JIMMA UNIVERSITY

SCHOOL OF GRADUATE STUDIES

COLLEGE OF NATURAL SCIENCES

DEPARTMENT OF CHEMISTRY

A RESEARCH PROPOSAL ON

PREPARATION OF BIOCHAR FROM METAL PROCESSING, BREWERY AND

MUNICIPAL SEWAGE SLUDGE, FOR THE REMOVAL OF PHOSPHOROUS
FROM AQUEOUS SOLUTION

By: Tagay Alemu

Advisor: Tsegaye Girma (Ph. D.)

Co-advisor: Abebe Diro (MSc)

January 2024

Jimma, Ethiopia
PREPARATION OF BIOCHAR FROM SLUDGE OF METAL PROCESSING,
BREWERY AND MUNICIPAL SEWAGE, FOR THE REMOVAL OF
PHOSPHOROUS FROM AQUEOUS SOLUTION

A research proposal submitted to the Department of Chemistry, Jimma University in partial

fulfillment of the requirements for the degree of Master of Science in Applied Chemistry
(Environmental Chemistry)

By: Tagay Alemu

Approved by
Advisor Signature Date
Tsegaye Girma (Ph. D.) ______________ ____________
Co-advisor
Mr. Abebe Diro (MSc.) ______________ ____________

Jimma University
College of Natural Sciences
Department of Chemistry
Department Head
Mr. Kasim Kedir (Assis. Prof.) _______________ _____________
Examiner ______________ ____________

January 2024

Jimma, Ethiopia

I
 Table of contents

Contents Page
Table of contents...................................................................................................................................II
List of figures.......................................................................................................................................V
Acknowledgement...............................................................................................................................VII
List of abbreviations and acronyms................................................................................................VIII
Abstract...............................................................................................................................................IX
CHAPTER ONE................................................................................................................................10
1.1. Introduction................................................................................................................................10
1.2. Statement of the problem.......................................................................................................11
1.3. Objectives................................................................................................................................13
1.3.1General objective:..............................................................................................................13
1.3.2 Specific objectives.............................................................................................................13

1.4 Significance of the study ..............................................................................................13

CHAPTER TWO...............................................................................................................................15
2.1 LITERATURE REVIEW.........................................................................................................15
2.1.1 Wastewater........................................................................................................................15
2.1.2 Phosphorus........................................................................................................................15
2.1.3 Phosphorus Cycle..............................................................................................................15
2.1.2 Sources of phosphorus......................................................................................................16
2.2 Eutrophication.........................................................................................................................17
2.2.1 Stages of the Eutrophication Process..............................................................................18
2.2.2 Effects of Eutrophication.................................................................................................18
2.2.3 Impacts on the Ecosystem..............................................................................................19
2.2.4. Effects on the phytoplankton community....................................................................19
2.2.5 Harmful Algal Blooms (HABs)......................................................................................19
2.2. 6. Socioeconomic Effects....................................................................................................20
2.2.7 Phosphorus Health Impacts.............................................................................................20
2.3 Phosphorus Treatment Technologies.....................................................................................21
2.4 Adsorption................................................................................................................................26
2.4.1 Adsorption Mechanisms...................................................................................................26

II
 2.4.1.1 Chemisorption............................................................................................................27
2.4.1.2 Physisorption............................................................................................................27
2.4.1.3 Biosorption.................................................................................................................28
2.4.2 Factors Affecting the Adsorption of Phosphorus...........................................................29
2.4.2.1 pH..............................................................................................................................29
2.4.2.2 Temperature.............................................................................................................30
2.4.2.3 Adsorbent Dosage......................................................................................................30
2.4.2.4 Contact Time..............................................................................................................30
2.4.2.5. Initial Concentration................................................................................................31
2.4.2.6 Interfering ions.........................................................................................................31
2.5 Filtration...................................................................................................................................31
2.5.1 Saturation time..................................................................................................................32
2.6 Biochar.....................................................................................................................................32
2.6.1 Understanding Breweries, Municipal Sewage, and Metal Processing Sludge..............32
2.6.1 Production of biochar.......................................................................................................34
2.6.2 Characteristics of the biochar........................................................................................35
2.6.3 Role of biochar in Phosphorus Removal.......................................................................36
2.6.4. Application of biochar in aqueous solutions..................................................................37
2.6.5 Using biochar for Phosphorus Removal........................................................................38
2.6.7 Potential challenges and limitations..............................................................................39
2.7 Characterization of biochar-based nanocomposites.............................................................39
CHAPTER THREE...........................................................................................................................41
3. Materials and Methods..............................................................................................................41
3.1 Study site and periods..........................................................................................................41
3.2 Chemicals and apparatus....................................................................................................41
3.2.1. Instrumentation and apparatus..................................................................................41
3.3. Collection and preparation of the adsorbents...................................................................41
3.4. Adsorbent characterization................................................................................................42
3.4.1 Proximate analysis of activated carbons.....................................................................42
3.4.1.1 Moisture content determination............................................................................42
3.4.1.2. Ash content determination....................................................................................42
3.4.1.3 Fixed carbon content determination.....................................................................43
3.4.1.5. Effects of pH:.........................................................................................................43
3.4.1.6 Point zero charge (PZC) determination...............................................................43

III
 3.4.1.7 Determination of the surface area.........................................................................44
3.4.1.8. FTIR (Fourier Transform Infrared) analysis......................................................44
3.4.1.9. Scanning electron microscopy (SEM) analysis....................................................44
3.4.1.10.XRD (X-ray Diffraction) analysis.......................................................................44
3.4.1.11. UV–Vis spectrophotometry analysis..................................................................45
3.5. Batch Adsorption Study.....................................................................................................45
3.5.1. Effect of initial pH value..............................................................................................46
3.5.2. Real wastewater samples.............................................................................................46
3.5.3. Regeneration of the biosorbents..................................................................................46
3.6. Data analysis.......................................................................................................................47
3.6.1 Nonlinear chi-square (χ2) statistic test................................................................47
3. 6.1. Nonlinear chi-square (χ2)...........................................................................................47
3.4. 6.2. Adsorption Isotherms..........................................................................................47
3.4.6.3. Adsorption kinetics...............................................................................................48
3.4.6.4 Expected outcomes and deliverables....................................................................48
4.1 WORK PLAN AND BUDGET BREAKDOWN.......................................................................49
4.1. Work plan...............................................................................................................................49
4.2. Budget breakdown of the study........................................................................................50
References..........................................................................................................................................52

IV
 List of figures
Figure 1 : Chemical and physical types of adsorption with their corresponding layers 27

V
 List of Tables
Table 1: comparison of different treatment technologies for phosphorous removal...............23
Table 2:Comparison of biological, chemical, and physical removal methods........................25
Table 3:Types of native biomass that have been used for preparing biosorbents....................29
Table 4: Work Time Schedule.................................................................................................49
Table 5 List of chemicals and its cost......................................................................................50
Table 6: List and cost of stationeries materials and safety equipment....................................50
Table 7: Budget summary.......................................................................................................51

VI
Acknowledgement

First, I would like to thank my Almighty God for giving me the health and strength to start
my research proposal. I am very grateful to my advisor Dr. Tsegaye Girma and Mr. Abebe Diro
for their guidance, constructive comments, valuable suggestions, advice, and support during
the preparation of this research proposal. My special thanks go to the Department of
Chemistry, College of Natural Sciences, and Jimma University for allowing me to develop
this proposal paper. Last but not least, I would also like to thank the Gesha woreda education
office for giving me a big chance to learn a Master of Science Degree in Environmental
Chemistry.

VII
List of abbreviations and acronyms
AC Activated Carbon

BSG Brewery spent grain

BSS Brewery sewage sludge

COD Chemical oxygen demand

ETB The Ethiopian birr

FT-IR Furrier transmitter infrared radiation

MSG Modified spent grain

MPS Metal Processing Sludge

MSS Municipal sewage sludge

Ppb Parts per billion

Ppm Parts per million

PZC Point of Zero Charge

rpm Revolution per minute

SEM Scanning electron microscopy

UV-Vis Ultraviolet – visible

XRD X-ray Diffraction

VIII
 Abstract
Many industries release untreated effluents into water bodies. These effluents may contain
hazardous chemicals that pose a significant risk to human health and can cause various
diseases such as kidney failure, skin rashes, muscle crumps, and bone weakness. One
effective method for removing phosphorus from wastewater is through adsorption using
biochar as the treatment medium. Pristine biochar although advantageous, has limitations. For
example, it has a low capacity to adsorb anionic pollutants. Several modifications are
commonly used to improve the environmental applicability of biochar, including acid and
base treatment, the addition of metal salts, and the use of oxidizing agents. However, there is
limited information on biochar derived from brewery wastewater sludge, sewage sludge, and
metal processing sludge. This research aims to create biochar by combining the above waste
materials. The goal of this study is to explore the potential use of these biochars for removing
phosphorus from an aqueous solution. The brewery sludge samples will be collected from the
Saint George Brewery Share Company, municipal sewage sludge will be obtained from the
Kaliti wastewater treatment plant, and metal processing sludge will be acquired from the
Ethiopian iron and steel factory in Addis Ababa. Biochars will be prepared following
established protocols and characterized using FTIR, SEM, and XRD analysis. Batch
adsorption experiments will be conducted to study the removal of phosphate from aqueous
solutions. The residual concentrations of the adsorbates were monitored using a UV-Vis
spectrophotometer. The kinetics and equilibrium data are analyzed by fitting them into
established models.

Keywords: Biochar, sewage sludge, adsorption, brewery sludge, pollutant

IX
 CHAPTER ONE

1.1. Introduction
Phosphorus (P) is an essential nutrient for plants. It is also the dominant contributor to
eutrophication, which damages the aquatic environment and water quality. Currently, large
amounts of P-containing products are widely used in human activities, such as in washing
powders, detergents, fertilizers, and pesticides, leading to increasing P levels in natural water
bodies.1. Municipal wastewater treatment plants can only partially remove P, leading to large
amounts of P being discharged into the environment. Additionally, runoff from agricultural lands
on which P-containing fertilizers and pesticides have been extensively applied is another
dominant cause of increasing P level. A level as low as 0.02 mg L/1 dissolved P can cause
eutrophication by initiating algae bloom and high consumption of dissolved oxygen, which pose
adverse effects on the environment. By contrast, insufficient plant-available P in the soil is
frequently reported in many countries. Some P-containing minerals, such as apatite, are the
domain sources for commercial P, which are expected to be depleted during the next 50 to 100
years.2.

Several technologies have been developed and used for the removal of phosphorus from
wastewater. These include phytoremediation coagulation– flocculation ion exchange adsorption
electrochemical and membrane technologies as well as their combinations. 3 Among various
methods, adsorption has received significant interest owing to its simplicity of operation, high
efficiency, and cost-effectiveness4. Adsorption has been widely recommended as a viable method
for pollutant treatment, especially when dealing with lower concentrations. Various carbon-rich
materials such as biochars have been previously investigated for their efficacy in removing
inorganic ions, from wastewater. They are widely regarded as a cost-effective solution for
mitigating phosphorus pollution5 6.Biochar can be produced by pyrolyzing any carbonaceous
organic matter, including agricultural and forestry waste, municipal and industrial leftovers, and
activated sludge 7. Biochar has good adsorption properties of pollutants in soil and water due to
its high porosity, large specific surface area and rich source of functional groups like carboxyl,
phenolic hydroxyl and carbonyl. However, pristine biochar has several drawbacks such as quite
low adsorption capacity for anionic pollutants, requires a long equilibration time, its properties

10
are also influenced by the biomass source, reaction medium, and processing conditions 8.
To enhance the properties of biochar for environmental applications, several modifications, such
as acid and base treatment, metal salt, or oxidizing agent modification, are frequently utilized.
For instance, biochars made from brewers' spent grain and sewage sludge mixed (80:20, wt%)
performed superior to biochars made from each material in removing ammonia-nitrogen from
the water 9. In comparison to pristine biochar, the adsorption of methylene blue was
increased by more than 50% when pulp and paper sludge was impregnated with Fe 2O3 10.
Activation of biochar with steam enhanced the decolonization of cationic and anionic dye-
11
laden contaminated wastewater . Biochar & magnetic Fe3O4 hybrids/“magnetic biochar”
effectively removed pharmaceuticals from aqueous solution 12. The engineered biochar loaded
with aluminum oxyhydroxides (AlOOH) had fast adsorption kinetics and good adsorption
capacity to phosphate in the secondary treated wastewater 13.

There is currently a lack of comprehensive information regarding the application of biochars

derived from brewery wastewater sludge, sewage sludge, or metal processing sludge in the
adsorption of phosphate ions. Phosphorous is naturally at low concentrations. The discharge of
untreated wastewater containing phosphorus can have harmful effects on the aquatic
14,15
environment, specifically by contributing to eutrophication. . The aim of this study is to
produce biochars using brewery wastewater sludge and sewage/metal processing sludge and to
examine the potential application of these biochars for the removal of the phosphorus from
aqueous solution.
1.2. Statement of the problem

In developing countries such as Ethiopia, several industries indiscriminately discharge their

waste into the environment without adequate treatment. These waste materials may contain
organic and inorganic pollutants. In recent years, there has been a growing interest in the use of
biochar as a cost-effective option for wastewater treatment. However, the low phosphorous
removal capacity of unmodified biochar limits its effectiveness as an adsorbent. This research
aims to develop a biochar material by combining brewery sludge, municipal sewage sludge, and
metal processing sludge to enhance its phosphorus removal capacity from aqueous solutions. The
biochar material will be fabricated through a thermochemical process under oxygen-limited
conditions to ensure carbon-rich and stable properties. The biochar will be tested for its ability to

11
remove phosphorus from aqueous solutions using batch experiments and compared with
unmodified biochar. These findings highlight the potential of biochar as a cost-effective and
environmentally friendly alternative for wastewater treatment and phosphorus recovery. This
research project aims to develop a biochar material by combining brewery sludge, municipal
sewage sludge, and metal processing sludge for enhanced removal of phosphorus from aqueous
solutions. The completion should range from a few words to a full sentence. The completion
should range from a few words to a full sentence.

To the best of our knowledge, there is no sufficient information on the preparation of biochars
made from brewery wastewater sludge and sewage sludge or metal processing sludge and their
applications for the removal of phosphorus. Phosphorus is a vital nutrient for all living organisms
and an essential nutrient in agricultural products. However, its depletion within the next 50 to
100 years is a significant concern based on current trends 4. The release of untreated wastewater
containing phosphorus can contribute to the deterioration of the aquatic ecosystem, particularly
by causing eutrophication. Therefore, the study aimed to produce biochars using brewery
wastewater sludge and sewage sludge/metal processing residue, and to investigate the potential
use of these biochars for removing from water and recovering phosphorus from aqueous
solutions. This study is to investigate the efficiency of biochar, produced from a combination of
brewery sludge, municipal sewage sludge, and metal processing sludge, in removing phosphorus
from aqueous solutions and compare its effectiveness to unmodified biochar. The removal of
phosphate from wastewater using biochar is a promising technology, but it is still in its early
stages of development. There are a number of challenges that need to be addressed before
biochar can be widely adopted for phosphate removal12.

12
 1.3. Objectives
1.3.1General objective:

 Synthesis of biochar from brewery, municipal sewage sludge, and metal processing sludge
for the removal of phosphorus from aqueous solution.

1.3.2 Specific objectives

 Preparation of biochars by mixing sewage sludge, brewery wastewater sludge, and metal
processing sludge from an iron and steel factory
 Chemical activation of biochar made from brewery sludge and sewage sludge using iron,
and magnesium salts
 Characterization of biochars using scanning electron microscopy (SEM), Fourier transform
infrared (FTIR), and X-ray diffractometer (XRD) analysis
 Screening out the biochar that have high efficiency of adsorption
 To determine the adsorption efficiencies of the synthesized activated carbons for the removal
of phosphate ions from aqueous solutions.

1.4 Significance of the study

 The study of biochar from brewery sludge, municipal sewage sludge, and metal
processing sludge for phosphorous removal has significant implications for
environmental protection and resource management. In general, the findings of this study
will have the following significance:
 Pioneering biochar: Explores uncharted territory by combining brewery, sewage, and
metal processing sludges to produce biochar with novel phosphorous adsorption
potential.

 Decoding Adsorption Mechanisms: Unveils the hidden secrets behind pollutant–

adsorbent interactions through characterization and data modeling, advancing our
understanding of environmental remediation processes.

13
 Optimizing wastewater treatment: Provides a foundation for designing efficient and
targeted phosphorous removal systems through kinetic and equilibrium analysis.
Broader Community:

 Waste-to-Resource Revolution: Promotes circular economy by transforming waste

sludges into valuable biochar, minimizing environmental impact, and promoting
resource recovery.

 Safeguarding Water Quality: Offers a sustainable and cost-effective solution for

reducing phosphorous pollution in wastewater and protecting public health and
aquatic ecosystems.

 Unlocking Economic Opportunities: Creates new avenues for waste management and
water treatment industries, fostering job creation and boosting local economies.

In essence, this study tackles a pressing environmental challenge with a sustainable

and innovative approach, benefiting both scientific advancement and societal well-
being.

14
 CHAPTER TWO

2.1 LITERATURE REVIEW

2.1.1 Wastewater

Water contamination is a common problem worldwide. The types and concentrations of natural
contaminates depend on the nature of the geological materials through which the groundwater
flows and the quality of the recharge water. Discharge of domestic and industrial effluent wastes,
leakage from water tanks, marine dumping, radioactive waste, and atmospheric deposition are
major causes of water pollution. 17

2.1.2 Phosphorus

Phosphorus is a macronutrient essential for the growth of plants and other biological organisms.
This element is one of the fundamental building blocks that constitute nucleic acids (DNA and
RNA), complex carbohydrates, and phospholipids. In most cases of freshwater bodies, the
limiting nutrient with regard to algal growth is probably phosphorus. Phosphorus 18. The common
forms of phosphorus present in aqueous solutions are orthophosphate, polyphosphate and organic
18,19
phosphate Generally, wastewater contains orthophosphate and small amounts of organic
phosphate. Industrial wastewaters from some industries might contain phosphate levels greater
than 10 mg/L.17 is a crucial nutrient for plant growth and development. However, excessive
phosphorus in aquatic ecosystems can lead to eutrophication and harmful algal blooms. biochar,
which is made from brewery sludge, municipal sewage sludge, and metal processing sludge, has
shown promise as a potential solution for removing phosphorus from aqueous solutions.
Activated carbon is commonly used for this purpose; however, biochar offers a potentially
lower-cost alternative. Several studies have demonstrated the effectiveness of biochar in
removing phosphorus from aqueous solutions. Biochar Properties for Phosphorus Removal
Biochar alone has limited phosphorous removal capacity due to its negatively charged surfaces
and lack of multivalent metal elements.

2.1.3 Phosphorus Cycle

The most significant difference in the phosphorous cycle compared with other element cycles is
that no gaseous compounds exist. Therefore, it is only found in soil and aquatic environments.

15
Because phosphorus is not readily available from the atmosphere, it is deemed the limiting
nutrient. Overall, inorganic phosphorus is discharged into water bodies from numerous natural
and human sources. When plants and animals die, decomposition of the biomass by bacterial
activities converts organic phosphorus to inorganic phosphorus, which is then released back into
the environment. The major steps of the phosphorous cycle in aquatic environments are
summarized below.18

Mineralization: Organic phosphorous compounds are mineralized to orthophosphate by

microorganisms such as bacteria (e.g., Bacillus Subtilis), and fungi (e.g., Penicillium). The
enzymes responsible for the decomposition of phosphorous compounds are phosphatases.

Assimilation: Microorganisms assimilate phosphorus into their cells.

Precipitation of Phosphorus: In the aquatic environment, the solubility of orthophosphate is

affected by pH and the presence of other minerals, Al 3+, Ca2+, Fe3+, and 4 Mg2+. Precipitation leads
to the formation of insoluble compounds, such as Fe3 (PO4)2.8H2O andAlPO4.2H2O.

Solubilization of Insoluble Phosphorus: Microorganism metabolic activity contributes to the

solubilization of phosphorous compounds. The process involves enzymes, production of organic
and inorganic acids, production of CO2, and production of H2S.

2.1.2 Sources of phosphorus

Because phosphorus is usually the limiting nutrient in lakes and rivers, to reverse or slow down
the eutrophication process, the inputs of phosphorus to the water bodies must be abridged. This
can be accomplished by identifying the sources of phosphorus and the potential mitigation
methods for their reduction. The natural source of phosphorus in lakes is the weathering of rock
and the decomposition of organic matter. However, it is extremely difficult to regulate the
natural inputs of phosphorus. As in the case of many lakes, the major sources of phosphorus are
anthropogenic. These nutrient sources are categorized as non-point sources and point sources 20,21

Point Sources

The most common sources of point discharges to water bodies are wastewater and industrial
wastewater effluent, runoff and leachate from waste disposal sites, and runoff from animal

16
feedlots. They tend to be continuous with little variability over time. All municipal sewage
contains phosphorus from human excrement and detergents containing polyphosphate. Total
measured phosphorous content in wastewaters in various countries showed that the average
concentration is approximately 1.4 g P/capital/day. Some industrial wastes also contain large
22
quantities of this nutrient Over the last decades, there has been a significant reduction of
number of point inputs of water pollution, because of their relative ease of identification and
control 23,24

 Non-point Sources

In contrast to point sources, non-point discharges are difficult to measure and control. Most of
the time, they are discrete and linked to seasonal agricultural activities or irregular events, such
as land fertilization, heavy precipitation, or septic leakage. Because of its long-range transport
ability, phosphorus is conveyed overland or underground to receiving waters. Among these
sources, agricultural runoff contributes the most to eutrophication. Phosphorus not taken up by
plants is bound to soil particles and is carried to lakes through soil erosion. Excessive application
25
of fertilizers and inadequate management practices enhance nutrient leaching into the water. In
addition, rainwater also carries some of the phosphorus to water bodies. 24

2.2 Eutrophication

Eutrophication is higher vitamin C intake decreased the risk of osteoporosis by excessive production
of algae and plants in an ecosystem because of enhanced enrichment of nutrients. Limiting
nutrients are nitrogen and phosphorus in most cases, and the general order of deficiency is P > N.
18

Naturally, eutrophication occurs in water bodies over a long period of time as they age and
become filled with sediments. However, an increase in the intensity of agricultural and industrial
activities due to the explosion of human population has accelerated the rate and extent of
eutrophication. Increasing economic growth also indirectly contributes to the issue because it
leads to changes in diets and agricultural extension to accommodate the demand. Once a lake has
become eutrophic, it could take 1,000 years or more to remediate. 26

17
 2.2.1 Stages of the Eutrophication Process

As with any ecological process, eutrophication is dynamic and indicates the functions and
structures of aquatic biological communities and their adaptation to new changes arising in the
27
water environment. The four main stages are described briefly below. The process is triggered
by the increase of excessive nutrients above regular values in the ecosystem. In the second stage,
an escalation of biological productivity leads to the production and overgrowth of aquatic plants
and algae. A thick layer of floating algae is formed.

The third phase corresponds to the death and decomposition of algae and aquatic plants at the
bottom of the water body. During this phase, the oxygen content is depleted and eventually is
used up as the decomposition of biomass accelerates. Anaerobic conditions appear in the water,
which leads to denitrification, followed by sulfate reduction. Hydrogen sulfide (H2S) is can be
formed as waste by sulfate-reducing bacteria. The fourth stage is manifest by the continuous
supply of water with nutrients and further degradation of water quality. The release of H 2S and
ammonia contributes to the process because nutrients are prevented from settling down. Several
chemical reactions brought about by anoxic conditions in water are as follows (CH 2O signifies
decomposing organic matter):

Aerobic respiration: CH2O + O2 → CO2 + H2O

Denitrification by bacteria: 5CH2O + 4NO3 → 2N2 + 4HCO3- + CO2 + 3H2O

Sulfate reduction: 2CH2O + SO42- + H+ → H2S + 2HCO3-

Methane formation: 2CH2O → CO2 + CH4

Iron reduction: CH2O + 7CO2 + 4Fe (OH) 3 → 4Fe2+ + 8HCO3- + 3H2O

2.2.2 Effects of Eutrophication

Eutrophication has become a global environmental issue; within a few decades, many aquatic
bodies have transformed into eutrophic conditions. The effect of eutrophication is not limited to
the ecological characteristics of water bodies but can also cause severe socioeconomic damage.

18
 2.2.3 Impacts on the Ecosystem

Various aspects of the ecosystem can be negatively impact by eutrophication. The intensive algal
growth causes the replacement of corals with filamentous algae, macro- algae, and numerous
filter feeders. Bottom-water hypoxia led to diminished aquatic vegetation and aquatic species.
High production of CO2 accompanied by high organic decomposition rate enhances water
acidification.

Eutrophication is also an ecological threat to benthic life in many coastal areas, mainly because
of the resulting hypoxia and anoxia conditions that occur during the third stage, as described
above. Nguyen et al 2018. Reported a total loss of benthic macrofauna biomass of 3 million
tonnes in some parts of the Baltic Sea due to increased nutrient enrichment. 28 observed loss of
submersed saprophyte beds due to the increase of suspended particles, which are trapped on the
seabed. Accelerated eutrophication negatively impacts important habitats (e.g., seagrass and
shellfish bed) together with fish nursery areas. Accumulation of hydrogen sulfide intensifies
stress on the ecosystem, creating toxic inhabitable environments underwater, resulting in mass
death of submerged aquatic vegetation, aquatic animals, and macro zoo benthos.

2.2.4. Effects on the phytoplankton community

In addition to proliferating extensive phytoplankton blooms in all aquatic habitats, excessive

addition of nutrients (P and N) also causes changes in the specification of phytoplankton. Some
phytoplankton species have changed to larger forms of diatoms. Changes in phytoplankton
communities in eutrophic waters result in significant fluctuations in other areas. Growth of
certain types of phytoplankton, which are beneficial for mussels and other aquatic species, is
impeded 18

2.2.5 Harmful Algal Blooms (HABs)

HABs are one of the growing frequent threats to aquatic ecosystems worldwide. They can cause
damaging effects to both aquatic animals in localized areas and the whole ecosystem through
activities such as poisoning by toxins and clogging of fish gills. While the effects of increasing
eutrophication on HABs are complicated, recent research suggests that the process is likely to
enhance the frequency and magnitude of these events. 29

19
Cyanobacteria, which bloom as the most harmful algae, can cause many nuisances or
impairments to the environment, such as thick scum mats on the surface water, production of
hepatotoxins and neurotoxins, and human death. In addition, booms of phytoplankton and
macroalgae circumscribe light penetration, causing low water clarity and hindering the
photosynthetic processes of benthic plants and sea grasses in the eight littoral zones. HABs also
indirectly affect marine animals because they pose threats to the health and reproduction of
invertebrates, which are the most essential nutrient sources of many oceanic animals. In the Gulf
of Finland, cyanobacterial blooms were the source of the momentous reduction in copepod egg
production.30

2.2. 6. Socioeconomic Effects

The recreational value of eutrophic waters is reduced because of unpleasant odors and views.
Excessive plant growth may hinder marine navigation. If the water is intended for potable use,
the treatment costs increase. Algal biomass may clog filters in treatment plants; therefore, they
must be cleaned more frequently. Many algae-release neurotoxins have detrimental effects on
fish, mussels, and other livestock. As a result, the fishery industry is damaged, leading to job
insecurity31

2.2.7 Phosphorus Health Impacts

Phosphorus is an essential nutrient for human health, but excessive levels of phosphorus can
have negative impacts. Consuming excessive levels of phosphorus can lead to health issues such
as kidney damage, cardiovascular problems, and bone disorders. In addition, high levels of
phosphorus in the diet can contribute to conditions such as hypophosphatemia and osteoporosis.
It is important to be mindful of the sources of phosphorus in your diet to avoid potential health
risks. While phosphorus is essential, excessive consumption can have adverse effects on your
overall well-being. High phosphorous intake is associated with osteoporosis, cardiovascular
disease, and kidney damage. Maintaining a balanced and moderate intake of phosphorus is
crucial for promoting good health. Consider incorporating more natural sources of phosphorus,
such as lean meats, nuts, and dairy products, and limit processed foods that may contain high
levels of added phosphorus. Furthermore, excess phosphorous consumption is linked to an
increased risk of cardiovascular disease. It is important for individuals, particularly those with

20
kidney disease, to be aware of their phosphorus intake and take steps to manage it appropriately
through dietary choices and preventive measures. Retention and accumulation of excessive
phosphorus can accelerate renal, bone, and cardiovascular damage.32

Overall, excessive consumption of phosphorus can have harmful effects on human health,
including kidney damage, cardiovascular problems, and bone disorders. In addition, individuals
with advanced kidney disease may have difficulty maintaining normal serum phosphorus levels
if they consume foods with high levels of phosphorous additives. Excessive phosphorus intake
has been associated with negative impacts on human health, including kidney damage,
cardiovascular problems, and bone disorders such as osteoporosis and low bone density.
Therefore, it is important to be aware of the phosphorous content in your diet and strive for
moderation to support overall health and prevent potential health complications.

Overall, excessive consumption of phosphorus can have harmful effects on human health,
including kidney damage, cardiovascular problems, and bone disorders.

. These effects can be exacerbated in individuals with kidney dysfunction or disease. It is

important to be mindful of the sources of phosphorus in your diet and strive for moderation to
support overall health and prevent potential health complications. Excessive consumption of
phosphorus can significantly disrupt the hormonal regulation of phosphorus, calcium, and
vitamin D, leading to impaired kidney function, disordered bone mineralization, and increased
risk of cardiovascular disease. Therefore, it is crucial to monitor and manage phosphorous intake
to maintain optimal health and prevent these potential negative impacts. Excessive phosphorous
intake can have negative impacts on human health, including an increased risk of cardiovascular
disease and bone disorders such as osteoporosis and low bone density. Individuals need to be
aware of their phosphorous intake and make informed dietary choices to prevent these potential
health complications.

2.3 Phosphorus Treatment Technologies

In the field of wastewater treatment technology, numerous techniques have been implemented to
remove phosphate. They fall into three main categories: biological, chemical, and physical.
Physical methods such as reverse osmosis and electrodialysis are expensive, whereas others are
ineffective, reaching only 10% removal efficiency. Enhanced biological treatment methods can

21
 33
achieve 97% removal of total phosphorus, but operational difficulties make it unstable .
Chemical techniques are the most effective and well-studied methods, including phosphate
precipitation with different salts such as calcium and aluminum. However, the use of salts
increases the costs, and the amount of sludge generated; therefore, this methods has not been
applied widely .34,35 Besides, phosphorus precipitation by metal salts makes the precipitate
unrecoverable for potential processing into fertilizer .36–38

Another chemical technique, adsorption, is economical because the only cost associated with the
adsorbents is transportation. Moreover, no sludge is generated from the process. Low-cost and
readily available materials or agricultural by-products have been extensively investigated for
several decades. Activated carbon derived from various wastes is effective in removing
phosphorus. Nonetheless, the process requires a high amount of energy and the application of
chemicals for activation. Many studies have been conducted to find raw materials that can be
used as they are or with little modification for phosphorous removal. Removal efficiency of
99,6%, corresponding to the operating conditions of 25 mg/L initial phosphate concentration, 2
g/L fly ash dosage, and 5,5 pH level. Phosphate removal of 99% using gas concrete as a building
material

22
Table 1: comparison of different treatment technologies for phosphorous removal

Process Advantages Disadvantages Eff. References

Quality

24,39
Chemical Flexible/Easy Sludge production 0.005-0.04
operation; effective; (significantly high if lime is mg P/L
precipitation
less space is added); P cannot be
required. recycled; chemicals added.

24,39
EPBR High P removal at Energy consumption; more 0.02 – 0.1
modest cost; space is required; cold mg P/L
minimal sludge climate might be a
production challenge; more
complicated configurations.

40
Crystallization Final product can be Increased salinity; complex 0.3-1 mg
used as fertilizer. process. P/L

40
Constructed No additional Susceptibility to climate; poor
sludge; low accumulation of heavy
Wetlands
installation and metals and hazardous
maintenance cost; pollutants.
habitat for some
animals

The biological removal of phosphate from wastewater by using biochar relies on the growth of
microorganisms that can convert phosphate into a less soluble form. These microorganisms are

23
typically fed with organic matter, which provides them with the energy they need to grow and
reproduce. As the microorganisms grow, they release enzymes that bind to phosphate, forming
insoluble precipitates. These precipitates can then be removed from the wastewater by
sedimentation or filtration. Biological removal of phosphate from wastewater using biochar is a
process in which microorganisms use biochar as a substrate for growth and phosphate removal.
The microorganisms can either assimilate the phosphate into their cells or precipitate it out of
solution.

The process of biological phosphate removal using biochar begins with the adsorption of
phosphate onto the biochar surface. The biochar then provides a substrate for the growth of
microorganisms, which then assimilate the phosphate into their cells. The microorganisms can
also produce enzymes that break down phosphate into simpler compounds that are more easily
assimilated by the microorganisms. The efficiency of biological phosphate removal using
biochar depends on a number of factors, including the type of biochar, the type of
microorganisms used, the pH and temperature of the wastewater, and the presence of other
nutrients in the wastewater.

Chemical removal of phosphate from wastewater by using biochar involves the addition of
chemicals to the wastewater that react with the phosphate to form insoluble precipitates. The
most common chemical used for phosphate removal is alum (aluminum sulfate). Alum reacts
with phosphate to form aluminum phosphate, which is a solid that can be removed from the
wastewater by sedimentation or filtration. Chemical removal of phosphate from wastewater
using biochar refers to the use of biochar to adsorb phosphate ions from wastewater through a
variety of chemical mechanisms, including ion exchange, surface precipitation, and
complexation. Ion exchange is a process in which phosphate ions in wastewater are exchanged
for other ions, such as chloride or hydroxide ions, on the surface of biochar. This process is
driven by the electrostatic attraction between the phosphate ions and the positively charged
surface of biochar.

Physical removal of phosphate from wastewater by using biochar involves the adsorption of
phosphate onto the surface of the biochar. Biochar has a high surface area and a porous structure,
which makes it an ideal adsorbent for phosphate. The phosphate is adsorbed onto the surface of

24
the biochar by electrostatic and chemical interactions. Once the biochar is saturated with
phosphate, it can be removed from the wastewater and the phosphate can be recovered or
disposed of. Physical removal of phosphate from wastewater using biochar refers to the use of
biochar to remove phosphate ions from wastewater through physical mechanisms, such as
sieving, filtration, and adsorption. Sieving is a process in which phosphate ions are removed
from wastewater by passing the wastewater through a porous medium, such as biochar. The pore
size of the biochar is small enough to trap the phosphate ions, but large enough to allow the
water to pass through.

Filtration is a process in which phosphate ions are removed from wastewater by passing the
wastewater through a fibrous medium, such as biochar. The fibers of the biochar trap the
phosphate ions, while allowing the water to pass through. Adsorption is a process in which
phosphate ions in wastewater adhere to the surface of biochar. This process is driven by the
physical attraction between the phosphate ions and the biochar surface. The efficiency of
physical phosphate removal using biochar depends on a number of factors, including the type of
biochar, the pore size of the biochar, the concentration of phosphate ions in the wastewater, and
the contact time between the biochar and the wastewater.

Table 2:Comparison of biological, chemical, and physical removal methods

Removal Advantages Disadvantages Safety Guidelines

Method

- Biochar can be a source of

- Can be affected by carbon for microorganisms,
- Low-cost and
Biological other ions in the which can lead to the
sustainable
wastewater growth of undesirable
biofilms

Physical - Low-cost and - Can be affected by - Biochar can also adsorb

sustainable other ions in the other pollutants from
wastewater wastewater, such as heavy

25
 metals and organic
compounds.

- Effective in - Biochar can also adsorb

- Can be affected by
removing other pollutants from
Chemical other ions in the
phosphate ions wastewater like organic
wastewater
from wastewater compounds.

2.4 Adsorption

Adsorption is the accumulation or enrichment of chemical substances onto a surface or interface.

The adsorbing phase is defined as the adsorbent, and the material being adsorbed the adsorbate.
The adsorbent is required to have an extremely large surface area on which the adhesion of
contaminants can occur. It can occur between two phases, such as: gas-liquid, gas-solid, liquid-
liquid, or liquid-solid interface. In the field of water treatment, adsorption has been proven as an
efficient removal process for numerous types of pollutants, where ions or molecules are removed
from liquids by adsorption onto solid surfaces 33

Solid surfaces are active and energetic sites, which are able to interact with solutes due to their
specific electronic and spatial properties. Since adsorption is a surface-based process, the surface
area plays an important role in determining adsorbents’ quality 13,41,42

2.4.1 Adsorption Mechanisms

Four main steps of the process can be summarized as follows

a) Solute is transferred from the liquid to adsorbent’s boundary layer.

b) External diffusion occurs, whereby the solute is transferred to the surface of the adsorbent
through the boundary layer.

c) The solute is diffused from the surface to active sites, termed intra-particle diffusion.

d) Sorption of the adsorbate to the solid phase, by several forces described below.

26
In most cases, two primary driving forces lead to the adsorption of a solute from an aqueous. The
first driving force is linked with the solvent disliking (lyophobic) character of the solute. A
hydrophobic substance tends to be adsorbed while a hydrophilic substance tends to stay in the
water. The solubility of a dissolved substance is essential in determining the intensity of the
adsorption process. The second driving force is the electrical attraction of the solute to the solid.
This type occurs as a result of chemical interaction or van der Waals attraction with the
adsorbent. The adsorption induced by van der Waals force is defined as physisorption, and the
other type of adsorption is termed as chemisorption. In adsorption processes, these two types
interact together and it is quite difficult to differentiate between the two

2.4.1.1 Chemisorption

In chemisorption, electrons in specific surface sites and solute molecules are exchanged,
resulting in the formation of a strong chemical bond. Chemically adsorbed adsorbents are
immobilized within the surface or on the surface. Since chemical reactions happen more rapidly
at higher temperatures, chemisorption is more predominant at high temperatures compared to
physical adsorption. It also has high adsorption enthalpy (40-800 kJ/mol). 43

2.4.1.2 Physisorption

In physisorption, intermolecular attractions occur between favorable energy sites. The adsorbate
is attached to the surface by weak van der Waals forces in physisorption; hence it is less strongly
attached to the surface compared to chemisorption. There is not any exchange of electrons in this
process. In contrary to chemisorption, physical adsorption is predominant at temperatures below
150 oC and its adsorption enthalpy is low (5-40 kJ/mol).44

45
Figure 1: Chemical and physical types of adsorption with their corresponding layers

27
 2.4.1.3 Biosorption

Biosorption is defined as the process of concentration of sorbate and a prefix ‘bio’ means that the
sorbent is of biological origin, a surface of biological matrix. Biosorption is a property of certain
types of inactive, non-living microbial biomass to bind and concentrate heavy metals from even
very dilute aqueous solutions. Biomass exhibits this property, acting just as a chemical
substance, as an ion exchanger of biological origin. The advantages of the process include low
operation costs. If low-cost sorbents are used, low quantity of sewage sludge disposed, COD of
wastewater does not increase

The process is simple in operation and very similar to conventional adsorption or ion-exchange,
except that sorbent of biological origin is employed. It exhibits this property, acting just as a
chemical substance, as an ion exchanger of biological origin. From these biological origins
abundant naturally existing materials, particularly of cellulosic nature, have been suggested as
potential bio sorbents for heavy metals. The different types of biomasses used for the
preparations of biosorbents are shown in Table 3.
28
Table 3:Types of native biomass that have been used for preparing biosorbents

Category Examples

Industrial wastes  Fermentation wastes,

 Food/beverage wastes,
 Activated sludges, and
 Anaerobic sludge, etc.

Agricultural wastes  Fruit/Vegetable wastes, rice straws, wheat bran, soybean halts, etc.

Natural residues  Plant residues, sawdust, tree barks, weeds, etc.

Others  Chitosan-driven materials, cellulose-driven materials, etc.

2.4.2 Factors Affecting Adsorption of Phosphorus

Adsorption is not a homogeneous process and a variety of factors affect its efficiency. Besides
physical properties of the adsorbent such as porosity, internal surface area, and external surface
area, wastewater’s properties also have significant influences on the overall removal efficiency.
The most important characteristics of the feed solution and the adsorbents are reviewed below. 46

2.4.2.1 pH

The effect of pH on the bio-sorption of phosphorus onto different adsorbents has been
investigated in many studies. Coir-pith carbon activated chemically by H 2SO4 achieved the
highest adsorption of phosphorus in the pH range of 6-10 In another study the effective pH range
for phosphate uptake by Aleppo pine sawdust to be 3.5-7.5. served that phosphorus was
effectively removed from wastewater by natural coir pitch in the pH range of 2.0 - 3.5. explored

29
that modified cotton stalks removed phosphorus efficiently in the pH range of 4 - 9. Varying
results on the influence of pH on the adsorption process indicate its complex nature. However,
most results infer that the optimum pH is slightly acidic to around neutral (4 - 7) for the majority
of sorbents.47

2.4.2.2 Temperature

Adsorption is affected by the relations between the properties of the adsorbent and the solute.
Thus, the effects of temperature are different for different adsorbents and solutes. In general,
numerous studies have shown that by increasing the temperature of the solution to a specific
range, the adsorption efficiency of different adsorbents also increases. Found that at pH 3, the
maximum amount of phosphate adsorbed per gram of added granular ferric hydroxide occurred
at 45 oC.48 showed that the phosphorus adsorption capacity of iron hydroxide eggshell increased
as the solution was heated from 20 to 45 oC. The higher phosphorus adsorption capability with
49
increasing temperature to the expansion of pore size at higher temperatures. Suggested that
elevated temperature leads to an increase in the rate of diffusion of phosphate ions, which in turn
enhances the adsorption efficiency. However, it is important to note that higher temperature is
29,50
not always beneficial for the process. In a study conducted by there was a decrease in the
phosphorus sorption capacity of modified giant reed as the temperature increased from 30 oC to
60 oC. The researchers proposed that desorption of phosphate ions from the adsorbent surface
might be accelerated at this temperature range.

2.4.2.3 Adsorbent Dosage

All scientific studies indicated that phosphorus adsorption increased with increasing adsorbent
dose up to a specific level, and then it remained constant. One simple explanation for this is that
by adding more adsorbent to the solution, more binding sites are available for the sorption
process. Thus, high amounts of phosphate ions can be adsorbed. In most studies, the range of
adsorbent dosage is between 0.5 and 2 g/L for 250 mL wastewater 5119,20

2.4.2.4 Contact Time

The design and economics of any adsorption system are heavily influenced by the process’
kinetics. The required contact time varies between different adsorbents and contaminants.
Generally, the adsorption of phosphorus by most adsorbents reached equilibrium in less than 1

30
hour. The adsorption of phosphorus by modified giant reed reached equilibrium after 25 minutes.
The adsorption of phosphorus on modified wheat residue reached equilibrium after 10 minutes,
whereas 30 min was required in the case of using hydroxide-eggshell observed the process
reached equilibrium after 40 minutes when using modified Aleppo pine. Contrariwise, several
studies reported slower uptake speed. 3 h was necessary for the removal process by coir pith
activated carbon to reach equilibrium. In another study, the phosphorus uptake by metal-loaded
orange waste only reached equilibrium after 15 hours. Some authors have concluded that
processes occurring in less than one hour are more favorable and get more ready acceptance in
the science community than those requiring longer contact times
2.4.2.5. Initial Concentration

Generally, the adsorption efficiency decreases if there is a significant increase in the initial
concentration of phosphate. The percentage adsorption of phosphate onto iron hydroxide
eggshell decreased from 95% to 64% when initial phosphate concentrate increased from 2.8
mg/L to 110 mg/L (However, in another study by they observed an increase in phosphate uptake
capacity when the initial concentration was raised from 100 mg/L to 300 mg/L. 34,52

2.4.2.6 Interfering ions

Since wastewater contains various anions, which may interfere in the process, many researchers
have studied their potential effects on the adsorption efficiency. Divya et al. (2012) stated that
the presence of anions like Cl2, SO4 2- , NO3 - and CO3 2- did not show any significant influence on
phosphate adsorption, whilst some actions such as Ca 2+, Mg2+, Cu2+, Fe2+ and Zn2+ facilitate the
process. These findings coincide with those reported by Chen et al. (2014). They concluded that
anions of Cl-, NO3 -, andSO4 2- had a negligible effect on phosphorus adsorption by natural pyrite.
29,53 2- 2-
On the other hand, a study conducted by showed that SO4 and CO3 had a negative
influence on the phosphate uptake of lanthanum-doped activated carbon fiber. These results
demonstrated the complex nature of adsorption process, especially when competing ions are
involved.

2.5 Filtration

Filtration is the mechanical or physical process of removing impurities (e.g., suspended solids,
coagulated particles etc.) from wastewaters by passing the liquids through a porous material,
31
called a filter. Regularly, the filter media can be sand, cloth, anthracite, activated carbon, garnet
sand, or a combination of these materials. The filtrate refers to the liquid passed through the
filter. Filtration process is primarily dependent on a combination of complicated chemical and
18
physical mechanisms, with adsorption being the most essential one There are two main types
of filters, gravity filter and pressure filter, with the former one being more commonly used. For
pressure filters, addition pressure is applied to the water, forcing it through the filter. Meanwhile,
for gravity filters, the gravitational force conveys the water through the filter.

2.5.1 Saturation Time

The saturation point is reached when the effluent concentration becomes equal to the initial
concentration, i.e., the pollutant is not adsorbed anymore. The time at which breakthrough
appears is an important property for determining the operation of a fixed bed column. It is
expressed in terms of normalized concentration, defined as the ratio of outlet concentration to
inlet concentration (Ct/Ci) as a function of time for a given bed height (High flow rates generally
cause the breakthrough and saturation time to occur faster because the contact time is decreased,
which hampers the phosphate diffusion into adsorbents’ pores. Although adsorption is a
relatively fast process, diffusion requires longer residence time of wastewater in the column. As
a result, low flow rates are generally favorable for effective removal of contaminants in fixed bed
column mode 22,52

2.6 Biochar
2.6.1 Understanding Brewery, Municipal Sewage, and Metal Processing Sludge

Normally, agricultural residues are the precursors due to their availability in large amounts and
inexpensive prices. A life cycle impact assessment of different biochar production methods,
conducted by Roberts et al., in 2010, has proven this point. Several papers have indicated that it
54
can be used as soil amendments to improve soil nutrient-holding capacity and benefit favorable
living microorganisms. It is also suggested that it can mitigate global warming by reducing
emissions of carbon dioxide and other greenhouse gasses from soils 55. Additionally, biochar has
been shown to remove different types of pesticides and other hazardous environmental pollutants
.56

32
biochar, made from brewery sludge, municipal sewage sludge, and metal processing sludge,
offers a unique combination of properties that enhance the phosphorus removal capacity of
biochar. This sludge’s contain various metals that can be activated to increase the adsorption
capacity of biochar, as demonstrated by studies using aluminum nanoparticles to modify
municipal sludge biochar for better phosphorus adsorption capacity. Aluminum Modification and
Phosphorus Adsorption Recent studies have shown that aluminum modification of biochar
greatly enhances its phosphorus adsorption capacity. Hou et al found that aluminum-containing
sludge had a better adsorption effect for phosphorus.

Their research showed that municipal sludge biochar modified with aluminum nanoparticles had
a phosphorus adsorption capacity of 6. 06 mg/g, indicating the potential of aluminum-modified
biochar for phosphorus removal. Enhanced Phosphorus Removal Capacity Recent research has
also explored the use of other metal elements, such as MgO, AlOOH, Fe, and Ca, to enhance the
phosphorus removal capacity of biochar. These metal elements, when chemically activated and
added to biochar, have shown significant improvements in phosphorus adsorption capacity. The
phosphorus removal capacity of biochar can be significantly enhanced by modifying it with
multivalent metal elements such as MgO, AlO (OH), Fe, and Ca. The modification of biochar
with metal compounds, such as aluminum, magnesium, iron, and calcium, has been shown to
improve its phosphorus adsorption capacity.

biochar made from brewery sludge, municipal sewage sludge, and metal processing sludge offers
a cost-effective alternative for phosphorus removal from aqueous solutions. biochar, made from
brewery sludge, municipal sewage sludge, and metal processing sludge, offers a unique
combination of properties that enhance the phosphorus removal capacity of biochar. The
unmodified biochar generally has a low phosphorus removal capacity due to its negatively
charged surfaces and lack of multivalent metal elements. However, recent studies have shown
that by modifying biochar with MgO, AlO (OH), Fe, and Ca, the phosphorus removal capacity
can be significantly enhanced.

The modification of biochar with these metal compounds increases its surface area and zero-
point potential, leading to a higher rate of phosphorus removal. The literature review
demonstrates that the phosphorus adsorption capacity of unmodified biochar is generally low due
to its negatively charged surfaces and lack of multivalent metal elements. However, by

33
modifying biochar with metal compounds such as MgO, AlO (OH), Fe, and Ca, its phosphorus
removal capacity can be significantly improved. This review of the literature highlights the
importance of modifying biochar with multivalent metal elements, such as Fe, Mg, Al, and Ca, to
improve its phosphorus adsorption capacity. The use of biochar, made from a combination of
brewery sludge, municipal sewage sludge, and metal processing sludge, offers an innovative
approach to phosphorus removal from aqueous solutions.

2.6.1 Production of Biochar

To produce biochar for phosphorus removal, a combination of brewery sludge, municipal sewage
sludge, and metal processing sludge is used. The sludges are first collected and processed to
remove any unwanted impurities. Then, the sludges are pyrolyzed at high temperatures to
convert them into biochar. During pyrolysis, metal oxides are generated and uniformly
distributed on the surface of the biochar. These metal oxides play a crucial role in the adsorption
of phosphorus from aqueous solutions. The modified biochar with metal compounds exhibits
increased specific surface area and zero-point potential due to the presence of metal oxides. This
enhances the overall phosphorus adsorption capacity of the biochar. The research literature
clearly demonstrates that the modification of biochar with metal compounds significantly
enhances its phosphorus adsorption capacity.

This is evident as the removal rate of phosphorus by unmodified biochar is generally less than
10%, but after modification with MgO and FeCl3, the removal rates can reach 74 .6% and 85%
respectively. Furthermore, the incorporation of multivalent metal elements into biochar through
modification with MgO, AlO (OH), Fe, and Ca has been shown to greatly enhance its
phosphorus adsorption capacity.

The surface activation of biochar using chemicals such as metal salts, alkali, and nano-particles
has also been found to improve the phosphorus adsorption capacity57.

However, it is important to note that the efficiency of biochar in removing anions, such as
phosphorus, is initially low due to its electronegativity and low anion exchange rate. The
literature highlights the importance of modifying biochar with multivalent metal elements, such
as Fe, Mg, Al, and Ca, to improve its phosphorus removal capacity. Several studies have
investigated the use of biochar for phosphorus removal from aqueous solutions. These studies

34
have shown that modifying biochar with metal compounds can significantly enhance its
phosphorus adsorption capacity.

The literature suggests that biochar's anion-removal efficiency is initially not satisfactory due to
its electronegativity and low anion exchange rate. However, through the modification of biochar
with metal compounds such as Fe, Mg, Al, and Ca, its physical and chemical properties are
altered to improve its phosphorus adsorption capacity. Furthermore, the presence of metal oxides
generated from pyrolysis uniformly distributed on the surface of the biochar enhances the
complexation reaction with phosphorus ions, leading to an increase in the overall phosphorus
removal capacity of the biochar. Overall, the literature indicates that the modification of biochar
with metal compounds significantly enhances its phosphorus adsorption capacity. Through
chemical activation and modification with metal compounds like Fe, Mg, Al, and Ca, the
phosphorus removal capacity of biochar can be significantly enhanced. These modifications alter
the physical and chemical properties of biochar, leading to an increase in its specific surface area
and zero-point potential. As a result, the biochar demonstrates improved adsorption capacity for
phosphorus, with removal rates as high as 85%. Pyrolysis is described as the thermochemical
degradation of raw, dried lignocellulosic materials in the absence of oxygen/air at elevated
temperatures to produce carbonaceous char, oil and combustible gases. 18. Depending on the
operating conditions, the pyrolysis process can be divided into three regimes: slow pyrolysis, fast
pyrolysis, and flash pyrolysis. Slower rates of heating increase the production of char, whereas
faster heating rates result in higher yield of liquid product. 58In general, a low temperature and
low heating rate condition, as in the case of slow pyrolysis, is ideal for a high biochar yield. On
the contrary, if the purpose is to maximize the yield of bio-oils, a high heating rate, short
residence time, and high temperature would be preferred . 58,59 Another important factor
influencing the properties of biochar is the quality of the biomass.

2.6.2 Characteristics of biochar

Based on the literature review, biochar modified with metal compounds such as Fe, Mg, Al, and
Ca exhibits several characteristics that enhance its phosphorus removal capacity: - Increased
specific surface area: The modification of biochar with metal compounds leads to an increase in
its specific surface area, allowing for more contact between the biochar and the aqueous solution
containing phosphorus. This increased surface area provides more active sites for the adsorption
of phosphorus ions, resulting in improved removal capacity. - Enhanced zero-point potential:

35
The modification of biochar with metal compounds also increases its zero-point potential, which
refers to the pH value at which the biochar has no net charge. A higher zero-point potential
allows for better adsorption of phosphorus ions, as it increases the electrostatic attraction
between the biochar and the charged phosphorus ions. Additionally, the modification of biochar
with metal compounds improves its anion exchange rate, addressing the low anion-removal
efficiency of unmodified biochar57. Moreover, the incorporation of multivalent metal elements
into the biochar matrix alters its physical and chemical properties. These modifications enhance
the phosphorus adsorption capacity of biochar, making it a more effective and efficient adsorbent
60 61
for removing phosphorus from aqueous solutions Furthermore, the literature also suggests
that surface activation by chemicals such as metal salts, alkali, and nano-particles can
significantly enhance the phosphorus adsorption capacity of biochar.

The use of biochar made from brewery sludge, municipal sewage sludge, and metal processing
sludge has shown promise in effectively removing phosphorus from aqueous solutions. The
modification of biochar with metal compounds, such as Fe, Mg, Al, and La, improves its
phosphorus adsorption capacity .Overall, the literature review highlights the effectiveness of
biochar derived from brewery sludge, municipal sewage sludge, and metal processing sludge in
removing phosphorus from aqueous solutions .In summary, the literature review suggests that
biochar made from brewery sludge, municipal sewage sludge, and metal processing sludge can
be a viable and efficient method for removing phosphorus from aqueous solutions . The literature
review indicates that biochar made from brewery sludge, municipal sewage sludge, and metal
processing sludge can be an effective and efficient method for removing phosphorus from
aqueous solutions. The literature review indicates that the modification of biochar with metal
compounds, such as Fe, Mg, Al, and Ca, can significantly enhance its phosphorus adsorption
capacity, making it a promising solution for removing phosphorus from aqueous solutions. Based
on the literature review, it can be concluded that biochar made from brewery sludge, municipal
sewage sludge, and metal processing sludge has shown potential in effectively removing
phosphorus from aqueous solutions. In conclusion, the literature review demonstrates that
biochar made from brewery sludge, municipal sewage sludge, and metal processing sludge can
effectively remove

36
 2.6.3 Role of biochar in Phosphorus Removal

The literature review suggests that biochar, derived from a combination of brewery sludge,
municipal sewage sludge, and metal processing sludge, shows great promise in effectively
removing phosphorus from aqueous solutions. Various studies have shown that unmodified
biochar has low phosphorus removal capacity due to its negative charge and lack of multivalent
metal elements. However, the modification of biochar with metal compounds such as Fe, Mg,
Al, and Ca significantly enhances its phosphorus adsorption capacity by increasing its specific
surface area, zero-point potential, and anion exchange rate. Furthermore, the use of biochar made
from brewery sludge, municipal sewage sludge, and metal processing sludge has been found to
be a cost-effective method for phosphorus removal. These findings suggest that biochar can
serve as an efficient and economical solution for phosphorus removal from aqueous solutions.
By utilizing waste materials such as brewery sludge, municipal sewage sludge, and metal
processing sludge, biochar not only offers a sustainable solution for waste management but also
provides a valuable resource for water treatment. The literature review also highlights the
potential of chemical activation to enhance the phosphorus removal capacity of biochar. By
modifying biochar with compounds like MgO, AlO (OH), Fe, and Ca, the adsorption capacity of
biochar can be significantly enhanced, making it a viable option for phosphorus removal.
Overall, the literature review emphasizes the potential of biochar from brewery sludge,
municipal sewage sludge, and metal processing sludge as an efficient and effective method for
removing phosphorus from aqueous solutions. The modification of biochar with metal
compounds has been shown to enhance its phosphorus adsorption capacity by increasing its
specific surface area and anion exchange rate, as well as improving its zero-point potential.
These findings suggest that biochar has the potential to play a significant role in addressing the
challenges associated with phosphorus pollution in water bodies.

2.6.4. Application of biochar in Aqueous Solutions

The application of biochar from brewery sludge, municipal sewage sludge, and metal processing
sludge in aqueous solutions shows great promise in effectively removing phosphorus. The
combination of these waste materials in the production of biochar not only provides a sustainable
and cost-effective solution for waste management but also results in a highly effective adsorbent
for phosphorus removal. The literature review indicates that biochar has shown significant

37
potential in addressing phosphorus pollution in water bodies. It is worth noting that unmodified
biochar has limited phosphorus removal capacity due to its negatively charged surfaces and lack
of multivalent metal elements.

Treatment Sorption of contaminants from wastewater onto biochar occurs due to its high surface
area and porosity62 . While most of the studies on biochar application are focused on soil
amendment, there has been a growing interest in using biochar to treat wastewater. Some studies
have shown that biochar can be an effective adsorbent for sorption of heavy metals from
wastewater). However, only a few researchers have investigated the possibility of using biochar
to remove phosphate from wastewater. Not only biochar embodies a low-cost technology, but the
used biochar can also be marketed as a fertilizer to enhance soil fertility.

2.6.5 Using biochar for Phosphorus Removal

In a recent case study, biochar produced from a combination of brewery sludge, municipal
sewage sludge, and metal processing sludge was used to remove phosphorus from an aqueous
solution. The results of the study showed that the biochar exhibited a higher phosphorus removal
capacity compared to unmodified biochar. The phosphorus removal capacity of the biochar was
enhanced through surface activation with chemicals such as metal salts, alkali, and nano-
particles. This chemical activation process increased the specific surface area and zero-point
potential of the biochar, allowing for stronger adsorption of phosphorus ions. The study also
found that the biochar had a higher anion exchange rate, which further contributed to its
enhanced phosphorus adsorption capacity. This research suggests that biochar has the potential
to be a highly effective adsorbent for phosphorus removal in aqueous solutions. Benefits and
Advantages of biochar The use of biochar in aqueous solutions for phosphorus removal offers
numerous benefits and advantages. Firstly, the use of biochar provides a sustainable solution for
waste management as it utilizes brewery sludge, municipal sewage sludge, and metal processing
sludge that would otherwise be disposed of. This not only reduces waste volume and disposal
costs but also contributes to the circular economy by converting waste materials into a valuable
product.

The use of biochar for phosphorus removal from aqueous solutions offers several benefits and
advantages. Firstly, the use of biochar provides a sustainable solution for waste management as it

38
utilizes brewery sludge, municipal sewage sludge, and metal processing sludge that would
otherwise be disposed of. This not only reduces waste volume and disposal costs but also
contributes to the circular economy by converting waste materials into a valuable product.
Furthermore, the production of biochar is cost-effective. The use of readily available waste
materials as feedstock for biochar production reduces costs and promotes an efficient use of
resources.

2.6.7 Potential Challenges and Limitations

While biochar shows promise for phosphorus removal from aqueous solutions, there are
potential challenges and limitations that should be considered. One potential challenge is the
variability in the composition of the feedstock materials, such as brewery sludge, municipal
sewage sludge, and metal processing sludge. This variability can affect the quality and
performance of the biochar, potentially leading to inconsistent phosphorus removal results.
Additionally, the effectiveness of the biochar may be influenced by factors such as pH,
temperature, and contact time. These factors can impact the adsorption capacity of the biochar
and may require optimization for different conditions. Furthermore, the use of biochar for
phosphorus removal may also have limitations in terms of scalability and application.

Therefore, further research and development are needed to optimize the production process,
improve consistency, and evaluate the performance of biochar in different environmental
conditions. Additionally, the efficient recovery of the biochar particles with adsorbed phosphorus
from the water stream after treatment poses a challenge. This challenge is related to the energy
and pressure gradient required for capturing back the biochar particles, which can result in a
significant carbon footprint. Overall, the literature highlights the potential of biochar derived
from brewery sludge, municipal sewage sludge, and metal processing sludge as a sustainable and
efficient adsorbent for phosphorus removal from aqueous solutions. The potential benefits of
using biochar for phosphorus removal from aqueous solutions are evident. However, there are
still challenges and limitations that need to be addressed. These challenges include the variability
in feedstock composition, the need for optimization under different conditions, and the
difficulties in efficient recovery of biochar particles. Additionally, the scalability and application
of biochar for phosphorus removal may also be limited.

39
 2.7 Characterizations of biochar-based Nano composite material

Phosphorus is an essential nutrient for plant growth, but it can also be a major pollutant in
wastewater. It can lead to eutrophication in water bodies, which can cause algal blooms and
oxygen depletion. Biochar-based Nano composite materials have been shown to be effective for
phosphorus removal from wastewater. These materials are typically made by impregnating
biochar with metal oxides or other nanoparticles.

This study characterized a Nano composite biochar material made by impregnating rice straw
biochar with iron oxide nanoparticles. The material was characterized using a variety of
techniques; including scanning electron microscopy (SEM), energy dispersive X-ray
spectroscopy (EDX), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy
(FTIR).

40
 CHAPTER THREE
3.Materials and Methods
3.1 The study site and periods
The study will be carried out at Jimma University main campus, Chemistry research laboratory.
Jimma university main campus is found in Jimma zone of Oromia regional state at Jimma town,
346 Km away from Addis Ababa, Ethiopia. The study will be conducted from September 2023
to April 2024.

3.2 Chemicals and apparatus

In this study, various chemicals will be used, including, sodium dihydrogen phosphate dihydrate,
ammonium molybdate, thiourea, sulfuric acid, nitric acid, potassium nitrate, hydrochloric acid,
and sodium hydroxide.
3.2.1. Instrumentations and apparatus

The apparatus that will be used in the study are conical flasks, cuvette, funnel, beakers, filter
paper, volumetric flasks, measuring cylinder, crucible, digital balance, furnace, shaker, oven, hot
plate, pH meter, magnetic stirrer, Ultra violate – Visible (UV–Vis) spectrophotometer, Scanning
Electron Microscope (SEM), Fourier Transform Infrared (FT-IR), X-ray Diffraction (XRD).

3.3. Collection and preparation of adsorbents

The brewery sludge (BS) sample will be collected from Saint George Brewery Share Company,
municipal sewage sludge (MSS) from the Kaliti wastewater treatment plant, and metal
processing sludge from the Ethiopian iron and steel factory (MPS) in Addis Ababa. The
63
adsorbents will be prepared using the method described in the literature . Biochars will be
prepared by mixing BS & MSS, BS & MPS, and MSS & MPS with a dried ratio of 0 -100 wt%
in ceramic cups in a muffle furnace at temperatures ranging from 200 to 600 °C for 2 h. Then,
the biochars (BS-MSS, BS-MPS, and MSS-MPS) will be cooled to room temperature. The
resulting biochars will then be ground and sieved to obtain fine particle sizes of 0.5-1 mm. The
samples will then be rinsed with distilled water to remove impurities. Finally, the products will
be dried at 80 °C and stored in plastic bags for future use. Activation of the biochar (BS-MSS)

41
using ferric chloride, phosphoric acid, and magnesium chloride will be made following the
procedures used in the literature 64–66

3.4. Adsorbent characterization

3.4.1 Proximate analysis of activated carbons
Proximate analysis such as moisture content, ash content, volatile matter and fixed carbon in
activated carbons and the point zero charge (pH pzc) of the biochars will be determined following
67
the methods described in Kebede et al . The morphological and functional groups on the
surface of the biochars will be studied by using SEM and FTIR, respectively. The crystal
structure of the biochars will be determined by using XRD analysis.

3.4.1.1 Moisture content determination

The moisture content of activated carbons will be determined through weighing of 2 g activated
carbons by electronic beam balance and added into dried crucibles. The dried crucibles with
adsorbents will be inserted into oven at 130 ºC for 2 h. After 2 h the adsorbents will be removed
from oven and cooled down to the normal temperature. Finally, the moisture contents will be
determined as in weight % as follows in Equation 1

¿
Moisture content.%=W 2−W 1¿−(W 3−W 1)(g) (w 2−w 1)(g) x 100

(1)

Where w1= weight of crucible, W2= weight of crucible and sample before drying W 3= weight of
sample and crucible after drying
oven dry weight(g)
𝐷ry mater (%) = ∗ 100 (2)
(2) initial sample weight(g)

3.4.1.2. Ash content determination

The ash content of activated carbons will be determined through weighing of 2 g activated
carbons by digital beam balance and added into weighed & dried crucibles. The dried crucibles
with adsorbents will be subjected into muffle furnace at 650 ºC for 3 h. After that the crucible

42
with adsorbents will be removed from muffle furnace and cooled down to the normal
temperature. Finally, the ash contents will be determined as in weight % by following Equation.

(W 3−W 1)( g)
Ash content (%) = x 100 ( 3)
(w 2−w 1)(g)

Where, W1 = weight of the crucible, W2 = weight of the crucible and sample before igniting, W3
= weight of crucible and sample after igniting

3.4.1.3 Volatile Matter content

The volatile matter content of adsorbents will be determined through weighing of 5 g activated
carbons by digital beam balance and added into weighed & dried crucibles. And then the
crucibles with adsorbents will be closed and placed in the muffle furnace. The sample will be
ignited in the furnace at 550 ºC for 10 min. After 10 min the sample will be removed from
furnace and cooled to room temperature and then weighted by using electronic beam balance.
Finally, the volatile matter contents of adsorbents will be determined as in weight % by
following Equation.

Volatile matter content ( % ) W 2−W 1 ¿−(W 3−W 1)(g) ¿ x 100

(w 2−w 1)(g)
(4)

Where, w1 represents weight of crucible, w2 weight of sample and crucible, w 3 represents weight
of crucible and sample after incineration for the given time.

3.4.1.3 Fixed carbon content determination

Fixed carbon contents of adsorbents will be calculated as the resultant summation of percentage
of all proximate analysis (moisture content, volatile matter content and ash content) and
subtracted from 100 %. The fixed carbon contents will be determined as in weight % as follows
in Equation1.

¿ carbon content ( % ) =100 %−(Moisture %+ ash %+Volatile matter %)

43
 3.4.1.5. Effects of pH:
By keeping all other parameters constant like contact time, adsorbent dose, initial concentration
of metal ions; only varying the pH value from 2, 4, 6, 8, and 10 the effect of pH will be
optimized.

3.4.1.6 Point zero charge (PZC) determination

Point zero charge is the point at which the net charge on the adsorbent surface is zero.That means
pH of initial adsorbent surface is equal to pH of finial adsorbent surface (pH initial =pHfinal). The
surface charge of the adsorbent depends on the pH of the solution and its pH of point zero charge
(pHpzc)[68]. The adsorbent surface will be negatively charged when pH > pH pzc and positively
charged if the pH < pHpzc. PZC of the BS, MPS and MSS activated carbons is going to be studied
through the following procedures. Ten series of test solutions (H 2PO4-) solution) 100 mL will be
prepared in conical flask by varying initial pH of the test solution from pH 3, 4, 5, 6, 7, 8, 9, 10,
11, 12. Then; 1 g of the adsorbents (BS, MPS and MSS activated carbons) will be added to each
test solutions. And the solutions will be shaken for 24 h at 200 rpm in room temperature 25 °C.
Finally, the pH will be measured and recorded. The net charge (ΔpH) on adsorbents surface will
be determined by the difference between initial pH and pH after 48 h. The pH values will be
plotted along the x-axis and ΔpH along y-axis.

3.4.1.7 Determination of surface area

Specific surface area of adsorbent will be calculated using the formula Sears method.

1.0 g of adsorbent will be mixed with 100 mL of distilled water and 20 g NaCl. The mixture will
be shake for five minutes. Its final pH will adjust to 4 with 0.1 M HCl. It was then titrated against
0.1 M NaOH to raise the pH from 4 to 9 and the volume (mL) of 0.1 M NaOH will be measured
in replicate and the average value was taken for the surface area calculation by sears method.
S = 32 × v − 25 (5)

Where, S is surface area of bio adsorbent per gram (m 2 /g), V is volume (mL) of 0.1M NaOH
required to raise the pH of the sample from 4 to 9. The numbers 32 and 25 are physical constants.

44
 3.4.1.8. FT-IR (Fourier Transform Infrared) analysis
The functional groups on the surface of the activated carbons (before and after adsorption) will
be studied by using FT-IR. It will be used to analysis chemical composition of the samples in the
wave number range of 400-4000 cm-1.

3.4.1.9. Scanning Electron Microscope (SEM) analysis

The morphological and microstructure of activated carbons will be investigated by using SEM.

3.4.1.10.XRD (X-ray Diffraction) analysis

XRD is used to determine the mineral compositions present in the material. a technique used to
analyze the crystal structure and phase composition of materials in the context of activated
carbon. By measuring the diffraction of X-rays at a specific angle (2θ), the presence of different
minerals can be identified. This nondestructive technique is particularly useful for determining
the phase purity of synthesized samples, as it can reveal the crystal structure and composition of
the material in the 2θ range of 10 to 80º.

3.4.1.11. UV-Vis Spectrophotometry analysis

The initial and final concentration of phosphate ions in solution will be measured using UV–Vis
spectroscopy at wave length of 𝜆 = 540 nm after reaction with Ammonium molybdate
[NH4]2MoO4

3.5. Batch Adsorption Study

Stock solutions of 1000 mg/L of H 2PO4- will be prepared by dissolving Na 2H2PO4 in distilled
water. All other concentrations in the adsorption experiments will be achieved by diluting the
stock solution with distilled water. A known amount of biochars (BS-MSS, BS-MPS, or MSS-
MPS) will be added to 40 mL solution phosphate ions. The initial pH will be adjusted using 0.1
M NaOH or HCl. The tubes will be shaken horizontally for 5 min to 24 h. Then, it will be
filtered using Whatman No. 1 filter paper. The residual concentration of MB in the filtrate
H2PO4- will be directly determined using a UV-Vis spectrophotometer, whereas that of phosphate
ions in the filtrate will be measured after the complexation reaction of phosphate with
ammonium molybdate followed by reduction with thiourea described in 69. The adsorption
efficiency (A%) and the amount of phosphate ions adsorbed per unit mass of the adsorbent (q t,
mg/g) at any given time (t, min) can be calculated using Eqs. (1) and (2). In these Eqs, C 0 and Ct

45
(mg/L) represent the initial concentration of H 2PO4- and the concentration at time t, respectively
70

A ( % )=
( C 0−C t
C0 )
× 100 ( 6 )

q t= ( C0 −Ct ) ( Vm ) (7 )

3.5.1. Effect of the initial pH value

The study will involve testing different initial pH levels for these solutions. To conduct the
experiment, separate solutions containing phosphate with a concentration of 10 mg/L will be
created. These solutions will then be agitated for an optimal duration, after which the remaining
concentrations of phosphate in the solutions will be analyzed. The purpose of this investigation is
to understand how the initial pH levels affect the retention or adsorption of phosphate in the
solutions.

q t=qe ( 1−exp ) ( 8)
−K 1 t

2
K 2qe t
q t= ( 9)
1+ K 2 qe t

3.5.2. Real wastewater samples

The efficiency of the adsorbents will be evaluated by testing their performance with wastewater
samples from wastewater treatment plants, the tannery industry, and the textile dyeing industry
in Addis Ababa. The first step involves determining the concentration of phosphate in the

46
wastewater. The biochar's effectiveness in removing phosphate from wastewater will be analyzed
as described above.
3.5.3. Regeneration of bio sorbents

First, the adsorbate will be adsorbed onto the adsorbents. The adsorbents will then be desorbed
using a 0.1 M NaOH or HCl solution. The content of phosphate will be measured after filtration.
After rinsing with distilled water and drying, the efficiency of phosphate adsorption on the
regenerated adsorbents will be determined in the next sorption cycle.
3.6. Data analysis
Besides the coefficient of determination, the nonlinear chi-square (χ2) statistic test will be used
to identify the best model fit to the observed experimental data. Statistical analyses will be
performed using Origin 8 software.
3. 6.1. Nonlinear chi-square (χ2)
Nonlinear chi-square (χ2) is a statistical measure used to assess the goodness of fit of a nonlinear
model to a set of observed data. It is similar to the traditional chi-square test used for linear
models, but it is specifically designed for nonlinear models. In the context of nonlinear
regression analysis, the nonlinear chi-square measures the discrepancy between the observed
values and the values predicted by the nonlinear model. It is calculated by summing the squared
differences between the observed and predicted values, and then dividing by the variance of the
observed values. The nonlinear chi-square can be used to evaluate the overall fit of the model as
well as to compare different nonlinear models to determine which one provides the best fit to the
data. A smaller value of the nonlinear chi-square indicates a better fit between the model and the
observed data.

3.4. 6.2. Adsorption Isotherms

To determine the maximum sorption capacity for phosphate adsorption, adsorbate solutions with
initial concentrations ranging from 5 mg/L to 100 mg/L will be prepared and analyzed after
shaking for 24 h. The experimental equilibrium data will be evaluated using the non-linear form
of Langmuir Eq. (3) and Freundlich Eq. (4) isotherm models.
Q max b Ce
q e= ( 1 0)
( 1+b C e )

47
 1
q e =K F C n (11)
e

Where, qe represents the amount of adsorbate adsorbed (mg/g), C e represents the equilibrium
concentration of the adsorbate in the aqueous phase (mg/L). The Langmuir constants, Q max
(mg/g) and b (L/mg) are related to the adsorption capacity and energy of adsorption,
respectively. Both Qmax and b can be calculated by plotting Ce vs. qe. KF (mg1-1/n L1/n/g) is the
adsorption coefficient based on the Freundlich equation; 1/n is the adsorption intensity based on
the Freundlich equation.
3.4.6.3. Adsorption kinetics

Separate solutions of 10 mg/L containing phosphate will be prepared. The samples will be
analyzed at various time intervals, ranging from 5 min to 24 h, as described above. The
experimental data will be analyzed using non-linear pseudo-first-order (Eq.5) and pseudo-
second-order kinetics (Eq. 6).

q t=qe ( 1−exp−K t ) ( 12 )
1

2
K 2qe t
q t= (13 )
1+ K 2 qe t

Where, k1 (min−1) represents the pseudo-first-order rate constant; k 2 (g/mg.min) represents the
pseudo-second-order rate constant; qt represents the adsorbed amount (mg/g) at any time t (min);
and qe represents the adsorbed amount at equilibrium.
3.4.6.4 Expected outcomes and deliverables

The project aimed to utilize biochars derived from waste materials to remove contaminants from
wastewater, thereby providing dual advantages of pollution mitigation. The batch adsorption
process will enable the recovery of phosphorus. The experimental parameters for batch
adsorption will be optimized to enhance the effectiveness of biochars using synthetic wastewater.
Subsequently, the performance of the biochars will be evaluated using real wastewater samples.
Therefore, this study will produce the following outcomes.

48
  Developed biochars by mixing brewery sludge, sewage sludge, and metal processing
sludge.
 Determined the optimal combination ratio of brewery sludge, sewage sludge, and metal
processing sludge to enhance the removal of phosphate ions in aqueous solutions.
 Environmental protection can be achieved by developing filter materials that effectively
remove phosphate ions from aqueous solutions.

4.1 WORK PLAN AND BUDGET BREAKDOWN

4.1. Work plan
Table 4: Work Time Schedule

49
 Time in the Months
Octob Marc
S/No Activities Nov Dec- Jan- Feb- April May- Jun-
er h
-23 23 24 24 24 24
2023 2024 2024

1 Research topic selection 

 
2 Develop research proposal

Taking proposal comment 

3
and submissions

4 Proposal presentation

Purchasing and arranging


5 required materials & 
chemicals
Sample collection and lab-  
6 
examination
     
7 advisor contact  

Final report writing and 

8
submission


9 Thesis defense

4.2.1. Budget breakdown of the study

The following tables shows the budget which will be required for this study

Table 5 List of chemicals and its cost

Chemicals Birr Cent

50
Thiourea (CH₄N₂S) 1,850 00

Ammonium molybdate [NH4]2MoO4) 1,530 00

Phosphoric acid (H3PO4) 1,700 00

nitric acid (HNO3) 1,240 00

Potassium nitrate (KNO3) 1,130 00

sodium dihydrogen phosphate dihydrate 1,090 00

Hydrochloric acid (HCl) 1,420 00

Sodium hydroxide (NaOH) 1,540 00

Table 6: List and cost of stationeries materials and safety equipment

Stationary materials and safety ware Birr Cent

Glove 900 00

Eye glass 850 00

Laboratory coat 1,200 00

Pen and paper 300 00

Binding and printing fee 2,150 00

Sample Collection 2,200 00

Transport fee 5,900 00

Table 7: Budget summary

Item description Total price

51
 Birr Cent
Purchasing chemicals 11,500 00
Stationeries materials and safety ware 13,500 00
Total 25,000 00

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