Waste Water
Waste Water
Waste Water
Water is a vital need not only for us humans, but also for the nature and the industry. Water is
used heavily in several industries to dilute solutions, to generate electricity, to cool and heat
fluids in heat exchangers, etc. However, water has different amounts and types of dissolved
salts in it. Before using water for a certain application, the concentrations and the types of the
dissolved salts in water must be examined and controlled. For this reason, tap water from our
laboratory’s faucet and wastewater supplied by our instructor were analysed. The preformed
experiments were done on two weeks. For tap water, chloride determination using Mohr’s
method, water alkalinity determination, and water hardness types and determination
experiments were performed in the first week using the proper experimental and titration
procedure for each analysis. On the second week, pH and electrical conductivity of tap water
were determined using a pH meter and the proper probes. For wastewater, BOD 5 analysis
started at the first week and completed on the second week where the amounts of dissolved
oxygen were determined using Winkler Method. The experimental results showed that the
analysed tap water contains only methyl alkalinity with 66 ppm CaCO 3, a total hardness of
110 ppm CaCO3, a pH of 7.54, an electrical conductivity of 530 µS, and a chlorine amount of
1.9176 ppm. On the other hand, the wastewater results showed a BOD5 value of 181.83 ppm.
i
Table of Contents
ABSTRACT……………………………………………………………………………...…….i
1. THEORY............................................................................................................................1
1.4 Alkalinity.....................................................................................................................2
1.4.1 p-Alkalinity..........................................................................................................3
1.4.2 m-Alkalinity.........................................................................................................3
1.6 pH Determination........................................................................................................4
2. PROCEDURE.....................................................................................................................6
2.4 pH Determination........................................................................................................8
3. EXPERIMENTAL DATA..................................................................................................9
4. CALCULATIONS............................................................................................................11
4.4 pH Determination......................................................................................................16
ii
4.5 Electrical Conductivity Determination......................................................................16
6. CONCLUSION.................................................................................................................21
7. RECOMMENDATIONS..................................................................................................22
8. REFERENCES..................................................................................................................23
iii
List of Figures
Figure 1: Images of solutions before and after titration in the presence of starch indicator for
2nd group
3
iv
List of Tables
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1. THEORY
1.1 Biochemical Oxygen Demand (BOD)
The determination of biochemical oxygen demand (BOD) is an empirical test that uses
established laboratory processes to assess the relative oxygen requirements of wastewater,
effluents, and polluted waterways. The test analyzes the amount of molecular oxygen used for
biochemical breakdown of organic material (carbonaceous demand) and the amount of
oxygen used to oxidize inorganic material such as sulfides and ferrous iron over a defined
incubation period. As they feed on the carbonaceous material in the trash, microorganisms use
this oxygen. This is significant because wastes with a high oxygen demand consume oxygen
in the receiving water, which can have a negative impact on the quality of life in that water.
The number of higher life forms living in that location and with a high oxygen demand
reduces as the oxygen level decreases. If the oxygen content falls too low, the only species
that survive will be those that are generally regarded nuisances, and the utility of the water
will be substantially decreased. As a result, it is critical to reduce the BOD of trash as much as
feasible.
The BOD test attempts to imitate what happens when waste enters receiving waterways, and
the results are typically assessed after a five-day incubation period. Under precisely regulated
and standardized settings, the amount of oxygen consumed in a sample within five days is
measured. In general, the five-day interval is insufficient for complete oxidation, but it allows
for microbial acclimatization and substantial (40 to 80 percent) oxidation. Over the course of
five days, the trash is oxidized by the bacteria contained in waste, depleting the dissolved
oxygen in the bottle. [1]
The Winkler test is used to assess the dissolved oxygen concentration in water samples.
Titration is used in the Winkler Method to measure the amount of dissolved oxygen in a water
sample. A sample bottle is completely filled with water (no air is left to skew the results). The
dissolved oxygen in the sample is then "fixed" by using a sequence of chemicals to create an
acid compound, which is subsequently titrated with a neutralizing compound, resulting in a
color shift. The point at which the color changes is referred to as the "endpoint," and it
corresponds to the dissolved oxygen concentration in the sample.
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1.3 Chemical Oxygen Needs (COD) Determination
The chemical oxygen demand (COD) test is commonly used to determine the organic strength
of household and industrial wastes. This test quantifies a waste in terms of the total amount of
oxygen required for oxidation to carbon dioxide and water. It is based on the fact that, with a
few exceptions, all organic compounds can be oxidized by the action of strong oxidizing
agents under acidic conditions. Organic matter is converted to carbon dioxide and water
during COD determination, regardless of biological assimilation of the substances. For
example, glucose and lignin are both completely oxidized. As a result, COD values are higher
than BOD values and may be much higher when biologically resistant organic matter is
present.
One of the COD test's major limitations is its inability to distinguish between biologically
oxidizable and biologically inert organic matter. Furthermore, it provides no evidence of the
rate at which the biologically active material would be stabilized under natural conditions.
The main advantage of the COD test is the short evaluation time. The determination can be
made in about 3 hours, as opposed to the 5 days required for BOD measurement. As a result,
it is frequently used as a substitute for the BOD test. [2]
1.4 Alkalinity
Water's alkalinity is a measure of its ability to neutralize acid. It is a total measure of all the
titratable bases in the sample. Most natural waters are alkaline due to the presence of
−¿ ¿ −¿¿
carbonate (CO−2
3 ), bicarbonate ( HCO 3 ) and hydroxyl (OH ) anions. Borates, phosphates,
silicates, and other bases, if present, also contribute to alkalinity. This feature is significant
when deciding whether water is suitable for irrigation and/or mixing some pesticides, as well
as when understanding and controlling wastewater treatment procedures. Alkalinity is
commonly quoted as being equal to calcium carbonate (CaCO3). [3]
Alkalinity Type
Titration Results Bicarbonate (
Hydroxide (OH −¿¿ Carbonate (CO−2
3 ¿ −¿ ¿
HCO 3 )
First State P=0 0 0 T
Second State P<T/2 0 2P T-2P
2
Third State P=T/2 0 2P 0
Fourth State P>T/2 2P-T 2(T-P) 0
Fifth State P=T T 0 0
Alkalinity is a gauge of a water sample's capacity to counteract acids. It is a collective quality
that results from the total neutralizing power of all bases found in a water sample. Using a
standardized acid titrant and volumetric analysis, alkalinity is determined. The endpoint is
indicated by a pH indicator, like phenolphthalein or methyl orange, changing color or by
using a pH meter.
alkalinity because the [OH −¿¿] can easily be derived from the sample pH. If the sample's
−¿¿ −2
original pH is less than 8.3, the phenolphthalein alkalinity is zero and [ OH ] and [CO 3 ] are
both equal to zero.
1.4.1 p-Alkalinity
water sample with an acid of known concentration and phenolphthalein as the indicator, it can
be discovered.
1.4.2 m-Alkalinity
−¿ ¿
Methyl orange is designated by the letter M. The hydroxide ( OH −¿¿), bicarbonate ( HCO 3 ),
and carbonate (CO−2
3 ) ions are the indicators used to calculate the total alkalinity. Methyl
orange only changes color when added to solutions with a pH between 3.1 and 4.4. Except for
carbonic acid, other acids are only dissolved in water in trace amounts; hence, m alkalinity,
which provides the total carbonate alkalinity, can be regarded as the total alkalinity.
Bicarbonate, carbonate, and hydroxide are the three types of alkalinity that are known to exist.
Each species' concentration will change as the pH changes. The amount of all types of
alkalinity in the water is measured as total alkalinity. Titrating a water sample with acid of a
3
known concentration and utilizing chemical indicators, such as phenolphthalein (P indicator),
methyl orange (M indicator), or a pH meter to define "endpoints" will yield the concentration
of each of the three species. A certain pH point causes the chemical indicators to change color
(the endpoint). As pH drops, the composition of alkaline species changes. Below pH 10.3,
carbonate falls below 8.3, and bicarbonate falls below 4.3, hydroxyl alkalinity disappears. At
or below pH 8.3, the phenolphthalein indicator changes from pink to clear. Below pH 4.3, the
methyl orange indicator changes from orange to yellow. Calculating the quantity of P and M
alkalinity involves determining the amount of acid necessary to cause a color change. The "O"
or hydroxide alkalinity is calculated using the P and M findings. These interactions can alter
or be disrupted depending on the ionic components of the water.
Hardness is most frequently linked to the water's capacity to precipitate soap. Due to
interactions between the hardness ions and the soap, cleaning effectiveness decreases as
hardness increases. Chemical hardness is frequently calculated as the total concentration of
polyvalent cations dissolved in the water. Ca and Mg are the most prevalent polyvalent
cations in freshwater.
Carbonate hardness and noncarbonate hardness are the two main types of hardness. The
presence of bicarbonate and carbonate salts is usually responsible for carbonate hardness.
Salts such as calcium chloride, magnesium sulfate, and magnesium chloride contribute to
noncarbonate hardness. The sum of carbonate and noncarbonate hardness equals total
hardness. Iron (Fe++), strontium (Sr++), and manganese (Mn++) may also contribute to hardness
in addition to Ca++ and Mg++ (APHA et al. 1998). However, their contribution is usually
negligible.
1.6 pH Determination
One of the most common environmental measurements is the determination of the pH level of
water wastewater, which is used frequently throughout water chemistry as a method-defined
parameter for controlling pH-dependent reactions, defining completion of analysis, and
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sample preservation. The concentration of H+ and hydroxide (OH −¿¿) ions in water (H2O) is
measured by pH. Water is neutral when the two ions are in equal concentrations, acidic when
H+ > OH −¿¿, and basic when OH −¿¿ > H +.
The ability of water to conduct an electrical current is measured by its electrical conductivity.
The concentration of dissolved charged chemicals (also known as salts) in water determines
the amount of electrical current that can be conducted.
Pure water is not a good electrical conductor. Ordinary distilled water has a conductivity of
about 10 x 10-6 W1*m-1 (20 dS/m) when in equilibrium with carbon dioxide in the air.
Because electrical current is carried by ions in solution, conductivity increases as ion
concentration increases. As water dissolves ionic species, conductivity rises.
Conductivity can be determined by passing an alternating electrical current (I) through two
electrodes immersed in a solution and measuring the voltage that results (U). The cations
migrate to the negative electrode, the anions to the positive electrode, and the solution acts as
an electrical conductor during this process.
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Because chloride ions are present in low concentrations in tap water, surface water, and
mineral water, chloride determination should be accomplished through titration with silver
nitrate (AgNO3) as a titrant.
2. PROCEDURE
2.1 Biochemical Oxygen Needs (BOD)
The experiment consists of two experimental groups. The first experimental group is used to
determine the amount of oxygen after the microorganisms consume oxygen for 5 days. The
second group experiments are used to obtain reference values before the amount of oxygen in
the sample is consumed by microorganisms.
3 mL wastewater is added to the 1st bottles in both groups with the help of a pipette.
The bottles are filled with dilution water so that there are no air bubbles in them.
Sodium thiocyanate solution (Na2S2O3· 5H2O) is filled into the burette for titration.
6
2 mL alkaline iodide azide reagent and 2 mL manganese sulfate solution are added
into the 1st and 2nd bottles with a pipette. The bottles are closed and the solution inside
is shaken for 2 minutes. The mixed solutions are left for 10 minutes.
2 mL of concentrated H2SO4 is added to both bottles and mixed again by closing the
lid. After mixing, the solution is poured into the erlenmeyer flask.
Sodium thiocyanate solution (Na2S2O3· 5H2O) is added until the solution turns light
yellow. Starch indicator solution is added to light yellow solutions until they turn dark
blue.
The value on the burette is read and titrated until the dark blue color disappears. The
titration results are noted.
50 mL of tap water is added into three erlenmeyer flasks. The same procedures are
applied to all three flasks; three repetitions are made for certainty in the experimental
process.
The phenolphthalein indicator is added into the erlenmeyer flask and the presence of
carbonate ion (CO3-) in the solution is determined with the help of the solution color.
The purple color indicates the presence of the ion.
The methyl orange indicator is added and the presence of the carbonate ion (HCO 3-) in
the solution is determined by the solution color. The yellow color indicates the
presence of the ion.
After the color change is set, the solution is titrated with sulfuric acid (H 2SO4) and the
titration results are noted.
50 mL of tap water is added into 3 erlenmeyer flasks. The same procedures are applied
to all three flasks; three repetitions are made for certainty in the experimental process.
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0,01N EDTA solution is filled into a clean burette.
The solution is titrated with 0.01N EDTA until a blue color is obtained. Titration data
are noted.
2.4 pH Determination
The pH probe is immersed in the tap water and the measurement is made. The result of
the pH measurement and the temperature are noted.
The conductivity probe is immersed in the tap water and the measurement is made.
The result of the conductivity measurement and the temperature are noted.
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5 ml of 5% K2CrO4 solution is added to both two flasks. The solution, which is
involving tap water, turns a cloudy yellow, while the solution, which is involving pure
water, turns a transparent yellow. Chloride ions (Cl-) in tap water cause a cloudy
solution to form. To obtain an accurate titration result, the pure water solution is also
turbid by adding CaCO3. For this reason, a cloudy yellow is obtained by adding
CaCO3 to the solution containing pure water.
Solutions are titrated with 0.0141N AgNO3 and titration results are noted.
3. EXPERIMENTAL DATA
In this section, the collected data for each preformed experiment is summarized in a form of
table.
Table 2: Alkalinity Found in 50mL Tap Water Sample Using 0.02N H2SO4 as a Titrant
Table 3: Total Water Hardness Found in 50mL Tap Water Sample Using 0.01N EDTA as a
Titrant
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Table 4: Chloride Amounts Found in 50mL Water Samples Using 0.0141N AgNO3 as a
Titrant and 5 mL 5% K2CrO2 as an Indicator
Table 5: Volume of 0.025N Na2S2O3 Used for Calculating Dissolved O2 Amounts in Samples
for BOD5 Analysis
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4. CALCULATIONS
Manganese sulfate solution and Alkali iodide solution were added into sample. 10 minutes
were waited. 2 ml of H 2 SO 4 solution was added into the sample. Starch solution was used as
an indicator. It is titrated with Na 2 S2 O3 solution.
A∗0.2∗1000 mg
Dissolved oxygen= ( )
B−C L
B: 300 mL (Bottle)
- First, the experiment was carried out using the second group.
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Table 7: Data for BOD
2.Group
1st Titration (1st Bottle) 2nd Titration (2nd Titration)
12,9 ml 14,4 ml
1.Group
1st Titration (1st Bottle) 2nd Titration (2nd Titration)
0,3 ml 4,5 ml
2.Group:
1st Bottle:
12.9∗0.2∗1000 mg
Dissolved oxygen= =8.6869
300−3 L
2nd Bottle:
14.4∗0.2∗1000 mg
Dissolved oxygen= =9.6969
300−3 L
- At the end of five days, the experiment was continued using the first group.
1.Group:
1st Bottle:
0.3∗0.2∗1000 mg
Dissolved oxygen= =0.2020
300−3 L
2nd Bottle:
4.5∗0.2∗1000 mg
Dissolved oxygen= =3.0303
300−3 L
( 8.6869−0.2020 )−(9.6969−3.0303)
BOD5=
3 /300
mg
BOD5=181.83
L
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Figure 1: Images of solutions before and after titration in the presence of starch indicator
for 2nd group
3 titrations were made with 50 ml of tap water sample and 0.02 N H 2 S O4 . In these
titrations, methyl orange and phenolphthalein were used as indicator. Phenolphthalein
gives pink color, methyl orange gives yellow color.
−2
C O3 p-alkalinity test is done with phenolphthalein. No color change was observed in the
tap water solution in the presence of phenolphthalein.
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p-alkalinity=0, so there are no C O −2
3 ions.
−¿¿
HC O3 m-alkalinity test is performed with methyl orange. Yellow color was observed.
The m-alkalinity value was determined as follows.
mg
(NxV ) H SO 4 =( )
2
eq . g CaC O 3
mg
(0,02 N x 3,3 ml)H SO 4 =( )
2
100
eq . g
2 CaC O 3
= 3,3 mg in 0,05 L
Figure 3: Images of solutions before and after titration in the presence of Methyl Orange
indicator
−¿¿
Since there is only HC O3 ion in water, there is no alkalinity formed by C O−2
3 and
O H−¿¿.
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4.3 Hardness Determination
Temporary hardness was determined by the alkalinity test performed above.
+¿ ¿
In this experiment, NH3+NH4Cl buffer solution and Eriochrome Black-T indicator were
used. 0,01 N EDTA solution was used for titration.
mg
(NxV ) EDTA Na =( )
2
eq . g CaC O 3
mg
(0,01 N x 10,4 ml) EDTANa =( )
2
100
eq . g
2 CaC O 3
15
Figure 4: Image of solutions before and after titration in the presence of Eriochrome Black-T
indicator
4.4 pH Determination
The pH of tap water was measured with a pH meter and found to be 7.54. The current
room temperature is 18.6 °C.
Two titrations are made, one with tap water and the other with distilled water. 0,0141 N
AgN O 3 is used. Potassium chromate solution was used as indicator.
16
mg
( NxV ) Ag NO =( )
3
eq . g Cl −¿
¿
mg
(0,0141 N x (7,6−0,8 ml)) Ag NO =( )
3
100
eq . g
2 Cl −¿
¿
= 0,09588 mg in 0,05 L
Figure 5: Image of solutions before and after titration in the presence of Potassium Chromate
Before discussing the resulted, we found it to more convenient to talk about the experimental
conditions and set up. This will help in understanding the how finding we found change with
the experimental parameters.
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Methyl Alkalinity 3,3 mg in 0,05 L
Water is the most important requirement for the survival of all living beings, whether
humans, animals, or plants. Water is the second most important element for survival after
air. According to research results, only 3% of the world's water is fit for human
consumption.[7]
Drinking contaminated water is extremely dangerous and can result in serious illness.
Water should be tested and purified before it is consumed, whether it is for drinking,
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cooking, or as an additive in food products. Nowadays, a large number of diseases are
waterborne.
Analyses of water chemistry are performed to identify and quantify the chemical
components and properties of water samples. The type and sensitivity of the analysis are
determined by the analysis’s purpose and the anticipated use of the water. Water used in
industrial processes, waste-water streams, rivers and streams, rainfall, and the sea are all
subjected to chemical water analysis. In every case, the analysis results provide
information that can be used to make decisions or to reassure that conditions are as
expected. The analytical parameters chosen are appropriate for the decision-making
process or to establish acceptable normalcy. Water chemistry analysis is frequently used
as the foundation for research into water quality, pollution, hydrology, and geothermal
waters. Some of the commonly used methods can detect and measure all natural elements,
inorganic compounds, and a wide range of organic chemical species. These analyzes to be
carried out in polluted waters are determined by taking into account the type of
contamination and the parameters given by the Ministry of Environment Dirty Water
Regulation. In this regulation, the discharge conditions and pollution limit values of the
wastewater of each industry are given to the environment.
The main experiments that should be performed in drinking water and household
wastewater are listed below.
pH
Electrical conductivity
Alkalinity
Hardness
Chloride
Chemical oxygen demand (COD)
Biochemical oxygen demand (BOD)
In our lab, the BOD test was looked at as the first of these analyses. Two of the four
bottles were filled with distilled water and diluted water for the BOD test, while the other
two were filled with waste water and diluted water. The first group of these was put on
hold for 5 days. The required indicators and solutions were added for the second group,
and titration was carried out. 8.6869 mg/L of dissolved oxygen was found in the first
bottle, which contained the waste water, and 9.6969 mg/L of dissolved oxygen was found
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in the second bottle, which contained the pure water, by doing the appropriate calculations
using the data from the second group. After 5 days, the same procedures were performed
for the 1st group. For the first bottle, dissolved oxygen was calculated to be 0.020 mg/L
and 3.0033 mg/L for the second bottle. 181,83 mg/L was discovered when this result was
introduced into the BOD5 equation.
Alkalinity testing was done next. p-alkalinity was initially examined for this test. When
fenophthalein was placed into tap water, no color change was noticed. This shows that the
p-alkalinity is zero. The m-alkalinity was then measured. Methyl orange was found to
have a yellow hue. The titrations and computations led to the discovery of 3,3 mg of
CaCO3 in 0.05 L for m-alkalinity. This test's conclusion revealed that there was only
HCO3 ion present and no alkalinity by CO3-2 and OH-.
The hardness test was done third. The alkalinity test revealed that there was temporary
hardness. The tap water was mixed with buffer solution and Black-T indicator. EDTA was
used for titration. The data from the titration were used to perform the necessary
calculations, and 5,2 mg of CaCO3 was discovered in 0.05 L. The overall hardness
measured is this. By deducting the m-alkalinity from the overall hardness, we may get the
permanent hardness. The measured permanent hardness is 1,9 mg/0.05 L.
The electrical conductivity and pH were measured using a pH and conductivity meter.
This device determined the pH of tap water to be 7.54. Tap water was determined to have
an electrical conductivity of 530 µs.
In the Chloride test, tap water and distilled water were both used. As an indicator,
potassium chromate was utilized. The relevant information from the titration with AgNO3
was used to find 0.09588 mg of chlorine in 0.05 L of tap water.
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6. CONCLUSION
Water is not only used in industry, but it is also used in every aspect of our lives for a variety
of purposes. Water is required in every unit of the chemical industry, either as process water
or for other purposes. Water is used as a raw material in many industries. Fresh water must
meet certain requirements, such as drinking water, agricultural irrigation water, boiler feed
water, or industrial water. Chemical analysis is used to determine these properties.
When water is used, it is also contaminated. Polluted waters are not used, and they pollute the
receiving environment, such as a creek, lake, or sea, where they have been thrown, causing
environmental harm. As a result, polluted water must be analyzed to determine what is
contaminated. Dirty waters are classified into three types. Domestic wastewater, industrial
wastewater, and rainwater from city streets and squares are all examples of wastewater.
Experiments on composite samples taken on a regular basis are required to determine the
degree of water pollution. The type of analysis that will be performed in clean water and
polluted water will be determined by the water's usage area.
In these experiments, tap water and waste water were examined. It has been learned how
water is analyzed with many tests. During the experiment, it was worked as cleanly as
possible and the titrations were done carefully.
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7. RECOMMENDATIONS
Water is one of the essential materials for sustaining life, and the amounts of metal ions and
the amount of oxygen must also be measured to ensure adequate consumables that are
hygienically safe. Alkalinity of water is its acid-neutralizing capacity. It is the sum of all the
titratable bases. The measured value may vary significantly with the end-point pH used. One
of the methods that can also be used for total alkalinity analysis is the method in which
bromocresol green is used as an indicator and the titration is done with 0.0100 M HCl
solution. For this analysis, a pH meter should also be used and titration with HCl should be
continued until the pH approaches 4. Near the end point of the titration, bromocresol green
changes from a blue base form to a yellow acid form; therefore, the green color indicates that
the pH is around 4.5. At the end of this analysis, alkalinity as mg CaCO 3/L water can be
found.
When we evaluate the duration of the COD test, the time taken to complete the analysis is
shorter. Detection can be made in approximately 3 hours instead of the 5 days required for
BOD measurement. For this reason, COD analysis can be preferred instead of BOD analysis.
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8. REFERENCES
[1] Ambrose R.B., Jr., Wool T.A. and Martin J.C. (1993) The Water Quality Simulation
Program, WASP5, U.S. Environmental Protection Agency, Athens, GA.
[2] Clair N. Sawyer; Perry L. McCarty; Gene F. Parkin (2003). Chemistry for Environmental
Engineering and Science (5th ed.). New York: McGraw-Hill.
[3] M.P. Roche, F.J. Millero, Measurement of total alkalinity of surface waters using a
continuous flowing spectrophotometric technique, Marine Chemistry, 60 (1998), 85-94.
[5] pH and Alkalinity, Kelly Addy, M.S., Linda Green, M.S., and Elizabeth Herron, M.A.,
Coastal Institute in Kingston, 1 Greenhouse Road, Kingston, Rhode Island July 2004.
[7] https://www.wwf.org.tr/calismalarimiz/tatli_su/#:~:text=Ya%C5%9Fam%C4%B1n
%20devam%C4%B1%20yeterli%20ve%20iyi,y%C3%BCzde%201'inden%20bile%20az.
(Access Date: 05.11.2022)
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