COLLEGE OF PUBLIC HEALTH AND MEDICAL SCIENCES

DEPARTMENT OF ENVIRONMENTAL HEALTH SCIENCE AND

TECHNOLOGY

Simultaneous Removal of Nitrate and Phosphate Ions from Aqueous Solution

Using Solid Waste from Alum and Sulphuric Acid Manufacturing Process

By
Yifru Waktole

A RESEARCH PAPER SUMMITTED TO DEPARTMENT OF ENVIRONMENTAL HEALTH

SCIENCE AND TECHNOLOGY, COLLEGE OF PUBLIC HEALTH AND MEDICAL SCIENCES,
JIMMA UNIVERSITY IN PARTIAL FULLFILLMENT FOR THE REQUIREMENT OF MASTERS
DEGREE IN ENVIROMENTAL HEALTH SCIENCE AND TECHNOLOGY

June, 2013
Jimma, Ethiopia

i
Simultaneous Removal of Nitrate and Phosphate Ions from Aqueous Solution
Using Solid Waste from Alum and Sulphuric Acid Manufacturing Process

By: Yifru Waktole

Advisors: - Mr. Seid Tiku (PhD candidate)

Mr. Fekadu Fufa (PhD candidate)

June, 2013
Jimma, Ethiopia

ii
DECLARATION

I proclaim that this piece of work is my own and all sources of materials used for this thesis work
have been properly acknowledged.

Name: Yifru Waktole

Place: Jimma, Ethiopia

Signature: _____________________________________

Date of submission: _____________________________________

This thesis was submitted for examination with the approval of university advisors

Name Signature Date

Mr. Seid Tiku (M.Sc., PhD candidate) _______________ _________________

Fekadu Fufa (M.Sc., PhD candidate) _______________ _________________

Department Head _______________ _________________

iii
ABSTRACT

Nitrogen and Phosphorous are limiting nutrients for plant growth. Contrary to this, phosphorous
between 20 to 100 µg/L and nitrogen between 500 to 1000 µg/L can cause eutrophication in most
aquatic systems. Therefore, developing low cost and efficient method of removing these
nutrients to protect the aquatic environment is mandatory. The objective of this study was to
investigate simultaneous nitrate and phosphate adsorption capacity of solid waste residue
collected from Awash Melkassa Aluminium Sulphate and Sulphuric Acid Factory. Batch
adsorption experiments were conducted to evaluate the effect of contact time, initial solution pH,
initial nitrate and phosphate ion concentration, adsorbent dose and effect of coexisting ions on
simultaneous removal of nitrate and phosphate ions. Besides, adsorption isotherms and kinetics
were analysed to determine the mechanism and rate determining steps during the adsorption
process. After conducting batch experiment, the equilibrium time was achieved within 90
minutes while the optimum pH and adsorbent dose were found to be 7 and 20 gm/L respectively.
The adsorption kinetics of nitrate and phosphate ions best fitted to the pseudo-second order
equation with R2 values 0.992 and 1 respectively. Moreover, isotherm studies showed adsorption
of nitrate and phosphate fitted better to Freundlich isotherm and Langmuir isotherm with R2
0.988 and 0.984 for phosphate and 0.991 and 0.955 for nitrate respectively. Studies on
reusability of the spent adsorbent showed nearly 50% the adsorbed phosphate can be desorbed
with 0.1M NaOH while that of nitrate is 99.75% showing there is a possibility of reusing. Last
but not least, application on wastewater showed promising result though there is decrease in
percent removal. At the optimums found during the batch experiment, AW residue collected
from Awash Melkassa Aluminium sulphate and Sulphuric acid factory can potentially remove
phosphate from wastewater. But, the untreated AW was not suitable to remove nitrate ion from
wastewater since its percent removal was from 27-30%.

Keywords: Simultaneous removal; batch adsorption; chemisorption; adsorption capacity; alum

waste

iv
ACKNOWLEDGEMENT

First, I would like to thank the Almighty God. Next, I would like to express my deepest gratitude
to my advisors Mr. Seid Tiku and Mr. Fekadu Fufa for their invaluable guidance, support and
advice. In addition, I would like to thank Jimma University and Department of Environmental
Science and Technology. Last but not least, I am very much grateful to my wife, Mr. Teressa
Urgessa, Mrs. Tigist Waktole and her husband, Mr. Keneni Waktole, Mr. Ephrem Haile, father
Frehiwot Gebremeskel, Mr. Mitiku Bajero, Mr. Seyoum Derib, Dawit Fasil and his wife; all
friends who were on my side from the beginning till now.

v
Table of contents

DECLARATION ........................................................................................................................ iii

ABSTRACT................................................................................................................................ iv
ACKNOWLEDGEMENT ........................................................................................................... v
LIST OF FIGURES .................................................................................................................... xi
ABBREVIATIONS ................................................................................................................... xii
CHAPTER ONE: INTRODUCTION .......................................................................................... 1
1.1 Background .......................................................................................................................1
1.2 Statement of the problem ..................................................................................................2
1.3 Significance of the study ...................................................................................................3
CHAPTER TWO: LITERATURE REVIEW ............................................................................ 10
2.1. Forms and sources of nitrogen in the environment .........................................................10
2.2. Forms and sources of phosphorus in the environment ....................................................10
2.3. Environmental impacts of nitrogen and phosphorous .....................................................11
2.4. Nitrogen and phosphorus removal methods ....................................................................12
2.4.1. Nitrate removal ............................................................................................................... 12
2.4.2. Phosphate removal ......................................................................................................... 12
2.5. Aluminum sulphate and sulphuric acid factory waste ....................................................13
CHAPTER THREE: OBJECTIVES OF THE STUDY ............................................................ 15
3.1. General objective.............................................................................................................15
3.2. Specific objectives...........................................................................................................15
CHAPTER FOUR: MATERIALS AND METHOD ................................................................. 16
4.1. Study area and period ......................................................................................................16
4.2. Study design ....................................................................................................................16
4.3. Study variables ................................................................................................................16
4.4. Conceptual framework ....................................................................................................16
4.5. Adsorbent preparation .....................................................................................................17
4.6. Effect of contact time ......................................................................................................17
4.7. Effect of initial pH...........................................................................................................17

vi
4.8. Effect of adsorbent dose ..................................................................................................17
4.9. Effect of initial concentration ..........................................................................................18
4.10. Effect of coexisting ions ..................................................................................................18
4.11. Desorption experiment ....................................................................................................18
4.12. Adsorption experiment on wastewater ............................................................................19
4.13. Chemical analysis ............................................................................................................19
4.14. Data analysis ...................................................................................................................20
4.14.1.Adsorption Kinetics ........................................................................................................20
4.14.1.1.Pseudo-First order kinetics ......................................................................................... 21
4.14.1.2.Pseudo-second order kinetics ..................................................................................... 21
4.14.2.Adsorption Isotherm .......................................................................................................22
4.14.2.1.Langmuir isotherm ..................................................................................................... 22
4.14.2.2. Freundlich isotherm ................................................................................................... 23
4.11.3. Dubnin and Radushkehvich isotherm........................................................................... 23
4.15. Data quality management ................................................................................................24
4.16. Ethical consideration .......................................................................................................24
4.17. Dissemination plan ..........................................................................................................24
CHAPTER FIVE: RESULT ...................................................................................................... 20
5.1. Effect of contact time ......................................................................................................20
5.2. Adsorption kinetics .........................................................................................................20
5.3. Effect of initial pH...........................................................................................................24
5.4. Effect of adsorbent dose ..................................................................................................25
5.5. Effect of initial concentration ..........................................................................................27
5.6. Adsorption isotherm ........................................................................................................28
5.7. Mean sorption energy ......................................................................................................30
5.9. Effect of co-existing ions ................................................................................................34
5.10. Desorption experiment ....................................................................................................35
5.11. Removal of phosphate and nitrate from wastewater .......................................................36
CHAPTER SIX: DISCUSSION ................................................................................................ 38
CHAPTER SEVEN: CONCLUSION AND RECOMMENDATION ...................................... 40
7.1. Conclusions .....................................................................................................................40

vii
7.2. Recommendations ...........................................................................................................40
REFERENCES .......................................................................................................................... 45
ANNEXES ................................................................................................................................. 49

viii
LIST OF ANNEXES

Annex 1 Laboratory wares were cleaned following the steps mentioned below.......................... 49
Annex 2 Determination of orthophosphate ................................................................................... 49
Annex 3 UV- Screening method .................................................................................................. 51
Annex 4 Argentometric method.................................................................................................... 52
Annex 5 Determination of BOD5 .................................................................................................. 54
Annex 6 Gravimetric method: Total suspended solids ................................................................. 56

ix
LIST OF TABLES

Table 1 Percentage composition of the chemical constituents in AW.......................................... 13

Table 2 Physical properties of alum waste ................................................................................... 14
Table 3 Parameters of pseudo-first and pseudo-second order of phosphate adsorption kinetics 24
Table 4 Parameters of pseudo-first and pseudo-second order of nitrate adsorption kinetics ....... 24
Table 5 Isotherm parameters for the removal of phosphate by untreated AW ............................. 30
Table 6 Isotherm parameters for the removal of nitrate ions by untreated AW .......................... 30
Table 7 Isotherm parameters for the removal of nitrate ions by untreated AW ........................... 32
Table 8 Physico-chemical characteristics of the wastewater ........................................................ 37

x
LIST OF FIGURES

Fig. 1 Conceptual framework ....................................................................................................... 17

Fig. 2 Calibration curves for (a) orthophosphate and (b) nitrate-nitrogen used in stannous
chloride method and UV-screening method respectively. ............................................................ 20
Fig. 3 Effect of contact time on simultaneous removal of nitrate and phosphate ions ................. 20
Fig. 4 Pseudo-first order kinetics of (a) phosphate and (b) nitrate adsorption ............................. 22
Fig. 5 Pseudo-second order kinetics of (a) phosphate and (b) nitrate adsorption ......................... 23
Fig. 6 Effect of pH on simultaneous removal of nitrate and phosphate ions ............................... 25
Fig. 7 Effect of adsorbent dose on the simultaneous remvoal of (a) phosphate and (b) nitrate ... 26
Fig. 8 Effect of initial concentration on the simultaneous removal of (a) phosphate and (b)
nitrate ........................................................................................................................................... 28
Fig. 9 Isotherm plots for (a) phosphate and (b) nitrate equilibrium adsorption ........................... 29
Fig. 10 D-R plot for (a) phosphate and (b) nitrate ....................................................................... 32
Fig. 11 Effect of contact time on simultaneous removal of nitrate and phosphate ions .............. 33
Fig. 12 Effect of co-existing ions on the simultneous removal of (a) phosphate and (b) nitrate . 35
Fig. 13 Effect of increasing NaOH concentration on simultaneous desorption of phosphate and
nitrate ........................................................................................................................................... 36

xi
ABBREVIATIONS

AW – Alum waste
APHA- American Public Health Association
CDC- Centre for disease control and prevention
RFEP- relative fitting error parameter

xii
CHAPTER ONE: INTRODUCTION

1.1 Background

Water pollution due to the excessive presence of nitrogen and phosphorus species is a
serious environmental problem worldwide, as both are implicated in eutrophication of
receiving surface waters (Khelifi et al., 2002; Painting et al., 2007; Weia et al., 2008
and Tiemeyer et al., 2009). Nitrogen is an important nutrient for plants and animals.
According to Vitosek et al., (2002) terrestrial ecosystems and headwater streams have
a considerable ability to capture nitrogen or to reduce it to N2 gas though the process
of denitrification. Nitrogen cycling and retention is thus one of the most important
functions of ecosystems. In contrast to the process of denitrification, when loads of
nitrogen from sources such as fertilizer, septic tanks, and atmospheric deposition
exceed the capacity of terrestrial systems, the excess may enter surface waters, where
it may have “cascading” harmful effects as it moves downstream to coastal
ecosystems (Galloway and Cowling, 2002).

Phosphorus like nitrogen is an inevitable element for the growth of animals and
plants. However, several million tons of phosphorus containing wastewater is
straightly discharged into the watercourses with the rapid development of industry
and agriculture annually. This in turn increases phosphate concentrations and altered
nutrition ratios that inevitably causes severe environmental pollution, such as the
eutrophication of the waterways which frequently cause fish kills, phytoplankton
blooms, and the deterioration of water quality (Song et al., 2011).

1
1.2 Statement of the problem

Contrary to their importance, excessive presence of nutrients, i.e., nitrogen and

phosphorus species is a serious environmental problem as it causes water pollution
(Sibrell et al., 2009). Agricultural over application of natural and synthetic fertilizers,
aquaculture, and municipal wastewaters, detergent manufacturing as well as mineral
processing industries are the main sources of nutrient release into the aquatic
environment (Saad et al., 2007; Katal et al., 2012; Khelifi et al., 2002 and Schick et
al., 2011).

These point and non-point sources of nutrients to both surface and ground water were
known to cause waster quality degradation. Due to water quality degradations such as
eutrophication stringent control over discharge of wastewater from municipal as well
as industrial sources established. As cited by Liang (2011) eutrophication threshold
for phosphorous (20 to 100 µg P/L) and for nitrogen (500 to 1000 µg N/L) in most
aquatic systems. According to Zhang et al., (2009), presence of trace amount of
phosphorus, exceeding about 1 mg/L, in treated wastewater can stimulate algal
growth (Eutrophication). Apart from water quality degradation, eutrophication can
cause specific health risks appear when fresh water, extracted from eutrophic areas, is
used for the production of drinking water. In such cases, the nervous, digestive,
respiratory and cutaneous systems may be affected by toxins excreted by harmful
algal blooms such as Cyanobacteria (CDC, 2004). Besides, presence of nitrate ions in
drinking water is a potential public health hazard and can cause infant
methemoglobinemia, “blue baby” syndrome (WHO, 2011).

Hence, nutrient removal from wastewater is imperative to protect eutrophication of

water bodies and health of human and animal. Various techniques such as chemical
precipitation, adsorption, reverse osmosis, biological removal, and constructed
wetlands have been employed for removal of nutrients from wastewaters (Zeng et al.,
2004). According to Olgun et al., (2013) and Saad et al., (2007), adsorption method
has become a popular method since it allows simple and economical operation
resulting in less sludge production and fewer disposal problems. Other attractive
feature of this method is nutrient-loaded filters can be used in agriculture as phosphate
fertilizer and soil conditioner (Zeng et al., 2004). In this study AW collected from
manufacturing of aluminum sulphate and sulphuric acid by kaolin process was used to
simultaneously remove nitrate and phosphate ions from aqueous solution.

2
1.3 Significance of the study

In this study, an industrial waste residue, generated during the manufacture of

aluminium sulphate from kaolin by sulphuric acid process was used as an adsorbent
for simultaneous removal of nitrate and phosphate from aqueous solution. A large
quantity of the waste residue is generated from each batch of alum production at
Awash Melkassa Aluminium Sulphate and Sulphuric Acid Factory, Ethiopia. The
waste discarded is highly acidic and hence it is considered as hazardous. Presently,
economically viable methods for the disposal or reuse of the solid waste are not
known. The results of the present study could be used for further investigation of the
adsorbent under column studies and field test of the solid waste for simultaneous
removal of phosphate and nitrate ions from real wastewater. Therefore, the solid
waste residue could be used for the reduction of the eutrophication of the water
sources in the future after further investigations. The use of the solid waste for
wastewater treatment could avoid the impact of the solid waste accumulation on the
environment.

3
CHAPTER TWO: LITERATURE REVIEW

2.1. Forms and sources of nitrogen in the environment

Nitrogen can take different forms in the environment. Nitrogen is capable of being
transformed biochemically or chemically and its transformations involve the
oxidation or reduction of the nitrogen atom through both biological and chemical
processes. The natural sources of nitrogen in water include biological nitrogen
fixation of atmospheric nitrogen by aquatic plants, decomposition, atmospheric
deposition, and weathering (Liang, 2011). Contrary to natural nitrogen cycle,
anthropogenic sources have played an important role in the total amount of the
nitrogen pools in aquatic environments. The sources of nitrate introduction in the
surface water and ground water include agricultural fertilizers, septic tank systems,
and animal waste disposal (Milmile et al., 2011). Liang (2011) presented non-point
sources such as fertilizer applied on agriculture land and livestock facilities, nitrogen
can be transferred either by runoff directly into surface water or via leaching into
groundwater, threatening the ground water quality and eventually entering surface
water bodies.

2.2. Forms and sources of phosphorus in the environment

Phosphorous can exist in various phosphate species. The common forms of

phosphorus in wastewater are polyphosphates (polymers of phosphoric acid),
organically bound phosphates, and the most abundant orthophosphates (Kamiyango et
al., 2009). Similarly, (Liang, 2011) presented typical levels of phosphorous in
wastewater takes different forms and were estimated by as orthophosphate 5 mg P/L
(50%), tripolyphosphate 3 mg P/L (30%), pyrophosphate 1 mg P/L (10%), and
organic phosphates 1 mg P/L (10%). On the one hand, orthophosphate is of
significant concern because it is not only the most abundant form of P in water and
wastewater, but also is the form that can be immediately utilized by organisms
Agricultural over-application of fertilizers, aquaculture, agri-food industries,
municipal wastewaters and detergent are the commonest sources that add
phosphorous in to water bodies (Hamoudi and Belkacemi, 2012).

10
2.3. Environmental impacts of nitrogen and phosphorous

Liang (2011) presented the Redfield ratio that reveals the molecular ratio of carbon,
nitrogen and phosphorus in phytoplankton as C: N: P = 106:16:1. Since carbon in
natural water is often considered as limitless because of the source of carbon dioxide
in the atmosphere, algae growth could be limited by the deficiency of either nitrogen
or phosphorus, and the limiting one is considered to be most important for
eutrophication control. Generally, the limiting nutrient in most fresh waters is
phosphorus, but in most sea waters is nitrogen. This is mainly because the
phosphorous supply in sea waters is abundant while phosphorous levels in fresh
waters are often low.

Eutrophication in its original use and etymology, ’eutrophic’ meant ’good

nourishment’, and eutrophication meant the process by which water bodies grew more
productive. It is a process driven by enrichment of water by nutrients, especially
compounds of nitrogen and/or phosphorus, leading to: increased growth, primary
production and biomass of algae; changes in the balance of organisms; and water
quality degradation. The consequences of eutrophication are undesirable if they
appreciably degrade ecosystem health and/or the sustainable provision of goods and
services (Ferreira et al., 2011).

(Liang, 2011) presented an estimation of the eutrophication threshold for phosphorous

between (20 to 100 µg P/L) and for nitrogen to be between (500 to 1000 µg N/L) in
most aquatic systems. When eutrophication takes place, the high concentrations of
nutrients in water bodies promote the growth of algae and aquatic plants. The
consequential bloom of algae and aquatic plants decreases the dissolved oxygen in the
water body to create hypoxia (DO level < 2 mg/L). (Zhao et al., 2009) also indicated
a reduced oxygen level harmfully affects fish and other aquatic life, microorganism
and insects’ growth as well as it causes natural resorts degradation. According to
(WHO, 2011) concerns for nitrogen also include health problems on humans and
animals as nitrogen in ammonia form is highly toxic to fish and other aquatic life and
as a result, NH3/NH4+ has stringent permit limits for wastewater treatment discharge.
Besides, excessive intake of nitrate by humans with drinking water or food can induce
methemoglobinemia (blue baby syndrome) or carcinogenic effects in infants.

11
Apart from eutrophication and blue baby syndrome, nutrient enrichment can cause
harmful algal bloom, which is defined as algal bloom that causes negative impacts to
other organisms via production of natural toxins, mechanical damage to other
organisms, or by other means (CDC, 2004). For instance, Cyanobacteria have been
reported as tainting fresh water and being toxic to humans, pets and other animals. It
has been reported that harmful algae blooms are global concerns and the problem is
common in over 45 countries worldwide and in at least 27 U.S. States (Liang, 2011).

2.4. Nitrogen and phosphorus removal methods

2.4.1. Nitrate removal

When it is found beyond the permissible value both in the environment and drinking
water, nitrate can bring in severe problems, including eutrophication and infection
diseases, such as cyanosis and cancer of the alimentary canal (Wang et al., 2007).
Due to the above problems both in human and aquatic environment, attention has to
be paid to remove nitrate from wastewater. Conventional methods used to remove
nitrate include, biological de-nitrification, reverse osmosis, electro-dialysis and ion
exchange. Since most of the above methods are high tech and subsequently need high
cost, adsorption is the focus of this study as its potential advantages include no
reagent requirements, no additional sludge generation, easy operation and low cost
materials in wastewater practices.

2.4.2. Phosphate removal

Since excess phosphate and nitrate concentration in the effluent discharge can lead to
eutrophication of the receiving water bodies, the amount of nutrient, i.e., nitrate and
phosphate in domestic, municipal and industrial discharges must be controlled using
wastewater treatment technologies. Many methods have been developed for
phosphate removal and they are broadly categorized in to three as: physical, chemical
and biological methods. Physical methods have proved to be either too expensive, as
in the case of electrodialysis and reverse osmosis, or inefficient, removing only 10%
of the total phosphorus (Zhao et al., 2009). Besides, enhanced biological treatment
can remove up to 97% of the total phosphorus and it is low-cost though variability in
chemical composition and temperature of wastewater would make the implementation
of this process not feasible for wastewater treatment (Zhao et al., 2009). Last but not
least, chemical removal techniques such as lime, aluminum sulfate and ferric salts are

12
the most effective and well-established even though cost associated with metal salts
and sludge production are their inherent problems. Therefore, adsorption is the focus
of this study as its potential advantages include no reagent requirements, no additional
sludge generation, easy operation and low cost materials in wastewater practices.

2.5. Aluminum sulphate and sulphuric acid factory waste

The process of manufacturing aluminium sulphate from mixture of kaolin and

sulphuric acid involves digesting kaolin with sulphuric acid. After the mixture of
kaolin and acid had been leached, it was cooled to room temperature and filtered to
remove leach residue. The residue separated is commonly discarded within the
factory’s compound. The chemical composition of the alum waste (AW) collected
from Awash Melkassa Aluminum sulphate and sulphuric acid factory is presented in
Table 1 as follows (Nigussie et al., 2007).

Table 1 Percentage composition of the chemical constituents in AW.

Chemical composition Percent (wt. %)

Kaolin 8.883
Al2(SO4)3 1.778
Al(OH)3 0.878
CaSO4 0.194
Fe2(SO4)3 0.023
Fe2O3 0.001
MgSO4 0.008
Na2SO4 0.007
K2SO4 0.005

A physical property of AW as presented by Negassa (2012) shows the adsorbent is

acidic and it has high percent porosity. The data on physical properties of the
adsorbent are given on Table 2.

13
Table 2 Physical properties of alum waste

Properties Value
pH in water 3.57
pH in KCl 3.37
Conductivity (µS/cm) 4.04
Bulk density (g/cm3) 0.26
Particle density(g/cm3) 2.10
Porosity (%) 87.7

14
 CHAPTER THREE: OBJECTIVES OF THE STUDY
3.1. General objective

• to assess common health and health related problems in Jiren Kebele, Jimma
town Ethiopia.

3.2. Specific objectives

• to assess iec and bcc activities in jiren kebele by 2012

• to assess sanitation and hygienic practice in jirenkebele by 2012.

• to assess health service utilization among the community at jiren kebele by

2012

• to assess safe water supplying the jirenkebele by 2012

• to design possible interventions on those identified problems in jiren kebele
by 2012

15
CHAPTER FOUR: MATERIALS AND METHOD

4.1. Study area and period

This study was conducted in Jimma town, Oromia Regional State at Jimma University
in graduate and staff research laboratory. The town has latitude and longitude
of 7°40′N 36°50′E. It has heavy rainfall and warm climate with a mean annual
temperature of 24.90C. The study was conducted from January to May, 2013.

4.2. Study design

The study design was batch adsorption experiment.

4.3. Study variables

Dependent variables Independent variables

Amount of nitrate or phosphate removed Contact time

(mg/g)
Initial solution pH
Initial concentration

Percent removal (%) AW dose

Coexisting ions

4.4. Conceptual framework

Effect of Effect of initial

contact time solution pH

Effect of Simultaneous removal

Effect of
initial of nitrate and coexisting
concentration
phosphate ions ions

Effect of
adsorbent dose 16
Fig. 1 Conceptual framework

4.5. Adsorbent preparation

A composite sample from different batches of alum solid waste residue was collected
from Awash Melkassa Alum Factory, East Shewa Zone, and Oromia Regional State,
Ethiopia. The collected samples were mixed and dried at laboratory room
temperature. The dried residue was ground using mortar and sieved using sieves of
mesh sizes (212 µm). Then, particle size of less than 212 µm was stored in an air tight
plastic bottle for further experimental uses.

4.6. Effect of contact time

Determination of equilibrium time was conducted using 100 ml test solution

containing 19.3 mg/L orthophosphate and 5.14 mg /L NO3-N with 20g/L adsorbent
dose in 250 ml Erlenmeyer flask. The pH of the solution was adjusted using pH meter
(HQ40D Hatch multi parameter PHC101 probe) and shaked at 150 rpm for 5, 10, 20,
30, 40, 50, 60, 90 and 120 minutes; the supernatant liquid was collected using
Whatman filter paper of pore size 0.45µm. Finally, the nitrate-nitrogen and
orthophosphate ion concentrations were determined by using UV screening method
and stannous chloride method respectively.

4.7. Effect of initial pH

Optimum pH for simultaneous removal of nitrate and phosphate ions was conducted
using 100ml test solution containing 11.83 mg/L orthophosphate and 3.36 mgNO3-
N/L with 20 g/L adsorbent dose in Erlenmeyer flask of volume 250ml. The pH
considered to see effect of initial solution pH were 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12;
after shaking speed (150 rpm) for equilibrium time the supernatant liquid was
collected using Whatman filter paper of pore size 0.45 µm.

4.8. Effect of adsorbent dose

The effect of adsorbent dose was investigated by varying the dose of AW from 4 g/L
to 32 g/L. Measured weights of the AW using analytical balance were added to 100ml
test solution containing 3.33 mgNO3-N/L and 10.38 mg/L orthophosphate in 250 ml
Erlenmeyer flask and shaked (150 rpm) for equilibrium time at optimum pH 7 for

17
simultaneous removal of nitrate and phosphate ions. After shaking was complete, the
supernatant liquid was collected using Whatman filter paper of pore size 0.45µm.

4.9. Effect of initial concentration

Effect of initial nitrate and phosphate ion concentration on simultaneous removal of

nitrate and phosphate ions was investigated by varying concentration of nitrate (3, 5,
9, 11, 12, 13, 14, 15, 17 and 19 mgNO3-N/L) and (0.2, 50, 80, 110, 140, 170, 200,
230and 260mg/L orthophosphate) in 250 ml Erlenmeyer flask and shaked (150 rpm)
for equilibrium time at optimum pH and optimum AW dose. After shaking was
complete, the supernatant liquid was collected using Whatman filter paper of pore
size 0.45 µm.

4.10. Effect of coexisting ions

Effect of three coexisting ions commonly found in domestic and municipal waste
water; chloride, bicarbonate and sulphate on simultaneous nitrate and phosphate
adsorption was examined by adding (5, 50 and 100 mg/L) of the respective anions
prepared from sodium chloride, potassium sulphate and sodium bicarbonate
respectively. Initial concentrations of phosphate and nitrate used were [PO43-]0: 19.3
mg/L and [NO3-N]0: 5.14 mg/L.

4.11. Desorption experiment

First, a known concentration of adsorbate (19.3 mg/L orthophosphate and 5.14 mg

NO3-N/L with 20 g/L AW dose in Erlenmeyer flask of volume 250ml) was allowed to
adsorb at equilibrium time. Then, the supernatant was analyzed for residual adsorbate
after separating the adsorbent by filtration preceded by centrifugation. After
separating the adsorbate loaded adsorbent, it was dried for 24 h at 1050C and shaked
to contact time with varying concentration of NaOH (0.1, 0.5 and 1.0 M) separately.

18
4.12. Adsorption experiment on wastewater

Adsorption experiment using AW for real wastewater was conducted after collecting
wastewater from wastewater discharge point near Jimma University. The adsorption
experiment on wastewater was carried out with 7.17 mg/L orthophosphate, 1.3
mg /L NO3-N, pH ~ 7.24, 90 min contact time and 20 g/L AW dose in 250 ml
Erlenmeyer flask.

4.13. Chemical analysis

Concentration of the adsorbates (nitrate and phosphate ions) in the stock, standard and
supernatant solutions were analyzed by Ultra violet screening method for nitrate ions
and stannous chloride method for phosphate ions by UV-Vis spectrophotometer (DR
500) at 220nm and 690 nm respectively according to standard method for examination
of water and wastewater, American public health association (APHA, 1995). The
calibration curves used during reading of phosphate (stannous chloride method) and
nitrate (UV-screening method) are shown in Fig. 2a and Fig. 2b respectively.

19
Fig. 2 Calibration curves for (a) orthophosphate and (b) nitrate-nitrogen used in
stannous chloride method and UV-screening methods respectively.

4.14. Data analysis

4.14.1. Adsorption Kinetics

The uptake of anions (nitrate and phosphate ions) by the alum residue was determined
by mass balance, as follows:
(C 0 − C t ) * V
qt = (1)
M
Where C0 (mg/L) and Ct (mg/L) are nitrate and phosphate concentrations at time 0 and
t, respectively, V is the volume of the solution (L), and M is the mass of alum waste (g)
(Boparai et al., 2010). The removed anions in percent were calculated by the following
formula:
(C0 − Ct )
A(%) = *100 (2)
C0

where C0 (mg/L) and Ct (mg/L) are initial and concentration at time, t, of nitrate and
phosphate, respectively.

20
Kinetics of adsorption, in terms of solute uptake rate, which governs the residence
time, is one of the important characteristics defining the efficiency of adsorption
(Krishnan and Haridas, 2008). Several kinetic models have been developed to
predict the adsorption kinetics and rate controlling step. In order to evaluate the
kinetics of simultaneous nitrate and phosphate adsorption, pseudo-first-order and
pseudo-second-order models were computed.

4.14.1.1. Pseudo-First order kinetics

Lagergren presented a first-order rate equation to describe the kinetic process of

liquid-solid phase adsorption pseudo-first-order model is expressed as:
d qt
= k1 (q e − qt ) (3)
dt

Where qe (mg/g) and qt (mg/g) are the amounts of the nitrate and phosphate adsorbed
on the adsorbent at equilibrium and at any time t, respectively; and k1 (min−1) is the
rate constant of the first order adsorption. After integration and applying boundary
conditions qt = 0 at t = 0 and qt = qt at time = t, the integrated form of Eq. (3) becomes;

ln(qe − qt ) = ln qe − k1t (4)

The value of k1 and qe can be obtained from the slope and intercept of the linear plot
of ln (qe– qt) versus t, respectively.

4.14.1.2. Pseudo-second order kinetics

The Pseudo-second order kinetic model presented by Ho and McKay is expressed as:
d qt 2
= k 2 (q e − q t ) (5)
dt

Where K2 (g.mg−1.min−1) is the rate constant of the second-order equation; qe (mg.g−1)

is the maximum adsorption capacity; qt (mg/g) is the amount of adsorption at time t
(min). After definite integration by applying the conditions qt =0 at t=0 and qt =qt at t
= t it becomes the following;
t 1 t
= + (6)
qt k 2 qe 2 q e

The value of qe and K2 can be obtained from the slope and intercept of the linear plot
of t/qt versus t, respectively.

21
4.14.2. Adsorption Isotherm

As Foo and Hameed (2010) described, an adsorption isotherm is an invaluable curve

describing the phenomenon governing the retention (or release) or mobility of a
substance from the aqueous media or aquatic environments to a solid-phase at a
constant temperature and pH. In addition, adsorption isotherm describes the fraction
of sorbate molecules that are partitioned between liquid and solid phases at
equilibrium (Boparai et al., 2010). In order to evaluate the relationship between the
amount of anion adsorbed and the anion concentration remaining in solution three
isotherm models; Langmuir, Freundlich isotherms and Dubinin and Radushkevich
were considered.

4.14.2.1. Langmuir isotherm

In 1916 Langmuir developed a theoretical equilibrium isotherm relating the amount of

gas sorbed on a surface to the pressure of the gas (Langmuir, 1916). Langmuir
isotherm is based on the assumption that the point of valance exists on the surface of
the adsorbent and that each of these site is capable of adsorbing one molecule. It is
assumed that the adsorption sites have equal affinities for molecules of adsorbate and
that the presence of adsorbed molecules at one site will not affect the adsorption of
molecules at an adjacent site. The Langmuir equation is commonly written as:
q max bC e
qe = (6)
1 + bC e

Where, is the amount adsorbed (mg/g) and is equilibrium concentration of

adsorbate (mg/L) while qmax and b are constants related to adsorption capacity and
energy of adsorption, respectively (Zeng et al., 2004).

Moreover, a dimensionless constant, commonly known as separation factor (RL)

defined by Webber and Chakkravorti can be represented as:

1
RL = (7)
1 + K LC0

where KL (L/mg) refers to the Langmuir constant and Co is denotes to the adsorbate
initial concentration (mg/L). RL value indicates the adsorption nature to be either
unfavorable (RL > 1), linear (RL = 1), favorable (0 < RL < 1) or irreversible (RL = 0)
(Foo and Hameed, 2010).

22
4.14.2.2. Freundlich isotherm

In 1906, Freundlich presented the earliest known sorption isotherm equation. This
empirical model can be applied to non-ideal sorption on heterogeneous surfaces as
well as multilayer sorption (Freundlich, 1906). This model is based on the assumption
that the number of active sites available for adsorption is dependent upon the
concentration of sorbate particles. That is, as the concentration of target species
increases, then the number of active sites increases until the point of saturation is
reached. The Freundlich equation is basically empirical but it is often useful as a
means for data description. The general form of Freundlich isotherm is given in the
following equation (Zeng et al., 2004).
1
qe = k f C e n (8)

Where kf and n are Freundlich isotherm constants related to adsorption capacity and
adsorption intensity, respectively and Ce is the equilibrium concentration (mg/L).

4.11.3. Dubnin and Radushkehvich isotherm

Another equation used during analysis was the Dubinin-Radushkevich (D-R) model
which is written as (Nigussie et al., 2007):
(
q e = q m exp − βε 2 ) (9)

Where qm is D-R constant.

The sorption data was modeled by D-R isotherm to determine the adsorption type as
physical or chemical. The linear form of D-R model is expressed by the following
equation.
ln qe = ln qm − βε 2 (10)

Where qe is the amount of nitrate or phosphate adsorbed per unit dosage of the
adsorbent (mol/g), qm the monolayer capacity (mol/g), Ce the equilibrium
concentration of nitrate or phosphate (mol/L), β is the activity coefficient related to
mean sorption energy (mol2/kJ2), and ε is the Polanyi potential described as:
1
ε = RT ln(1 + ) (11)
Ce
The mean sorption energy, E (KJ/mol), can be calculated as:
1
E= (12)
− 2β

23
4.11.4. Intraparticle diffusion equation

Intraparticle diffusion model based on the theory proposed by Weber and Morris was
tested to determine if the particles diffusion is the rate-limiting step for the nitrate and
phosphate adsorption onto AW (Benghalem et al., 2010). According to this theory
(Anand et al., 2009):

q t = k p t 0 .5 (13)

Where qt is the amount of nitrate or phosphate adsorbed (mg/g) at a given time t

(min); kp (mg g-1 min-1/2) is the intraparticle diffusion rate constant. The KP value was
obtained from plotting of qt versus t0.5.

4.11.5. Relative fitting error parameter

The best fit model was determined by evaluating the relative fitting error parameter
(RFEP) value which was computed using the equation:

0 .5
 SSR 
RFEP

=  n − 2 
 q ave 
  (14)
where, qave is average qe, n is number of data point and SSR is squared sum of
residuals (Han, 2012).

4.15. Data quality management

Data quality was maintained by conducting triplicate experiments and mean values
were reported. Calibration of the analytical equipment was conducted at each set of
analysis using freshly prepared standard solution. Blank and Control experiments
were conducted; blank and control corrected values were reported.

4.16. Ethical consideration

Formal letter was written from Jimma University to Awash Melkassa aluminium
sulphate and sulphuric acid factory and all concerned bodies and institutions.

4.17. Dissemination plan

The final result of the study will be presented to Jimma university scientific
community and Department of Environmental Health Science and Technology. The

24
manuscript will be sent for consideration of publication on an international peer
reviewed journal.

25
CHAPTER FIVE: RESULT

5.1. Effect of contact time

The experimental result showed that the removal of phosphate ion increased from 0
mg/g to 0.0962 mg/g within the first 60 min and almost remained constant afterwards
until equilibrium time while the amount adsorbed for nitrate ion increased from 0 to
0.07 mg/g in the first 60 min and showed the same pattern as phosphate (Fig. 3). The
equilibrium time was achieved at 90 min for both adsorbates. Therefore, 90 min was
taken as equilibrium time for the rest of the experiments.

Fig. 3 Effect of contact time on simultaneous removal of nitrate and phosphate ions
([PO43-]0: 11.83 mg/L, [NO3-N]0: 3.36 mg/L, dose: 20 g/L, pH~7 and agitation rate:
150 rpm)

5.2. Adsorption kinetics

Adsorption kinetics for simultaneous nitrate and phosphate removal was examined by
applying the pseudo-first and pseudo-second order kinetics. From Tables 3 and 4, the
kinetic data well fitted to pseudo-second order kinetics with R2 1 and 0.992 for
phosphate and nitrate respectively (Figs. 5a and 5b). Similarly, R2 value for the

20
pseudo-first order kinetics of phosphate was 0.698 while that of nitrate was 0.915
(Figs. 4a and 4b). This indicates the kinetics data better fitted to pseudo-second order
kinetics than pseudo-first order kinetics for both adsorbates. The plots of pseudo-first
and pseudo-second order kinetics for phosphate and nitrate ions are given in Figs. 4
and 5, respectively. The parameters of the pseudo-first and pseudo-second order
equations for phosphate and nitrate adsorption on AW are given in Tables 3 and 4,
respectively.

21
Fig. 4 Pseudo-first order kinetics of (a) phosphate and (b) nitrate adsorption ([PO43-]0:
19.3 mg/L, [NO3-N]0: 5.14 mg/L, dose: 20 g/L, pH ~ 7 and agitation rate: 150 rpm)

22
Fig. 5 Pseudo-second order kinetics of (a) phosphate and (b) nitrate adsorption ([PO43-
]0: 19.3 mg/L, [NO3-N]0: 5.14 mg/L, dose: 20 g/L, pH ~ 7 and agitation rate: 150 rpm)

23
Table 3 Parameters of pseudo-first and pseudo-second order of phosphate adsorption
kinetics

Pseudo-first order Pseudo-second order

Parameters Value Parameters Value

qe (mg/g) 0.962 qe (mg/g) 0.962

qe, cal (mg/g) 0.003 qe, cal (mg/g) 0.962

K1 (min-1) 0.048 K2 (g/(mg.min) 41.206

R2 0.698 R2 1

Table 4 Parameters of pseudo-first and pseudo-second order of nitrate adsorption

kinetics

Pseudo-first order Pseudo-second order

Parameters Value Parameters Value

qe (mg/g) 0.071 qe (mg/g) 0.071

qe, cal (mg/g) 0.110 qe, cal (mg/g) 0.006

K1 (min-1) 0.082 K2 (g/(mg.min)) 2318.144

R2 0.915 R2 0.992

5.3. Effect of initial pH

Fig. 6 reveals that high phosphate removal efficiency (0.5887 – 0.5885 mg/g) between
pH 5-9 where as high nitrate removal was achieved at pH 7 (0.046 mg/g NO3-N ). The
removal of phosphate in the pH range mentioned was found to be to be 0.589 mg/g.
These shows simultaneous removals of both adsorbates were found to be higher at pH
7. Hence, pH 7 was selected as optimum pH to conduct the rest adsorption
experiments so as to simultaneously remove nitrate and phosphate ions.

24
Fig. 6 Effect of pH on simultaneous removal of nitrate and phosphate ions ([PO43-]0:
11.83 mg/L, [NO3-N]0: 3.36 mg/L, adsorbent dose: 20g/L, pH~7 and agitation rate:
150 rpm)

5.4. Effect of adsorbent dose

The effect of adsorbent dose was studied by varying the dose between 4 and 32 g/L. It
was observed that the percent removal of phosphate ions onto AW increased from
99.364% to 99.932% with increasing AW dose from 4 to 32 g/L. Similarly, percent
removal of nitrate increased from 22.34% to 32.20% with the increased dose of AW
(Figs. 7a and 7b). Based on this result 20 g/L was selected as optimum dose to
conduct the rest adsorption experiment during simultaneous removal of nitrate and
phosphate.

25
Fig. 7 Effect of adsorbent dose on the simultaneous remvoal of (a) phosphate and (b)
nitrate ([PO43-]0: 10.38 mg/L, [NO3-N]0: 3.33 mg/L, dose: 4-2 g/L, pH~7 and agitation
rate: 150 rpm)

26
5.5. Effect of initial concentration

The effect of initial adsorbate concentration on the adsorption was investigated by

varying the initial concentration of phosphate between 0.2 mg/L and 260 mg/L and
that of nitrate-nitrogen between 3 and 19 mg/L. The results showed that the
percentage removal increased from 70 to 99.97% with an increase in the phosphate
concentration from 0.2 to 260 mg/L (Fig. 8a) while that of nitrate decreased from
26.33 to 6.53% with the increase in the concentration of nitrate-nitrogen (Fig. 8b).

27
Fig. 8 Effect of initial concentration on the simultaneous removal of (a) phosphate
and (b) nitrate ([PO43-]0: 0.2 to 260 mg/L, [NO3-N]0: 3 to 19 mg/L, dose: 20 g/L, pH~
7 and agitation rate: 150 rpm)

5.6. Adsorption isotherm

The adsorption data obtained from simultaneous removal of nitrate using AW were
analysed according to the two commonly used non-linear isotherms, Langmuir
isotherm and Freundlich isotherm. The result showed adsorption of phosphate and
nitrate well fitted to Freundlich isotherm with R2 values 0.988 and 0.991 respectively.
Likewise, experimental data of both adsorbates well fitted to Langmuir isotherm with
R2 equals 0.984 for phosphate and 0.955 for nitrate. Moreover, Freundlich and
Langmuir isotherm constants determined by non-linear regression are given in Tables
5 and 6. The isotherm plots of the equilibrium adsorption of phosphate and nitrate are
respectively given in Fig. 9a and Fig. 9b.

28
Fig. 9 Isotherm plots for (a) phosphate and (b) nitrate equilibrium adsorption ([PO43-
]0: 0.2 to 260 mg/L, [NO3-N]0: 3 to 19 mg/L, dose: 20 g/L, pH~7, agitation rate: 150
rpm and temperature: 299K)

29
Table 5 Isotherm parameters for the removal of phosphate by untreated AW

Freundlich isotherm Langmuir isotherm

Parameters Value Parameters Value

kf (mg/g) 5.361 qmax (mg/g) 13.150

n 2.727 b (L/mg) 0.367

R2 0.988 R2 0.984

RFEP 1.619 RL 0.010-0.932

RFEP 2.199

Table 6 Isotherm parameters for the removal of nitrate ions by untreated AW

Freundlich isotherm Langmuir isotherm

Parameters Value Parameters Value

kf (mg/g) 0.034 qmax (mg/g) 0.065

n 4.740 b (L/mg) 0.594

R2 0.991 R2 0.955

RFEP 3.825E-6 RL 0.081-0.359

RFEP 1.931E-5

5.7. Mean sorption energy

The D-R isotherm can be used to model the adsorption process. This can be achieved
by computing the mean sorption energy according to Eq. (11), where sorption energy
less than 8 KJ/mol shows physiosorption, while value of mean sorption energy greater
than 8 KJ/mol shows chemisorption. The D-R isotherm plots for phosphate and nitrate
are given in Fig. 10a and 10b. The mean sorption energy computed from the D-R

30
equation for phosphate was found to be 8.506 KJ/mol while that of nitrate was 3.272
KJ/mol (Table 7).

31
Fig. 10 D-R plot for (a) phosphate and (b) nitrate ([PO43-]0: 0.2 to 260 mg/L, [NO3-
N]0: 3 to 19 mg/L, dose: 20 g/L, pH ~ 7, agitation rate: 150 rpm and temperature:
299K)

Table 7 Isotherm parameters for the removal of nitrate ions by untreated AW

D-R phosphate D-R nitrate

Parameter Value Parameter Value

qm 5.474E-4 qm 2.150E-6

β (mol2/KJ2) 0.00691 β (mol2/KJ2) 0.0467

R2 0.996 R2 0.992

ED-R (KJ/mol) 8.506 ED-R (KJ/mol) 3.272

RFEP 6.128E-11 RFEP 8.659E-16

5.8. Intraparticle diffusion equation

Analysis of equilibrium data using intraparticle diffusion model depicted, intraparticle

diffusion is not the rate determining step as the graph of qt versus t0.5 did not pass
through the origin as shown in Figs. 11a and b.

32
Fig. 11 Effect of contact time on simultaneous removal of nitrate and phosphate ions
([PO43-]0: 11.83 mg/L, [NO3-N]0: 3.36 mg/L, dose: 20 g/L, pH ~ 7 and agitation rate:
150 rpm)

33
5.9. Effect of co-existing ions

The effect of common coexisting ions such as chloride, sulfate, and bicarbonate in
wastewater on the simultaneous adsorption of phosphate and nitrate was investigated
by varying the concentration of the anions from 5 to 100 mg/L in the solution. The
result showed that the presence of individual or the mixture of the three ions in the
solution did not significantly affect the removal efficiency of phosphate when
compared with the removal efficiency of phosphate without the presence of the ions
in the solution (Fig. 12a). The removal efficiency of phosphate without the presence
of the ions was represented by ‘control’ in Fig. 12a. On the contrary, increase in
concentration of all the coexisting ions had significantly affected the removal
efficiency though the effect of chlorides are not as prominent as bicarbonate and
sulfate indicated in Fig. 12b.

34
 (b)

Fig. 12 Effect of co-existing ions on the simultneous removal of (a) phosphate and
(b) nitrate ([PO43-]0: 19.3 mg/L, [NO3-N]0: 5.14 mg/L, dose: 20g/L, pH ~ 7 agitation
rate: 150 rpm)

5.10. Desorption experiment

From the experimental results of the effect of pH given in subsection 5.4, the
adsorption of phosphate and nitrate significantly decreased in the extreme pHs. This
could suggest that desorption of the adsorbates can be effective using either extreme
acidic or basic pH. The data found from the desorption experiment showed nearly
50% of the adsorbed phosphate was desorbed by 1.0 M NaOH. Unlike phosphate
100% desorption of nitrate was observed using 1 M NaOH. The results of desorption
experiments are given in Fig. 13.

35
Fig. 13 Effect of increasing NaOH concentration on simultaneous desorption of
phosphate and nitrate ([PO43-]0: 19.3 mg/L, [NO3-N]0: 5.14 mg/L, agitation rate: 150
rpm)

5.11. Removal of phosphate and nitrate from wastewater

Applicability of the adsorbent for simultaneous removal of phosphate and nitrate

collected from wastewater discharge point near Jimma University was investigated.
The physicochemical characterization and adsorption experiments of the wastewater
were conducted at Jimma University, department of environmental health science and
technology graduate and staff research laboratory. Adsorption experiment on the
wastewater revealed 77.5% and 4.6% phosphate and nitrate removal from the sample,
respectively. The analysed physico-chemical characteristics of the wastewater are
shown in Table 8.

36
Table 8 Physico-chemical characteristics of the wastewater

Physicochemical characteristics Value

DO (mg/L) 1.46

BOD (mg/L) 1530

pH 7.24

DO in percent saturation (%) 24.00

Conductivity (µs/cm) 958

Temperature (0C) 22.9

Turbidity (NTU) 46.8

Total dissolved solid (mg/L) 479

Total suspended solid (mg/L) 114

Chloride (mg/L) 8.9

Orthophosphate (mg/L) 7.17

Nitrate-nitrogen (mg/L) 1.3

37
CHAPTER SIX: DISCUSSION

This survey also found that 16(11.85%, N=135) of them were pregnant and among
these, 13(81.2%) were attended ANC at least once and the rest (18.8%) of them did
not attend ANC. This finding is not similar with the finding in Yem special
Woreda(14) in which about28.5% women have received antenatal care at least once
during their last pregnancy with the majority 71.5% reported that they did not attend
ANC for their last pregnancy. This difference could be due to the presence of
additional NGOs that work on maternal health in addition to governmental health
institute. Despite of this fact still some (18.8%) did not attend antenatal care which is
in contrary to WHO recommendation for all pregnant women to attend ANC at least
four times. And the finding in Awetu Mendera is still not similar with the 2010
DTTP report conducted in Ginjo gudru kebele, Jimma town, on which among all of
the total pregnant women attended ANC at least once. This could be due to absence
of urban health extension worker in Awetu Mendera.

Concerning to delivery service utilization, on the other hand, among the total
deliveries 18(5.6%) in the last 12 months, 16(88.9%) of them gave birth at health
institution and 2(11.1%) of them were at home and of these all of them were
conducted by TBA by using gloves. This finding is incomparable with the findings in
North Gondar Zone (15), in which the magnitude of home delivery in this finding was
less relative to the previous finding indicating some improvement and this could be
due to government effort to achieve the MDG but still there are some women (11.1%)
who did not use safe delivery service.

Among the total surveyed households, 88.9% of them had ITN during survey with the
mean number of ITN 1.96. Among these, 189(65.6%) of them used ITN always,
90(31.2%) of them used it sometimes and 9(3.1%) of them did not use ITN due to
different reasons like the problem of allergy responded by majority of them. This
finding is inconsistent with the study conducted in Arbaminch Town (19) in which
ITN coverage rate was 58.8% and utilization rate was 73%. The difference could be
due to an improved emphasis on malaria prevention by distributing ITNs for the
community even though the problem of utilization is there.

38
The finding on waste disposal system in this survey revealed that majority (35.5%) of
households dispose in open field, in garbage or waste container (31.5%), by burning
(22.8%) with the least (10.2%) using pit and this finding is comparable with the
previous findings conducted in Ethiopia which indicated lack of adequate access to
public solid waste management services, and in Addis Ababa about 37% use open
dumping, 22% burning, 33% burying and 11% composting for waste disposal but not
consistent with findings of Kersa Demographic Surveillance and Health Research
Centre (KDS-HRC) in which only 6.9% used garbage or temporary storage site (7,8).

Concerning to the HIV test, only 118(36.4%) of the respondents were tested for
HIV/AIDS and 206(63.6%) of them did not tested for HIV/AIDS which is almost
consistent with the previous study conducted in Addis Ababa(20)and the common
reasons forwarded for not being tested were feeling of not being exposed for the risks
of acquiring HIV/AIDS 85(41.26%), afraid to had HIV/AIDS test 79(38.35%) and
being married and feeling of none concern for married 42(20.39%) which indicates
community awareness on HIV/AIDS was less which is also similar with the previous
study. From the totally surveyed HHs, about 8(2.5%) mentally ill client was found.
Out of this, 3(37.5%) had medical follow up but the rest did not.

39
CHAPTER SEVEN: CONCLUSION AND RECOMMENDATION

7.1. Conclusions

Simultaneous phosphate and nitrate removal from aqueous solutions was studied
using AW. Based on the results of this study, the following conclusions were drawn.

Static test were conducted with macro invertebrate larvae in 150 ml glass beaker with
in different dilutions. The de-chlorinated tap water was used as the diluent medium
(prepared by passing tap water through a distiller). Experimental vessels were filled
with de-chlorinated tap water and allowed to cool to laboratory temperature to ensure
constant temperature of diluent medium. The sewage concentration series used in the
dilution in this study was 0 (control), 10, 30, 50, 70 and 90 % (reference) for a time
period of 1, 3, and 7 hour. Each test solution had three replicates. Each replicates has
ten (10) organisms. The mortality of the organisms was recorded at the end of the
specified exposure times. Dead organisms were collected at each interval, labeled and
preserved in 70% ethanol. Surviving organisms at the end of the 7 hour period were collected,
labeled and preserved in 70% ethanol. At the end of each interval the identification of the
macro invertebrate was undertaken to the family level using different identification key ( ).
Laboratory temperatures were controlled with the use of air-conditioners to around
room temperature.

7.2. Recommendations

Various studies have shown that macroinvertebrates are often sensitive to toxicants,
and represent a large proportion of the biomass in aquatic systems (Buikema et al.,
1982). Macro invertebrate larvae were collected by rinsing rocks into a jug of river
water and with kick net mesh size 250µm by wading at the middle of the stream of
Ofale in Dedo District, Jimma Zone, Ethiopia. The stream passes through agricultural
area and is not prone to industrial and domestic waste pollution since there is no
indication of such pollution. The stream bed was mainly silt, pebble and cobble
stones. It has on average a riparian vegetation of about 1 m on both sides of the
stream.
Macro invertebrates were gently rinsed off the net with river water into a 10 L bucket
filled with aerated stream water. The transit time to the laboratory was approximately
one hour. Collected organisms were placed in the buckets containing stream water
from the sample site and transferred to the laboratory around the icepack to prevent

40
overheating. The majority of the test organisms were mainly (there were also other
families) from the families of the mayflies (Ephemeroptera); Hepetageniidae, Canidae
and Baetidae and from Odonata family; Coenagriidae. Macroinvertebrate, are
sensitive to handling, and were gently transferred to the laboratory streams. The
macro invertebrates were not identified until the end of the experiment.

41
REFERENCES

Anand, S., Soma, G., Sujana, M. and Vasumathi, N., (2009). Studies on fluoride
adsorption capacities of amorphous Fe/Al mixed hydroxides from aqueous
solutions, Journal of Fluorine Chemistry 130(8): 749-754.

APHA (1995). Standard Methods for Examination of Water and Wastewater. 4500-P
and 4500-NO3. USA.

Baraka, M. A., El-Tayieb, M. M., El Shafai, M. and Mohamed, Y. N., (2012).

Sorptive Removal of Phosphate from Wastewater Using Activated Red Mud.
Australian Journal of Basic and Applied Sciences 6(10): 500-510.

Benghalem, A., Ghaffour, N., Ramdani, A. and Taleb, S. (2010). Removal of excess
fluoride ions from Saharan brackish water by adsorption on natural
materials. Desalination 250(1): 408-413

Boparai, K. H., Joseph, M. and O’carroll, D., (2010). Kinetics and thermodynamics of
cadmium ion removal by adsorption onto nano zerovalent iron particles.
Journal of Hazardous Materials xxx: xxx-xxx.

CDC (2004). About Harmful Algal Blooms. http://www.cdc.gov/nceh/ciguatera/

Cengeloglu, Y., Tor, A., Ersoz, M. and Arslan, G., (2006). Removal of nitrate from
aqueous solution by using red mud. Separation and Purification Technology
51(2): 374-378.

Dai, J., Yang, H., Yan, H., Shangguan, Y., Zheng, Q. and Cheng, R., (2011).
Phosphate adsorption from aqueous solutions by disused adsorbents: Chitosan
hydrogel beads after the removal of copper (III). Chemical Engineering
Journal 166: 970-977.

Ferreira, G. A., Andersen, H.J., Borja, A., Bricker, B. S., Campa, J., Da Silva, C.M.,
Garces, E., Heiskanen A., Humborg, C., Ignatiades, L., Lancelot, C.,
Menesguen, A., Tett, P., Hoepffner, N. and Claussen, U., (2011). "Overview
of eutrophication indicators to assess environmental status within the
European Marine Strategy Framework Directive." Estuarine, Coastal and
Shelf Science 93(2): 117-131.
45
Foo, Y. K and Hameed, H. B., (2010). Insights into the modeling of adsorption
isotherm systems. Chemical Engineering Journal 156: 2–10.

Freundlich, H. M. F., (1906). Over the adsorption in solution. Journal of physical

chemistry 57:385–470.

Galloway, J. and Cowling, E., (2002). Reactive nitrogen and the world: 200 years of
change. Ambio 31: 64-71.

Hamoudi, H. and Belkacemi, K., (2012). Adsorption of nitrate and phosphate ions
from aqueous solutions using organically-functionalized silica materials:
Kinetic modeling. Fuel xxx: xxx-xxx.

Han, S, D., Batchelor, B., Park, H, S. and Abdel-Wahab., (2012). As(V) adsorption
onto nanoporous titania adsorbents (NTAs): Effects of solution composition.
Journal of Hazardous Materials 229– 230: 273-281.

Kamiyango, W. M., Masanba, L.R.W., Sajidu, I.M.S. and Fabiano, E., (2009).
Phosphate removal from aqueous solutions using kaolinite obtained from
Linthipe, Malawi. Physics and Chemistry of the Earth 34: 850–856.

Katal, R., Baei, S. M., Rahmati, T.H. and Esfandian, H., (2012). Kinetic, isotherm and
thermodynamic study of nitrate adsorption from aqueous solution using
modified rice husk. Journal of Industrial and Engineering Chemistry 18:295–
302.

Khelifi, O., Kozuki, Y., Murakami, H., Kurata, K., Nishioka, M., (2002). Nutrients
adsorption from seawater by new porous carrier made from zeolitized fly ash
and slag. Marine Pollution Bulletin 45: 311–315

Kose, E. T. and Kivanc, B., (2011). Adsorption of phosphate from aqueous solutions
using calcined waste eggshell. Chemical Engineering Journal 178:34– 39

Krishnan, A. K., and Haridas, A., (2008). Removal of phosphate from aqueous
solutions and sewage using natural and surface modified coir pith. Journal of
Hazardous Materials 152: 527-535.

Langmuir, I., (1916). The adsorption of gases on plane surface of glass, mica and
platinum. Journal of American chemical society 40:1361–1368.

46
Liang, Q., (2011). Simultaneous phosphorus and nitrogen removal using aluminum
based water treatment residual. Fort Collins Colorado State University 1-100.
Unpublished research.

Milmile, N.S., Pande, V.J., Karmakar, S., Bansiwal, A., Chakrabarti, T. and
Biniwale, B.R., (2011). Equilibrium isotherm and kinetic modeling of the
adsorption of nitrates by anion exchange Indion NSSR resin. Desalination
276: 38-44.

Negassa, S., (2012). Phosphate sorption capacity of solid residue of Awash Melkassa
Aluminum Sulphate and Sulphuric Acid Factory. Unpublished research.

Nigussie, W., Zewge, F. and Chandravanshi, S.B., (2007). Removal of excess fluoride
from water using waste residue from alum manufacturing process. Journal of
Hazardous Materials 147: 954-963.

Olgun, A., Atar, N. and Wang, S., 9 (2013). Batch and column studies of phosphate
and nitrate adsorption on waste solids containing boron impurity. Chemical
engineering journal 222:108–119

Özacar, M., (2003). Adsorption of phosphate from aqueous solution onto alunite.
Chemosphere 5: 321-327.

Painting, J.S., Devlin, J.M., Malcolm, J. S., Parker, R. A., Mills, K.D., Mills, C., Tett,
P., Wither, A., Burt, J., Jones, R. and Winpenny, K., (2007) Assessing the
impact of nutrient enrichment in estuaries: Susceptibility to eutrophication.
Marine Pollution Bulletin 55:74–90

Saad, R., Belkacemi, K. and Hamoudi, S., (2007). Adsorption of phosphate and
nitrate anions on ammonium-functionalized MCM-48: Effects of experimental
conditions. Journal of Colloid and Interface Science 311(2): 375-381.

Schick, J., Caullet, P., Paillaud, J., Patarin, J., and Mangold-Callarec, C., (2011).
Nitrate sorption from water on a Surfactant-Modified Zeolite. Fixed-bed
column experiments. Microporous and Mesoporous Materials 142: 549-556.

Sibrell, L. P., Montgomery, A.G., Ritenour, L. K. and Tucker, W. T., (2009)

Removal of phosphorus from agricultural wastewaters using adsorption media
prepared from acid mine drainage sludge. Water research 43: 2240-2250.

47
Song, X., Pan, Y., Wu, Q., Cheng, Z. and Ma, W., (2011). Phosphate removal from aqueous
solutions by adsorption using ferric sludge removal from aqueous solutions by
adsorption using ferric sludge. Journal of desalination 280: 384-390.

Tiemeyer, B., Kahle, P. and Lennartz, B., (2009). Phosphorus losses from an
artificially drained rural lowland catchment in North-Eastern Germany.
Agricultural water management 96:677 - 690.

Vitousek, P., Mooney, H., Olander, L. and Allison. S., (2002). Nitrogen and nature.
Ambio 31:97-101.

Wang, Y., Gao, B., Wen-Wen Yue, W. W. and Yue, Q., (2007). Adsorption kinetics
of nitrate from aqueous solutions onto modified wheat residue. Colloids and
Surfaces A: Physicochemical Engineering. Aspects 308: 1-5.

Weia, X., Viadero, C. R., and Bhojapp, S., (2008). Phosphorus removal by acid mine
drainage sludge from secondary effluents of municipal wastewater treatment
plants. Water research 42:3275 – 3284.

WHO (2011). Nitrate and nitrite in drinking-water.

www.who.int/water_sanitation_health/dwq

Zeng, L., Lia, X. and Liu, J., (2004). Adsorptive removal of phosphate from aqueous
solutions usingiron oxide tailings. Water Research 38: 1318-1326.

Zhang, G., Liu. H., Liu, R. and Jiuhui, Q., (2009). Removal of phosphate from water
by a Fe-Mn binary oxide adsorbent. Journal of Colloid and Interface Science
335(2): 168-174.

Zhang, J., Shen, Z., Shan, W., Chen, Z., Mei1, Z., Yangming Lei1,Y. and Wang,
W., (2010). Adsorption behavior of phosphate on Lanthanum(III) doped
mesoporous silicates material. Journal of Environmental 22(4) :507–511

Zhao, Y., JunWang, Luan, Z., Peng, X., Liang, Z. and Shi, L., (2009). Removal of
phosphate from aqueous solution by red mud using a factorial design. Journal
of Hazardous Materials 165: 1193–1199.

48
ANNEXES

Annex 1 Laboratory wares were cleaned following the steps mentioned below
1. Rinse material with tap water
2. Soak in detergent overnight
3. Rinse with tap water
4. Soak in 2% HNO3 over night
5. Rinse with distilled water
6. Dry plastic wares at 55±5°C and glass wares at 105±5°C in oven for 12 hrs

Annex 2 Determination of orthophosphate

I. Apparatus

A). Glassware: 1000mL volumetric flask, 250 ml Erlenmeyer flasks, 10 ml Mohr

pipette, clean quartz spectrophotometric cuvettes, 100mL graduated cylinder and
250mL were used.

B). Spectrophotometer: DR 500 UV-Vis spectrophotometer

II. Reagent

A) Phenolphthalein Indicator: 0.2g phenolphthalein was dissolved into 200mL

deionized water and 200mL ethanol.

B) Ammonium Molybdate Reagent: 25g (NH4)6 MO7O24 .4H2O was dissolved in

175 ml distilled water. Cautiously add 280 ml con. H2SO4 was cautiously added to
400 ml distilled water. Then cooled to add molybdate solution, and afterwards diluted
to 1litter.

C) Stannous Chloride Reagent: 2.5 g fresh stannous chloride dissolved in 100mL

glycerol (also known as glycerine) and heated on water bath for 2 h; stirred with rod
to enhance dissolution. This reagent is stable and requires neither preservatives nor
special storage.

D) Stock phosphate solution: Dissolve in distilled water 0.7165 anhydrous KH2PO4

and dilute to 1000 ml; 1.00ml = 500 µg PO43-- P

49
E) Standard Phosphate Solution: 219.5mg of KH2PO4 dissolved and dilute to
1000ml; 1 ml=50.0 µgPO43- - P).

F) Strong-acid solution: 300 ml concentrated H2SO4 was slowly added to about 600
ml distilled water. After cooling, 4.0 ml concentrated HNO3 added and diluted to 1L.

Procedure for stannous chloride method

A) Determination of Orthophosphate:

1. The following series of phosphate standards were prepared by measuring the

indicated volume of standard phosphate solution in to separate 100 ml volumetric
flasks (graduated cylinders).

Standard phosphate solution (ml) Phosphate (PO34) µg/100 ml

0 0
1 5
2 10
3 15
4 20
5 25
6 30

1. To the sample, 0.05 ml (1 drop) of phenolphthalein indicator solution was added.

When the sample turned pink, strong acid solution was added drop wise until the
colour disappeared.
2. With a measuring pipette, 4 ml acid-molybdate solution was added to each of the
standards and sample.
3. Thoroughly mixing was carried out by inverting each flask four to six times
4. With medicine dropper, 0.5 ml (10 drops) of stannous chloride solution was added
to each of the standards and sample
5. The flasks were stoppered and mixed by inverting each flask four to six times.
6. After 10 minutes, but before 12 minutes, the colour was photometrically measured
at 690 nm using distilled water as a blank.
7. A calibration curve was constructed using the standards and the amount of
phosphate in µg in the sample was determined from the curve.

50
8. Calculation: mg PO 34− /L = µg PO 34- /ml of sample

Annex 3 UV- Screening method

Apparatus
• DR 500 UV-Vis spectrophotometer with curette that transmits UV light.

Reagents

Nitrate-free water: Deionized water was used to prepare all solutions and
dilutions.

Stock nitrate solution: KNO3 was dried in an oven at 105°C for 24 h and
0.7218 g was dissolved in water and dilutee to 1000 ml; 1.00 ml = 100
µg NO3- -N.

Intermediate nitrate solution: 100 ml stock nitrate solution was diluted to

1000 ml with water, 1.00 ml = 10.0 µg NO3- -N.

Hydrochloric acid solution: HCl = 1 N.

Procedure

Treatment of sample
1 ml 1 N HCl was added to 50 ml clear sample solution and mixed thoroughly.

Preparation of standard curve

Calibration standard was prepared in the range of 0 to 7 mg NO3- -N/L by
diluting to 50 ml the following volumes of intermediate nitrate solution: 0,
1.00, 2.00, 4.00, 7.00… 35.0 ml. NO3- standards were treated in same manner
as samples.

Spectrophotometric measurement
Absorbance was read using distilled/deionized water as the reference at a
wavelength of 220 nm to obtain NO3- reading and a wavelength of 275 nm to
determine interference due to dissolved organic matter.

Calculation
- Two times the absorbance reading at 275 nm was subtracted from the
reading at 220 nm to obtain absorbance due to NO3- .

51
 - A standard curve was constructed by plotting absorbance due to NO3-

against NO3- -N concentration of standard.

- Using corrected sample absorbance, obtain sample concentrations was
obtained directly from standard curve. Note: If correction value is more
than 10% of the reading at 220 nm, do not use this method.

Annex 4 Argentometric method

Reagent

A) Potassium chromate indicator solution:

50 g K2CrO4 was dissolved in a litre of distilled water.

AgNO3 was added to the solution until a definite red precipitate was formed.

The solution was allowed to stand for 12 h.

The solution was filtered and dilute to 1 L with distilled water.

B) Standard silver nitrate titrant, 0.0141 N:

2.395g AgNO3 was dissolved in distilled water and dilute to 1000 ml.

Standardized against 0.0141 N NaCl solution. 1.00 ml = 500 µg Cl- and stored
in a brown bottle.

C) Standard sodium chloride, 0.0141 N:

824g NaCl (dried at 140Oc) was dissolved in distilled water and dilute to 1000
ml, 1.00 ml = 600 µg Cl-

D) Special reagents for removal of interference:

i. Aluminum hydroxide suspension: dissolve 125 g Aluminum potassium

sulphate or aluminium ammonium sulphate, in 1L distilled water. Warm to
600c and add 55 ml conc. NH4OH slowly with stirring. Let stand about 1 hr
transfer to a large bottle, and wash precipitate by successive additions, with
thorough mixing and decanting with distilled water, until free from chloride.
ii. Phenolphthalein in indicator solution .
iii. Sodium hydroxide 1 N.
iv. Sulphuric acid, 1 N.

52
 v. Hydrogen peroxide, 30%

Procedure argentometric method

1. The appropriate sample volume was measured for the indicated chloride range
using the following table and transfer to a 250 ml Erlenmeyer flask.

Sample Volume ml Alkalinity Range mg/L as CaCO3

100 1-50
50 51-100
25 101-200
10 201-500

2. The total volume was brought to 100 ml with distilled water if the sample size
was less than 100 ml.
3. A colour comparison blank was prepared by placing distilled water in a similar
flask and the volume must be equal to that of the sample.
4. One ml potassium dichromate indicator solution was added to the blank and the
sample and afterwards mixed.
5. Silver nitrate tartant was carefully added drop by drop to the colour comparison
blank until the yellow colour changes to a brownish tine.
6. The ml silver nitrate titrant consumed was recorded
7. If the sample was turned yellow, gradually add silver nitrate titrate was gradually
added from a burette. Shaken the flask continuously and continue adding the
titrant until the sample turns the same.
8. The ml silver nitrate titrant consumed was recorded
9. Calculation
mg Cl/L = (A-B) X N X 35,450
ml of sample
Where
A= ml nitration for sample
B= ml titration for blank and
N= normality of silver nitrate
mg NaCl/L = (mg Cl/L) x 1.65

53
Note:
1. Titrate directly sample in the PH range 7 to 10. Adjust sample PH to 7 to 10
with H2SO4 or NaOH if not in this range

2. For highly collared samples clarification with aluminium hydroxide suspension

is necessary
3. If sulphide, sulphite thiosulphate is present, add 1 ml hydrogen peroxide and
stir for 1 minute.

Annex 5 Determination of BOD5

Reagent and Apparatus

• BOD bottles; 300 ml capacity

• Incubator (20OC ± 1O C)
• Stir plate, stir bar, ring stand, burette, 200 ml beaker, and burette holder
• 250 ml Graduated Cylinder
• Containment vessel, baking soda, wash beaker, solution beaker, and pipette for
handling concentrated sulphuric acid.
a). Phosphate buffer solution: Dissolve 8.5g KH2PO4, 21.75 g K2HPO4 33.4g
Na2HPO4 7H2O, and 1.7g NH4Cl in about 500 ml distilled water and dilute to 1L. The
PH should be 7.2 without further adjustment. Discard reagent (or any of the
following reagent) if there is any sign of biological growth in the stock bottle.
b). Magnesium sulphate solution: Dissolve 22.5g MgS4. 7H2O in distilled water and
dilute to1L.
c). Calcium chloride solution: dissolve 27.5g CaCl2 in distilled water and dilute to
1L.
d). Ferric Chloride solution: dissolve 0.25g FeCl3. 6H2O in distilled water and dilute
to 1L
e). Acid and alkali solutions, IN: for neutralization of caustic or acidic waste sample.
f). Sodium sulphite solution 0.025N: Dissolve 1.575g Na2SO3 in 1000 ml distilled
water. This solution is not stable; prepare on the day of use.
g). Nitrification inhibitor: 2-chloro-6- (trichloro methyl) pyridine.

54
h).Glucose-glutamic acid solution: Dry reagent-grade glucose and reagent-grade
glutamic acid at 103OC for 1h. Add 0.150 g glucose and 0.150g glutamic acid to
distilled water, dissolve and dilute to 1 1iter. Prepare fresh immediately before use.
Procedure
1. a) Using your best engineering judgment, determine the dilution for the glucose-
glutamic acid control (BOD5= 198 mg/L) and for the raw and treated wastewater
samples.
b) Check proposed dilutions with instructor before proceeding.
2. a) Prepare four dilution water blanks by filling each bottle with the dilution
water/seed mixture.
b) Prepare four raw wastewater samples. Add the appropriate volumes of raw effluent,
X1 ml, as determined in step 1. Add (300-X1) ml of dilution water. Make sure you
shake the sample bottle thoroughly prior to pipetting sample. Samples for this lab can
be pipetted directly from the sample bottle to assure that uniform samples are
pipetted. Shake bottle between additions of raw wastewater to different BOD bottles.
c) Prepare four treated wastewater samples as in part b with appropriate volumes of
treated wastewater, X2, and dilution water (300-X2) as determined in step 1. Make
sure you shake the sample bottle thoroughly prior to pipetting sample as in part b
above.
d) Prepare eight glucose-glutamic acid samples as in part b, with appropriate volumes
of glucose-glutamic acid, X3, and dilution water (300-X3) as determined in step 1.
3. Add water to the reservoir at top of BOD bottle. Refill during incubation period to
avoid total evaporation of water.
4. Determine the DO (day = 0) on one bottle of raw wastewater, treated wastewater,
and dilution water blank, and two bottles of the glucose-glutamic acid control. (See
DO determination below).
5. Put remaining samples in incubator (20OC).
6. Repeat step three for days 3, 4, and 5.

55
Annex 6 Gravimetric method: Total suspended solids

Preparation of glass-fibber disk

1) Insert disk with wrinkled side up in filtration apparatus

2) Apply vacuum and wash disk with three successive 20-mL portions of
distilled water continue suction to remove all traces of water.
3) Remove filter from filtration apparatus along with the Gooch crucible, and dry
in an oven at 103 to 1050C for 1 hour. If volatile solids are to be measured,
ignite at 550 +500C for 15 minutes in a muffle furnace.
4) Cool in desiccators to balance temperature and weighing until a constant
weight is obtained or until weight loss is less than 0.5 mg between successive
weightings.

SAMPLE ANALYSES

І) Assemble filtering apparatus and filter by suction. The filter paper was wetted
with small volume of distilled water to moisten it.
2). Filter a measured volume of well mixed sample through the glass fibre filter.
3). Wash with three successive 10-mL volumes of distilled water, allowing
complete drainage between washings and continue suction for about 3 minutes
after filtration is complete.
4) Remove the crucible and filter combination from the crucible adapter if a
Gooch crucible is used.
5) Dry for at least І hour at 103 to 1050C in an oven, cool in desiccators to balance
temperature, and weigh.
6) Calculation
mg suspended solids/L = (A-B)x1000
ml sample
Where:
A= Weight of filter + dried residue, mg
B= Weight of filter, mg

56