins and gives a distinctive odor to many substances.

The major reservoirs for sulfur in the global cycle are pyrite and gypsum in the lithosphere
and in seawater. Very little sulfur is present in living organisms, but within the marine muds and
terrestrial bogs where organic matter accumulates under anaerobic conditions considerable
amounts are present. Increasing amounts of atmospheric sulfur compounds are the direct result of
human activities and are principal components of air pollution in industrial areas. Most are short‐
lived in the air and wash out forming acid rain downwind from the industrial sites.

The sulfur cycle resembles that of nitrogen in several respects, for example the short‐term
movements of both elements is through the atmosphere as a result of the metabolism of bacteria.
The gases move rapidly in a closed cycle from the air to the soil and back.

Sulfur Cycle
There are several sub cycles:

1.) A long, deep time cycle of weathering, erosion and deposition.

2.) A predominately atmospheric cycle where bacteria metabolize dead organic matter and release
sulfur to the atmosphere where it has a short residence time before being washed back to the soil
by precipitation.

3.) A marine cycle where evaporation of sea spray releases sulfur to the atmosphere temporarily and
from where it falls back into the sea.

4.) A soil–plant cycle where organic sulfur in manure or other fertilizer is used to sustain soil
microbes and plants.

SULFUR BALANCE

Mass Balance flowchart derived from the Sulfur Cycle by K. Zheng, Y. Huang and H. H. Lou
The figure above represents or illustrates the global sulfur fluxes in teragrams per year (Tg S/year).
By using this illustration, we can get the necessary values for the Sulfur content. The formula is just
simply “Accumulation = In – Out”.

For Example:

Calculate the annual accumulation in the Atmosphere with the following data (in Tg Sulfur/year):
Human Mining (149), Industry (93), Plants (20), Volcanoes (10), Biogenic Gases (22) and Deposition
(84).

Calculation

Accumulation = In – Out

Accumulation = Human Mining + Industry + Plants + Volcanoes + Biogenic Gases – Deposition

Accumulation = (149 + 93 + 20 + 10 + 22 – 84 ) Tg Sulfur/year

Accumulation = 210 Tg Sulfur/year

WATER CYCLE

This material balance and water accounting report used the accounts compiled for the
physical asset and flow accounts for water resources of the Philippines for the baseline period, 2015.
Ideally, the accounts should cover all water resources in the country. However, the data provided
doesn’t ensure a hundred percent accuracy because of the different changes occurring during the
year and some of which might be unaccounted for. Hence, the data used for this study are those
readily obtained within the statistical system.

The following data are gathered in the stock water in Ambuklao, Angat, Binga and San
Roque Dams which were provided by the National Power Corporation (NPC) while storage
capacities of all dams in the country were sourced from the National Irrigation Administration.
Data on the volume of water in Laguna de Bay was sourced from the Laguna Lake Development
Authority (LLDA). Surface area and average depth of the other nine major lakes, namely, Lanao,
Taal, Mainit, Naujan, Buluan, Bato, Buhi, Dapao and Sebu, were available from various online
sources. These were used to estimate the volume of water in lakes. The ten major lakes comprise
about 93.5% of the total area of lakes in the country. During a training and data assessment
workshop with experts from the United Nations Economic and Social Commission for Asia and the
Pacific (UNESCAP), it was established that fishponds also occupy a significant portion of the
country’s land cover and hence, considered also as a water resource. The data on the volume of
water in fishponds was provided by the Bureau of Fisheries and Aquatic Resources (BFAR).

Since the data needed are already given, the general formula for the Hydrological Balance
around the Philippines is equal to:

Mass In = Mass Out

Mass In- is equal to all of the water entering the water system of the Philippines

Mass Out- is equal to all of the water leaving the water system of the Philippines

In order to acquire the value of the overall amount of water, we need to determine the
overall supply of water in the Philippines. Based on the SEEA Central Framework, there are three
main types of water resources, namely: surface water, groundwater and soil water. Currently, there
are no available data on the stocks of groundwater and hence, the opening and closing stocks cover
only surface water and soil water. Also, surface water resources ideally should cover artificial
reservoirs, lakes, rivers and streams, and fishpond. However, stocks of water in rivers and streams
are not yet obtained and thus, surface water in this compilation includes only artificial reservoirs,
lakes and fishponds. As observed in Figure 1, the stock of water in the country showed a decline of
about 20.4 percent for the year 2015. At the beginning of the year, the stock of water amounts to a
total of 94.62 billion cubic meters (BCM) comprised of surface water at 80.96 BCM (85.6%) and soil
water at 13.66 BCM (14.4%). At the end of 2015, the total stock of water decreased to 75.31 BCM, with
54.28 BCM (72.1%) coming from surface water and 21.03 (27.9%) from soil water. (“Developing the
Water Accounts and Material Flow Accounts of the Philippines”, 2018).
 I. The Overall Opening and Closing Stocks of Water Resource

Opening Stock: The amount of water at the start of the year.

Surface Water: 80.96 MCM

Soil Water: 13.66 MCM

Total: 94.62 MCM

Closing Stock: The amount of water at the end of the year.

Surface Water: 54.28 MCM

Soil Water: 21.03 MCM

Total: 75.31 MCM

II. The Opening and Closing Stocks of Different Water Sources

As observed in Figure 1, the stock of water in the country showed a decline of about 20.4
percent for the year 2015. At the beginning of the year, the stock of water amounts to a total of 94.62
billion cubic meters (BCM) comprised of surface water at 80.96 BCM (85.6%) and soil water at 13.66
BCM (14.4%). At the end of 2015, the total stock of water decreased to 75.31 BCM, with 54.28 BCM
(72.1%) coming from surface water and 21.03 (27.9%) from soil water.
 Although the total stocks of water showed a decline, the trends for the two types of water
resources were different. While surface water stock decreased by 33 percent, from 80.96 BCM to
54.28 BCM, soil water stock increased by 54 percent, from 13.66 BCM to 21.03 BCM (Figure 2). This
can be attributed to the dissimilarities in their changes in stocks. Abstraction as input to the
economy from surface water is greater than that from soil water. Also, amount of rainfall retained
after evaporation is much greater for soil water than that of surface water.

Looking into further details of surface water resources, Figure 3 shows that there is not
much difference between the opening and closing stocks of lakes (from 74.99 BCM to 76.06 BCM),
artificial reservoirs (3.33 BCM to 3.49 BCM) and fishponds (2.64 BCM to 3.28 BCM). It should be
noted, however, that the largest reduction in stock – abstraction of water as input to the economy,
cannot be disaggregated further into lakes, artificial reservoirs and fishponds using the currently
available data.

We can outline three types of flow: from the environment to the economy, within the
economy, and from the economy to the environment. Based on the currently available data, flows
from the environment to the economy are broadly covered in this compilation, describing the
sectors and industries utilizing the abstracted water from the environment. However, there is very
limited information on the other two types of flows, particularly on the reuse of water between
industries and wastewater generation.

Figure 4 illustrates that the largest portion of abstracted water (61.9%) is sourced from
artificial reservoirs, rivers and streams, and lakes. All sectors and industries use abstracted water
from the surface, either directly or distributed to them by another industry. This is followed by soil
water with 31.9%. Groundwater and seawater comprise less than 10% of abstracted water.
 Of the 46,279 million cubic meters (MCM) of abstracted water, 94 percent is used or
consumed by the economic unit that abstracted it. The remaining 6 percent is intended to be
distributed by concessionaires such as Maynilad, Manila Water and local water districts to other
industries and to households. Four percent reaches the users for final consumption while 2 percent
is lost during the distribution process.

As shown in Figure 6, the agriculture sector is the largest user of water abstracted for own
use (98.02%). This includes surface and groundwater used for irrigation and livestock and poultry
production as well as soil water used by rainfed crops. This is followed by households, specifically
those whose main source of water supply were either dug well, rivers, streams, lakes, harvested
rainwater, or other sources, with 1.92 percent. Other industries using water abstracted for own use
are water collection, treatment and supply, and manufacturing (salt production), with both around
0.03 percent.
 Meanwhile, as presented in Figure 7, the largest consumer of distributed water is the
household sector, utilizing 59.5 percent of the total distributed water. This is followed by the mining
and quarrying, manufacturing and construction sectors, consuming an aggregate percentage of
23.95. Other industries use up 15.37 percent of the total distributed water. Among the sectors under
other industries, the wholesale and retail trade sector, accommodation and food service sector, and
real estate sector have the largest reported water expenses, which translate also to water use.
Agriculture, electricity, gas, steam and Developing the Physical Asset and Flow Accounts for Water
Resources of the Philippines A-33 air-conditioning supply, and sewerage consumed 0.8 percent, 0.3
percent and less than 0.1 percent of the total distributed water, respectively.

III. Summary Sheet for Hydrological Balance Around the Philippines In a Year

Using the general formula, amount in is equal to amount out;

Presented in a table form is the Supply Table, Physical Flow Accounts for Water Resource expressed
in million cubic meters,

Solving for the total amount of available water for use is equal to,
  Overall supply = total supply abstracted water + total supply wastewater + total supply
reused water + total supply return flows
 Overall supply = 46,279 + 394.25 + 786.12 + 676.58
 Overall supply = 48,135.95 Million Cubic Meters

This amount must be equal to the overall amount of water used in a year. Presented in a table form
is the Use Table, Physical Flow Accounts for Water Resource expressed in million cubic meters,

Solving for the total amount of used water in a year is equal to,

Overall utilized water = total used abstracted water + total wastewater + total reused water +
total used return flows

Overall utilized water = 46,279 + 394.25 + 786.12 + 676.58

Overall utilized water = 48,135.95 Million Cubic Meters

From the given data and the overall computed value,

Overall supply water = Overall utilized water

48,135.95 Million Cubic Meters = 48,135.95 Million Cubic Meters

 NITROGEN CYCLE

Nitrogen is in all over the place. In point, N2 gas marks up about 78% of Earth's atmosphere

by volume, far surpassing the O2 we often think of as "air".

The biogeochemical nitrogen cycle is intricate with nitrogen taking place in valence states
from -3 to +5 5 and where many of the transformations are carried out by a few organisms only, at
normal temperatures and pressures. Although plentiful on earth, 96% is found in the lithosphere
or in soil organic matter and does not take part in the biogeochemical cycle. In terrestrial schemes,
only four per cent of the nitrogen occurs in biomass.

Nitrogen is an essential nutrient but nitrogen compounds are also possible toxicants. The
hazard of unwanted side effects is increasing, i.e. through the increased use of nitrogen fertilizers.
By the end of this century, man-made additions of combined nitrogen to terrestrial ecosystems will
be as large as the amount added through biological nitrogen fixation.

Nitrogen Cycle
 An understanding of the different routes of the nitrogen biogeochemical cycle is required
before attempts can be complete to quantify the nitrogen cycle of ecosystems, regions, or the earth.
The inorganic nitrogen cycle, which was earlier considered somewhat simple, is becoming more
complex as our knowledge grows.

Amount of nitrogen Proportion

(Tg) (%)
Lithosphere 57,400,000,000 93.8
Atmosphere 3,800,000,000 6.2
Hydrosphere 23,000,000 0.04
Biosphere 900,000 0.001

The nitrogen cycle in an ecosystem is significant. The design of nitrogen cycling varies as
an ecosystem progresses to its peak state, and it is also affected by disorders such as management
practices.

An understanding of the nitrogen cycle in numerous types of distinctive ecosystem of the

world will offer us the jigsaw pieces needed to conceptualize a convincing image of the global
nitrogen cycle, intrinsically related to other major elements such as carbon, phosphorus and sulfur.

Nitrogen Balance

ATMOSPHERE
14
R4

1 2 3 4 5 6 7 8 9 10

11
TERRESTRIAL SYSTEMS O AQUATIC SYSTEMS

12 13
 Nitrogen Cycle Label Flow (Tg/yr)
1. Denitrification of bacteria D1 160
- -
2. Nitrification by bacteria to NO3 /NO2 in soil. NO1 25
3. Terrestrial food webs T 58
4. Nitrogen fixation by bacteria in land N1 194
5. Ammonification by bacteria and fungi NH4+. A1 0.03
- -
6. Nitrification by bacteria to NO3 /NO2 in NO2 33
ocean
7. Denitrification by bacteria to N2. D2 130
8. Marine food webs M 10
9. Nitrogen fixation by bacteria in ocean N2 179
10. Runoff R 50
11. Fertilizers F 27
12. Nitrous sediments NS 23
13. Nitrous sediments fall to ocean floors. NSD 31
14. NH3+ +OH  NOx NOX 8

Calculation

Mass In = Mass Out

D1+NO1+T+NO2+D2+F+NS+NOX=N1+A1+M+N2+R+NSD

(160+25+58+33+130+27+23+8)Tg Nitrogen/yea r= (194+0.3+10+179+50+31)Tg Nitrogen/year

464 Tg Nitrogen/year = 464.3Tg Nitrogen/year

Certain activities of humans are making variations to the nitrogen cycle and the amount of
nitrogen that is stored in the land, water, air, and organisms. The use of nitrogen-rich fertilizers
can add too much nitrogen in neighboring waterways as the fertilizer washes into streams and
ponds. The waste related with livestock farming also adds great amounts of nitrogen into soil and
water. The increased nitrate levels cause plants to grow fast until they use up the supply and die.
The number of plant-eating animals will rise when the plant supply upsurges and then the animals
are left deprived of any food when the plants die.
 CARBON CYCLE
Carbon is the backbone of life on Earth. We are made of carbon, we eat carbon, and our
civilizations—our economies, our homes, our means of transport—are built on carbon. We need
carbon, but that need is also entwined with one of the most serious problems facing us today: global
climate change. Most of Earth’s carbon—about 65,500 billion metric tons—is stored in rocks. The
rest is in the ocean, atmosphere, plants, soil, and fossil fuels.
Carbon flows between each reservoir in an exchange called the carbon cycle. Any change in
the cycle that shifts carbon out of one reservoir puts more carbon in the other reservoirs. Changes
that put carbon gases into the atmosphere result in warmer temperatures on Earth.
Over the long term, the carbon cycle seems to maintain a balance that prevents all of Earth’s
carbon from entering the atmosphere (as is the case on Venus) or from being stored entirely in
rocks. This balance helps keep Earth’s temperature relatively stable, like a thermostat.

Image credit: Biogeochemical cycles: Figure 3 by OpenStax College, Biology, CC BY 4.0; modification
of work by John M. Evans and Howard Perlman, USGS
 Globally, about 20.2 gigatons of carbon dioxide per year are emitted to the atmosphere by
fossil fuel combustion, and 1.6 gigatons of carbon per year are emitted due to misuse of lands
through activities such as deforestation. According to the National Center for Atmospheric
Research, the mass of the atmosphere is 5.148 × 1018 kg (or 5.148 x 106 gigatons) air. Assume that
an average global increase in atmospheric carbon dioxide concentration is 2.1 ppm per year, and
that all carbon in the atmosphere is contained in carbon dioxide. Much of the carbon which flows
through the atmosphere is deposited into various “sinks” on the earth, i.e., on the land and in the
water. Of the carbon not accumulated in the atmosphere, 0.5 gigatons is absorbed by trees for
photosynthesis, 34 wt% of this carbon is either consumed by non-tree vegetation or accumulated
in the soil, and the rest of the carbon is deposited into oceans, lakes, and rivers.

Question:
What is the global flow rate of carbon from the atmosphere into oceans, lakes, and rivers?

A basic carbon mass balance in the atmosphere is,

Cacc = Cin – Cout
The carbon generation and consumption terms are omitted in Eq. (1) because atoms cannot be
created or destroyed. The carbon accumulation (Cacc), input (Cin), and output (Cout) terms are to be
determined using the information given in the problem statement.

Cin = m1 × [Mw C] / [Mw CO2] + m3

= 20.2 [Gt CO2] × 12 [g C/mol] / 44 [g CO2/mol] + 1.6 [Gt C/yr]
= 7.1 [Gt C/yr]
Cacc = Mair × x2 × [Mw C] / [Mw CO2]
= 5.148 × 1018 [kg air] × 2.1 × 10-6 [kg CO2 / kg air] × 12 / 44
= 2.95 x 1012 [kg C]

CONCLUSION

Greenhouse gases such as sulfur dioxide, nitrogen dioxide, and carbon dioxide have been
recognized as the leading cause of global climate change (Abeydeera et.al.,2019). Climate change
has caused a number of problems, including global warming, environmental imbalances,
technological issues, economic issues and societal issues (Liu et.al.,2019).

The atmospheric carbon dioxide concentration rose from a pre-industrial value of about 280
ppm to 391 ppm in 2011 and more than 400 ppm in 2014. The increase in carbon emissions is mainly
due to industry, transport and energy supply. Residential and commercial buildings,
forestry/deforestation and agricultural sectors also contribute substantial amounts of carbon
dioxide, methane and other greenhouse gases (Huisingh et.al.,2015).

In the earth’s crust sulfur is widely distributed mainly in the form of sulfide minerals, sulfate
minerals, and sulfur. Sulfur plays an important role in protein structure and function that make up
living organisms. However, if concentration of sulfur in certain forms is too high, it will be toxic to
proteins (Hu & Xu, 2002).

Human activity is having a serious effect on the natural nitrogen cycle, especially due to the
development of industrial fertilizer production, where non-reactive atmospheric nitrogen is
transformed into reactive nitrogen compounds. One impact of reactive nitrogen compounds is
pollution of surface water and groundwater which has negative impact to the oxygen and water
cycle.
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https://www.khanacademy.org/science/biology/ecology/biogeochemical-cycles/a/the-
carbon-cycle
2. Developing the water accounts and material flow accounts of the philippines” progress
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in a Mass and Energy Balance Course”,

5. Kevin E. Trenberth, Lesley Smith, “The Mass of the Atmosphere: a Constraint on Global
Analyses,” National Center for Atmospheric Research
http://www.cgd.ucar.edu/cas/abstracts/ files/kevin2003_6.html
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https://byjus.com/biology/oxygen-cycle-environment/
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weather/biogeochemical-cycles/sulfur-cycle/
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9. The Earth Observatory, NASA, http://earthobservatory.nasa.gov/Features/CarbonCycle/

carbon_cycle4.php
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https://www.khanacademy.org/science/biology/ecology/biogeochemical-cycles/a/the-
nitrogen-cycle
11. The sulfur cycle. Retrieved from: https://www.cliffsnotes.com/study-guides/biology/plant-
biology/biogeochemical-cycles/the-sulfur-cycle
Volume 63, Issue 18