MATHEMATICAL MODELLING OF WATER QUALITY IN PINACANAUAN

RIVER
 Chapter I

INTRODUCTION

1.1 Background of the Study

Water is one of the most essential natural resources for the existence and survival of the

entire life on this planet. All living organisms need large quantity and good quality of water to

continue their life (Kang, Gao, & Xie, 2017). Preserving this natural resource therefore is a

very essential factor to have a quality life and to ensure the availability of this resource for the

next generations.

As populations and economics grow, water quality is degrading at an alarming rate due to

the increase of pollutant loadings in this natural resource. High organic loadings can reduced

dissolved oxygen to levels that are fatal to parts of the aquatic ecosystem and can cause

intolerable odors. Toxic heavy metals and other micro-pollutants can accumulate in the bodies

of aquatic organisms, including fish, making them unfit for human consumption even if they

themselves survive (Loucks & Beek, 2005). In addition, these pollutants can cause water borne

diseases and can end up in surface and ground water bodies. Addressing this concern, models,

water quality analysis, and evaluation techniques were developed in order to attain water

quality.

Water quality models are very useful in describing the ecological state of the water system

and to predict the change in this state when certain boundary or initial conditions are altered

(Lindenschmidt, 2005). Model will also help to explore various water pollution scenarios and

solve water quality planning and forecasting tasks (Ruzgas, Inga Ruzgiene, & Tomas, 2014).

Also, model can become a helpful tool in the management process, enabling the user to explore

new horizons of the imaginations, to compare choices, and to identify pathways toward

superior solutions to practical problems (Orlob, 1983).

 River water quality is of great environmental concern since it is one of the major available

fresh water resources for human consumption (Jarvie, Whitton, & Neal, 1998). One of the most

popular river water in the Province of Cagayan is the Pinacanauan River. This river supplies

water to more than 500 ha of farms in 8 Barangays of Peñablanca and 4 Barangays of

Tuguegarao City (Espejo, Tungpalan, Negi, & Alex, 2015). From the study of Espejo et.al,

they found out that the quality of water of Pinacanauan River falls within class B but the

dissolved oxygen of their two sampling sites on the month of January is below the standard

value.

Therefore, the main purpose of this study is to develop a comprehensive process

engineering approach on water quality modelling in Pinacanauan River by means of methods

and tools in order to determine the condition of the river water and formulate solutions.

1.2 Statement of the Problem

The study focusses on the water quality modelling of Pinacanauan River. It aimed to answer

the following questions:

1. What are the major pollutants present in river?

2. What is the current ecological status of the river?

3. Can the developed model be used as an evaluation technique in analyzing water quality

of the river?

1.3 Objectives of the Study

Generally, the study aimed to develop a water quality modelling in Pinacanauan River by

means of methods and tools.

Specifically it aimed to:

1. identify the major pollutants present in the river.

2. asses the current ecological status of river.

3. calibrate and validate a reliable tool for quick analysis of the water quality of the river.
1.4 Theoretical Framework

Analysis of the System

Formulation of Objectives

Review of Theoretical Background

Formulation of the Model

Creation of a Model Structure

Formulation of Equations

Formulation of Methods of Solution

Selection of a Computer Code

Calibration of the Model

Validation of the model

Statistical assessment of paired observations and simulations

Sensitivity Analysis

Figure 1: Theoretical Framework of the Study

1.5 Conceptual Framework

Figure 2, shows the conceptual framework of the study. In developing the Mathematical

model, the primary parameters for water quality analysis (biochemical oxygen demand, BOD,

dissolved oxygen DO, nitrites, phosphate, and temperature) are the necessary inputs.

INPUT PROCESS OUTPUT

Collected Data Mathematical Model

Mathematical for Water Quality
Bench-mark Data from
Modelling Analysis
DENR-EMB

Figure 2: Conceptual Framework of the Study

1.6 Scope and Limitations

The locale of the study will be at the Pinacanauan de Tuguegarao River. This study will

focus on assessing the water quality of the river and developing a water quality model that

could serve as a forecasting tool of Pinacauan’s water quality. The study shall be limited to

three station points that were designated by the EMB-WQMA program using the 2015, 2016

and 2017 monitoring results. The parameters that will be considered in this study will be based

on the standard limit set by the DENR Administrative Order 34, for Class B waters: pH,

temperature, TSS, BOD, DO, total coliform, and fecal coliform.

1.7 Significance of the Study

It is becoming more and more apparent that effective analysis and interpretation of water

pollution data play a crucial role in attaining good water quality. The damages brought about

by pollution must be estimated immediately and accurately to establish governmental

regulations for environmental protection. In this regard, the development of a reliable water

quality model is of great importance in assessing the current water quality of Pinacanauan

River.
 The mathematical model developed could be applied both at the pre-designing stage of

measures and facilities and in their practical use. Modeling of water levels in the river then

plays a major role in establishing justified and reasonable programs for long-term measures for

pollutant discharge reduction, rational use of water resources, estimation of the impact in the

environment of technological improvements, development of methods and monitoring

facilities, prediction and quality management of the environment, etc.

1.8 Locale of the Study

Data gathering on the water quality of Pinacanauan River is done at Department of

Environmental and Natural Resources – Environmental Management Bureau (DENR-EMB).

Data analyses were conducted at Cagayan State University – Carig Sur, Tuguegarao City,

Cagayan.

1.9 Definition of Terms

Biochemical Oxygen Demand - measures the approximate concentration of dissolved oxygen

required by bacteria or micro-organisms to decompose organic matter in wastewater or surface

water.

Dissolved Oxygen – measures the concentration of oxygen dissolved in water. The higher

the DO, the better the condition for the growth and productivity of aquatic resources.

Nitrates - include nitrate salts of ammonium, sodium, potassium, and calcium. These come

from soil fertilizers during agricultural runoff as well as in sewage discharge and septic

systems, where they are formed as by-products of the decomposition of animal or human

wastes.

Phosphates - Measure the quantity of phosphorus present as phosphates. It is a common

constituent of fertilizers and organic wastes in sewage and industrial effluent.

Pollution Load - amount of pollutant being discharged into the environment; the product

of the wastewater quality or concentration and the volumetric rate of discharge.

Surface Water - all waters open to the atmosphere and subject to surface runoff.

Total Suspended Solids - concentration of undissolved solid particles in water (e.g., silt,

decaying plant and animal matter, and domestic and industrial wastes), which is indicative

of the extent of sedimentation resulting from land-based activities.

Water Quality - characteristics of water that define its use in terms of physical, chemical,

biological, bacteriological, or radiological characteristics by which the acceptability of water is

evaluated.
 Chapter 2

REVIEW OF RELATED LITERATURE

2.1 Pinacanauan River

The Pinacanauan de Tuguegarao River is one of the foremost water resources in Cagayan

Valley. It is also renowned tourism spot in the province. The clear Pinacanauan River serves

as a national swimming pool for outdoor recreation, source of domestic water for consumption

of nearby communities and support the National Irrigation Administration (NIA) for irrigating

the rice fields and other agricultural lands. (Dayag, Gazmen, & Quizon, 2016).

However, in recent years, pollution of rivers has increased steadily. This situation has arisen

as a result of rapid growth of population, increased urbanization, expansion of industrial

activities, dumping of domestic and raw sewage into nearby water courses, increased use of

fertilizer and agrochemicals, lack of environmental regulations and their tardy implementation

(Aina & Asedipe, 1996).

2.2 Parameters

Philippine water quality is assessed based on the set beneficial use as defined in DAO 1990-

34. Under this DAO, there are 33 parameters that define the desired water quality per water

body classification. Accordingly, a water body must meet the corresponding criteria of each

applicable parameter 100 percent of the time to maintain its designated classification. In the

absence of a water quality index, an interim methodology based on compliance to DAO 1990-

34 is used for all surface waters. Table 1 presents the parameters monitored to assess the water

quality per type of water body (DENR-EMB, 2014).

 Water Body Water Quality Parameter
Inland surface water  Dissolve oxygen (DO)
 Biochemical Oxygen Demand (BOD)
 Total suspended solid (TSS)
 Phosphates
 Nitrates
 Heavy metals
 Cyanide as free cyanide
Groundwaters  Fecal Coliform
 Nitrates
 Salinity (chloride content)
Coastal and marine waters  Fecal Coliform
 Total Coliform
 DO

Table 1: Monitored Water Quality Parameters per Type of Water Body

Water Body Classification and Usage of Freshwater ( (DENR-EMB, 2014)

 Class AA Public Water Supply Class I – Intended primarily for waters having water

that are uninhabited and/or otherwise declared as protected areas, and which require

only approved disinfection to meet the latest PNSDW.

 Class A Public Water Supply Class II – Intended as source of water supply that will

requiring conventional treatment (coagulation, sedimentation, filtration and

disinfection) in order to meet the PNSDW.

 Class B Recreational Water Class I – Intended for primary contact recreation

 Class C – Fishery water for the propagation and growth of fish and other aquatic

resources. Recreational Water Class II for boating, fishing or similar activities. For

agriculture, irrigation, and livestock watering

 Class D – Navigable Waters

Table 3 and Table 4 shows the standard water parameter for the different water classifications.
Parameter Unit AA A B C D
BOD mg/L 1 3 5 7 15
Chloride mg/L 250 250 250 350 400
Color TCU 5 50 50 75 150
Dissolved mg/L 5 5 5 5 2
Oxygen
Fecal MPN/100 <1.1 <1.1 100 200 400
Coliform ml
Nitrate mg/L 7 7 7 7 15
Phosphate mg/L <0.003 0.5 0.5 0.5 5
Temperature C 26-30 26-30 25-31 25-32 26-30
Total mg/L 25 50 65 80 110
Suspended
Solid
Oil and <1 1 1 2 5
grease

Table 2: Water Quality Guidelines for Primary Parameter

Parameter Unit AA A B C D
Ammonia mg/L NDA 0.5 0.5 0.5 7.5
as NH3-N
BOD mg/L NDA 20 30 50 120
COD TCU NDA 60 60 100 200
Color mg/L NDA 100 100 150 300
Fluoride MPN/100 NDA 2 2 2 4
ml
Nitrate as mg/L NDA 14 14 14 30
NO3-N
pH NDA 6.0-9.0 6.0-9.0 6.0-9.0 5.5-9.5
(Range)
Phosphate mg/L NDA 1 1 1 10
Surfactants C NDA 2 3 15 30
(MBAS)
Total mg/L NDA 70 85 100 150
Suspended
Solid
Oil and mg/L NDA 5 5 5 15
grease

Table 3: Effluent Standards

2.3 Governing Laws

2.3.1 Conservation Law

A conservation law or theorem states that a certain defined quantity remains constant no

matter what changes may occur. This quantity has the same numerical value before and after

the changes occurred. Forces may act on an object between some initial and final time, or

between some initial or final position, but certain quantities have the same value in the final

state as it had in the initial state (The University of Iowa).

2.3.1.1 Conservation of Mass

The law of conservation of mass states that mass is neither created nor destroyed. It is

represented by the continuity equation


   u   0
t

where ρ is the fluid density, and u is the fluid velocity (Multiphysics CYCLOPEDIA, 2015).

In a controlled volume system fixed in space with the density ρ= ρ(x,y,z,t) and the velocity

v=v(x,y,z,t), the mass balance is given by:

(ρ x ) (ρ y ) (ρ z ) ρ

  
x y z t

2.3.1.2 Conservation of Momentum

The Law of conservation of momentum states that the mass times the velocity of the center

of mass is constant (Nave, n.d.). It is represented by the Navier-Stokes equation for liquids

solved together with the continuity equation.

The Navier-Stokes equations govern the motion of fluids and can be seen as Newton's

second law of motion for fluids.

v x v v v h 2v 2vx 2vx 

x-momentum:  v x x  v y x  v z x  g  v  2x   
t x y z x  x y 2
z 2 
 v y v y v y v y h 2vy 2vy 2vy 
y-momentum:  vx  vy  vz  g  v 2   
t x y z y  x y 2
z 2 

v z v v v h 2v  2vz 2vz 

z-momentum:  v x z  v y z  v z z  g  v  2z   
t x y z z  x y 2 z 2 

2.3.1.3 Conservation of Energy

Identified as Newton’s Law of Motion, it states that an object moves with a velocity that is

constant in magnitude and direction, unless acted on by a nonzero net force (Serway, Faughn,

Vuille, & Bennett, 2006)

2.3.2 Hydrodynamics and Transport

2.3.2.1 Fick’s First Law

The simplest description of diffusion is given by Fick's laws, which were developed by

Adolf Fick in the 19th century with the first stating that the molar flux due to diffusion is

proportional to the concentration gradient (Multiphysics CYCLOPEDIA, 2015).

Molecular diffusion is a transport process that originates from molecular activity with

concentration gradient as its driving force. The molecular diffusion is described by the

molecular diffusion coefficient Dm (Eldho)

c
Specific mass flux: q   D m
x

c
Molecular diffusion: q   D m
x

c
Turbulent Diffusion: q  ε D
x

c
Dispersion: q  K
x
 v x
Momentum Flux: T  ρv
y

v x
Turbulent Momentum Exchange: T  ρv t
y

T
Heat Flux: q T  ρc p D T
x

2.3.2.2 Mass Transport Phenomena

Mass transfer describes the transport of mass from one point to another and is one of the

main pillars in the subject of Transport Phenomena. Mass transfer may take place in a single

phase or over phase boundaries in multiphase systems. In the vast majority of engineering

problems, mass transfer involves at least one fluid phase (gas or liquid), although it may also

be described in solid-phase materials (multiphysics CYCLOPEDIA, 2015)

 T T T    2T  2T  2T  T
 v x  vy  vz   D T  2  2  2   
 x y z   x y z  t

2.3.2.2.1 One Dimensional Transport Equation

c c 2 c
 vx K 2 I
t t x

where: vx is the mean velocity in the x-direction

c is the concentration average over the cross section

I is the sink or source term that descrbes the reaction of the substance with its

environment.

2.3.2.2.2 Two Dimensional Transport Equation

c  c c   2 c 2 c 
  v x  v y    K x 2  K y 2   I
t  x y   x y 
2.3.2.2.3 Three Dimensional Transport Equation

c  c c c   2 c 2 c 2 c 
  v x  vx  v x    K x 2  K y 2  K z 2   I
t  t t t   x y z 

2.3.2.3 Heat Transfer

Heat transfer from systems of high temperature to systems of lower temperature (Nave, Heat

Transfer, n.d.).

 T T T    2T  2T  2T  T
 v x  vy  vz   D T  2 _ 2  2   
 x y z   x x x  t

2.4 Mathematical Model

Mathematical model is a device used to translate or described how the object of interests

behaves into a language of mathematics. Mathematical modeling aims to describe the different

aspects of the real world, their interaction, and their dynamics through mathematics

(Quarteroni, 2009). According Glenn Marion, mathematical modelling can be used to develop

scientific understanding through qualitative expression of current knowledge of a system.

Marion added that mathematical modelling can helped in testing the effect of changes in a

system and aid decision making.

Mathematical model can be classified as empirical and mechanistic. Empirical models

define a mathematical relationship between quantities in a data set. These are obtained from

the general appearance of a data set without regard for underlying biological ideas. Mechanistic

models attempt to show how certain quantities in a data set are causally linked to other

quantities, independent of any links suggested by data (Ledder, 2015).

 The second important distinction between different models is whether the model is

deterministic or stochastic. In deterministic models, the evolution of the system is completely

determined by the initial (starting) value of the model. In contrast, stochastic models allow for

randomness—they are well-suited to describe processes that are not well defined and the model

variables’ values are defined by their probability distribution rather than a unique value

(Livshits & Coleman, 2008). The four categories of models implied by the above method

classification are:
Empirical Mechanistic
Predicting cattle growth from a
Planetary motion, based on Newtonian
Deterministic regression relationship with feed
mechanics (differential equations)
intake
Genetics of small populations based on
Analysis of variance of variety
Stochastic Mendelian inheritance (probabilistic
yields over sites and years
equations)
Table 4: Categories of Model (Marion, 2008).

2.4.1 Formulation of Mathematical Model

The formulation of the mathematical model composed of series of steps as shown in Figure

3. The steps are conceptualization, selection of model type, computational representation,

calibration and verification, and validation.

 Goals and Objectives

Conceptualization

Sensitivity Analysis

Selection of model type

Computational
Representation

First sample Calibration and

field data set Verification

Second and
additional Validation
field data sets

Application

Figure 3: Formulation of Models (Orlob, et al., 1983)

According to (Orlob, et al., 1983), the first step of the modeling procedure is

conceptualization. One of its importance is to know the locations of control structures and

tributaries along a river, or to know whether various portions of a lake can be considered

essentially deep or shallow. Conceptualization will involve a choice regarding the possible

(spatial) segregation of the water body into a number of discrete segments and layers. Besides

a spatial separation of the water body it may be necessary to include a grouping and
differentiation of biotic species according to how one visualizes their roles in the ecology of

the water body.

With the conceptualization of the modelling problem comes also model formulation. It is

useful to distinguish between various types of model and to discuss briefly their characteristics.

Formulation of the model according to (UNESCO.org, n.d.) involves a decision about the type

of model, elimination of the relationships that do not affect the output results, examination of

alternative types of models and careful relationships of base data collection. This information

is integrated into a conceptual model, in general through the introduction of simplifying

assumptions and qualitative interpretations regarding the flow and the transport process.

Computational representation includes formulation of equations, formulation of methods

of solution, and selection of a computer code. In formulation of equations, it is possible to state

the relationships involved in some formal mathematical or statistical way. Adoption of a

hierarchical approach to this process often results in a clearer set of equations in which the

influence of primary and secondary relations can be more easily appreciated. Some preliminary

data may be needed to guide the choice. For the formulation of methods of solution, only in a

few special cases it may be possible to solve the equations analytically, but most models

involve the use of numerical methods for solving partial differential equations, interpolation,

etc. The choice of the appropriate numerical technique is crucial for numerical stability and

accuracy and also for minimizing computational effort. For selection of a computer code, the

decision depends on the project goals. If a modelling is intended only to provide a first

approximation, a simple code may be appropriate. The form of input and output results, and

the choice of the language, are in dependence of the available facilities.

The calibration of the model is one of the most critical, difficult, and valuable steps in the

model application process. After a pollutant transport model is calibrated to a satisfactory

degree, it is often applied to predict and simulate the future contaminant migration.
(UNESCO.org, n.d.) Calibration includes experimental design, model structure identification,

parameter estimation, and verification. Model structure identification begins by identifying the

large subdivisions of a model and proceeds by fitting these together in diagrammatic form with

a flow chart. It is better the model to be created from different modules (separated parts) and

every part to be developed, tested and calibrated apart. Parameter estimation deals with the

computation of values for the parameters that appear in the model equations, once the structure

of these relationships has been properly identified. Verification is the determination of whether

the correct model has been obtained from a given single set of experimental data. Calibration

and verification represent the bulk of the procedure for model development and testing, once

an experimental data set has been obtained. (Orlob, et al., 1983)

Validation of the model refers to the testing of the adequacy of the model against a second,

independent set of field data. Because validation thus entails the design and implementation of

new experiments, it is unfortunately a step in the analysis that is all too rarely attempted .

(Orlob, et al., 1983).

According to (UNESCO.org, n.d.), it is impossible to apply the model as representative

without suitable proof. The validation of the model depends on the local possibilities. Model

validation, evaluation, confirmation, or testing is the process of assessing the degree of

reliability of the calibrated model using one or more independent data sets. Ideally it is possible

to compare the output results from the model with the observed data.

Sensitivity analysis establishes the relative magnitudes of changes in the simulated model

output responses to changes in the model parameter values. It examines the distribution of

model responses that are possible, given the distributions of estimated parameter values.

(Orlob, et al., 1983)

 Sensitivity analysis is used before and after calibration mainly to test the responsiveness

and sensitivity of the numerical model to every input parameter. It is useful for: examining the

likely uncertainty in simulation results due to uncertainty in model input parameters, and

examining how well parameters are likely to be estimated from the available data for model

calibration. Sensitivity analysis provides important information on how uncertainties in the

model parameters affect the model results. If the model results are highly sensitive to a

particular parameter, the uncertainty associated with that parameter will significantly affect the

ability of the model to make meaningful interpretations and predictions. It is the mean of

determining the model parameters. (UNESCO.org, n.d.)

2.4.2 Water Quality Models

Water quality predictive models include both mathematical expressions and expert

scientific judgement. They include process-based (mechanistic) models and databased

(statistical) models (Loucks & Beek, 2005). The mathematical model of the stream water

quality (Sileika, 1996) is based on the solution of the mass balance equation expressed for

particular pollution parameter along the selected stream. The effect of reservoir on pollution

was expressed by regression equations obtained from the simplified evaluation of the long-

term monitoring at upstream and downstream of the reservoirs (Ruzgiene & Ruzgas, 2014).

Water quality models can range from a zero-dimensional model to a three-

dimensional representation. Zero-dimensional models are used to estimate spatially averaged

pollutant concentration at minimum cost and this model cannot predict the fluid dynamic of

the system. For one-dimensional models, the system geometry was formulated conceptually

as a linear network or segments or volumes section. One-dimensional models are used mostly

in the formulation of models of river water quality by only simulating longitudinal

differences in the river. Also, lakes and estuaries uses two- or three- dimensional models in

order to represent the spatial heterogeneity of the water bodies (Bowie, et al., 1985)

According to (Loucks & Beek, 2005), a water quality model can be applied to describe the

main water quality process for different types of water system such as streams, rivers, lakes

reservoirs, estuaries, coastal waters and oceans.

2.4.2.1 Mass-Balance Principles

According to (Mirbaghery, Abaspour, & Zamani, 2009) model formulation is based on the

mass balance for particular substance. The statement of the mass balance is given as:

Accumulati on  inflow  outflow  sources or sinks

Mass balance is the basic principle of water quality models. Model According to (Loucks

& Beek, 2005), components of mass balance include: first, changes by transport (Tr) into and

out of the segment; second, changes by physical or chemical processes (P) occurring wthin the

segment; and third, changes by sources/discharges to or from the segment (S).

t  t  M i   M i   M i 
 M i  t    t    t  
t
Mi
 t  Tr  t  P  t  S

The changes by transport include both advective and dispersive transport which are

2.4.2.1.1 Advective transport

A transport by flowing water is called the advective transport (Loucks & Beek, 2005).

Advective transport, T XoA ( M / T ) of a constituent at a site XO is the product of the average water

 
velocity, v Xo L / T  , at that site, the surface or cross-sectional area , A L2 , through which

 
advection takes place at that site and the average concentration, C Xo M / L3 , of the constituent

T XoA  v Xo  A  C Xo
 The advection transport depends on water velocity. The water moving with velocity vx

transports the particles of pollutants through the elementary area y and z. The pollutant mass

crossing the area during the time interval t and concentration C is quantified as (Benedini &

Tsakiris, 2013):

M  Cyzv x t

2.4.2.1.2 Dispersive transport

Dispersive transport results from concentration differences. In which if the water column

is stratified, dispersion in the vertical direction is important and if the dispersion in horizontal

direction can be in one or two dimensions (Loucks & Beek, 2005).

The dispersive transport, T XoD M / T  , across a surface area is assumed to be proportional

C
to the concentration gradient 
, at site Xo times the surface area A. Letting D Xo L2 / T 
x X  Xo

, be the dispersion or diffusion coefficient at site x.

C
TXoD   D Xo  A 
x X  Xo

A physically meaningful mathematical description of diffusion is the Fick law that is based

on the analogy to heat conduction. Variability of concentration in the water causes a dispersion

(Benedini & Tsakiris, 2013). The mass crossing the area is:

C
J x yzt  ( E ) x yzt
x
2.4.2.1.3 Mass Transport by Advection and Dispersion

According to (Loucks & Beek, 2005), if the advective and dispersive terms are added and

the terms at a second surface at site X o  x are included. A one dimensional equation results:

t  t  C C 
 M i  t   v XoC Xo  v Xo v C Xo  v  D Xo  D Xo v   A
t
Mi
 x Xo x Xo v 

 
Where Q Xo L3 / M is the flow site Xo

In the study of (Hussain, Atshan, & Najam, 2012), they presented a simple mathematical

model for river pollution. The model consist of a pair of coupled reaction advection-diffusion

equations for pollutant and dissolved oxygen.

 APS x, t   APS x, t  APS x, t 

   Z  PS x, t dx
t x 2 x

 AX S x, t   2  APS x, t  AX S x, t 

 DX     S  X S x, t 
t x 2 x

The equations above account expansion of the pollutant and the dissolved oxygen

concentrations. In which they assumed that the river (Shat Al-Diwanya in Iraq) has a uniform

cross-sectional area. In their study, they studied the simplified case by analytical steady state

solution for the zero dispersion and they found out that the concentration of pollution and

dissolved oxygen level remain within the critical value of these parameters and approximately

consistent with the values that measured for different stations of AL-Diwaniya city.

Another study approach used by (Ani E. C., 2010) was the Fickian advection-dispersion

based on the convective-diffusive mass transport in running waters as shown in the equation

below.
 c  cV X    c 
   DX   S s  St
t x x  x 

Mathematical models proposed in this thesis have different complexity levels and are

able to simulate releases from different types of pollution sources. Based on the study, they

used two kinds of model namely the (1) numerical models, eploying the PDE itself (one-

dimensional advective-dispersion equation), implemented in COMSOL Multiphysics and (2)

analytical models, employing the analytical solutions of ADE (advective-dispersion equation),

implemented in MATLAB.
 CHAPTER 3

METHODOLOGY

A. Model Formulation

Model formulation is based on the mass balance for particular substance. The statement of

the mass balance is given as:

Accumulation  inflow  outflow  sources or sinks

The mathematical model consists of one-dimensional advection-dispersion mass

balance equation of the given pollution parameter, corresponding, initial and boundary

conditions.

The assumptions in such model are:

1. The density of polluted water is constant and similar to clean water density.

2. The substance is well mixed over the cross section. (The assumption has been proved

based on the measurements done).

3. Only longitudinal hydrodynamic dispersion occurs.

The one-dimensional equation for the conservation of mass of a substance in solution, i. e.

the one dimensional advection-dispersion equation for the concentration of Dissolved Oxygen

(DO), Nitrate (NO3), Nitrate (NO2), Ammonia (NH4), Orthophosphate (PO4), Biochemical

Oxygen Demand (BOD5), Organic Nitrogen (NORG) and Temperature (T) can be written for

a river flow systems assuming steady-state, non-uniform, as follows:

C  AD X C   AD X x  dc S
    (1)
t Ax Ax dt V

Storage Advection Dispersion Source & sink

Where:
C= concentration of pollutant (mg/L)
T= time (s)
X= distance (m)
A= Cross-sectional area perpendicular to x (m2)
DX= dispersion coefficient (m2/s)
VX= water velocity perpendicular to x (m/s)
S = source or sink pollutant (mg/s)
V = volume (L)
Dispersion coefficient will be determined using:

D X  2.10nV X D 0.833 (2)

Where:
DX: Longitudinal dispersion coefficient (m2/s)
N: Manning’s roughness coefficient
VX: mean velocity (m/s)
D: mean depth (m)
Sources and sinks for the model in the unit of the volume are as follows:

1. For Biochemical Oxygen Demand:

S  k 1 L  k 3 L (3)

2. For dissolved oxygen:

s   K 1 L  K 2 o  K NH 4 NH 4  K NO2 NO2  K 2 O5  K A  A1  A2  (4)

3. For Ammonia:

S  K NH 4 NH 4  K Kg NORG (5)

4. For Nitrite:

S  K NH 4 NH 4  K NO2 NO2 (6)

5. For Nitrate:
 S  K NO2 NO2  K B  A1  A2  (7)

6. 6. For Organic-N:

S   K kg NORG (9)

7. For Orthophosphate:

S   K PO41 PO4  K PO42  A1  A2  (10)

Where:
K1= Bioxidation coefficient for BOD (1/day)
K3 = Coefficient of settling effects (1/day)
L= BOD Concentrations (mg/ L0
K2 = Re-aeration Coefficient (1/day)
O3 = Oxygen saturation point (mg/L)
O = DO Concentration (mg/L)
KA= DO from chlorophyll-A (1/day)
A1 = Chlorophyll-A Phytoplankton (mg/L)
A2 = Chlorophyll-A sessile algae (mg/L)
KNO2 = Nitrite or nitrate rate (1/day)
NO3=Nitrate concentration (mg/L)
KB=Nitrate uptake by algae (1/day)
NO2 = Nitrite concentration (mg/L)
KNH4 = Ammonia decay rate (1/day)
NORG = Organic N concentration (mg/L)
NH4 = Ammonia concentration (mg/L)
Kkg = Organic-N decay rate (1/day)
KPO41=Orthophosphate decay rate (1/day)
KPO42= Orthophosphate uptake by algae (1/day)
PO4= Orthophosphate concentration (mg/L)
B. Model Conceptualization

Model conceptualization involves the stretch of river having different stations and with

specified reaches. The parameters of BOD5, DO, Nitrification, Orthophosphate, and

temperature will be measured for a given period. Reaches will be further subdivided into units

called computational elements. Each computational element will be modelled as a constant

volume, completely mixed reactor with input, output, and reaction terms. The mathematical

model contains subroutine covering the quality parameters, determination of coefficients,

temperature calibration and hydraulic subroutine. These subroutines interact together with the

main model to simulate the water quality parameters.

Generally, these subroutines simulate each quality parameters by defining the nature of the

sources/sink, S, in the mass balance equation. The element consists of two parts: The first

contains the forcing function inputs which eneter directly into the mass balance equation. The

second consisting of the reactive components which are specific to the particular water quality

variable being modeled.

The hydraulic parameters were calculated via the Manning’s Equation:

1
Q AR 0.67 S 0.5 (10)
n

Where:
Q = flow rate (m3/s)
n = roughness
A = cross section area (m2)
R = hydraulic radius (m)
S = slope

C. Calibration Coefficient

In the model, the coefficients of BOD, DO, Nitrification, Orthophosphate can be calculated

and calibrated according to the stream temperature by the general formulas:

 (log X 2  log X 1 )
k 20 
(t 2  t1 ) (11)

kT  k20  (T  20) (12)

Where:
X = concentration of constituents (mg/L)
t = time (day)
kT = chemical reaction coefficient at temperature T (1/day)
k20 = chemical reaction coefficient at 20 0C (1/day)
ϴ = temperature correction factor
K20 = can be calculated by the measured data for the distance between the two stations

and compare it with the data in the reference books. Then, considering the measured

temperature, the coefficients can be calibrated.

D. Solution Scheme

An implicit finite difference scheme is to be used for the numerical solution of the

advection-diffusion equation. In this method the finite difference approximation will express

the values and the partial derivative of each function within a four point grid formed by the

intersections of the space line i-1, I and i+1 with the time lines tn and tn+1. A control volume is

will be defined and situated around the grid point i. The boundaries of this control volume are

river bed, the water surface and the two cross-sections situated at i-1 and i+1, respectively, as

shown in the figure.

 For a discrete time interval change in Δt, beginning at tn and collecting term in

concentration (C), the resulting finite difference form is:

  AD   Δt     AD   AD   Δt   AD   Δt 
 Q i 1   x   C in11  1.0  Q i   x    x   C in 1   x   C in11  Z i
  Δx  i 1  v i     Δx  i 1  Δx  i 1  v i   Δx  i  v i 

(13)

Where:

z i  C in  Si Δt  ΔtQ xi C xi (14)

vi 
1
 Ai xi  Ai 1xi 1  (15)
2

Δt  Δx/Vx (16)

Assigning all terms on the left-hand side of equation (13) the letters α, β, and γ and by using

equation (15) in Equation (14) the following coefficients results for time n+1:

t t
 1  D x i 1  Qi 1 (17)
xi2
vi
 Δt Δt
β  1  D x i  D x i 1   Qi (18)
Δx i
2
vi

t
 i  D x i (19)
xi2

Using equation (17) through (19) in equation (13), yields the algebraic equation:

 i Cin11   i Cin 1   i Cin11  z i (20)

The term Zni in equation (14) will vary depending on the constituent considered. This term is,

as it is defined in equation (14), takes into account the source and the sink. At each time step,

Equation (10) is to write once for each computational element, i, n+1; therefore, 1≤i≤n, which

results in a system of n simultaneous equations and n unknown.

E. Initial and boundary condition

If the concentration at first station in upstream river are known at the beginning of the

simulation period, they can be used as initial conditions, and user can calculate the

concentration of constituents in the other application.

Since the ratio ∆x/∆t in the numerical scheme should be approximately equal to the current

velocity of water in the prototype, constituents will travel a distance x in a time interval t. This

if, and only advection operates the downstream boundary condition can be given approximately

by cin  cin11 where cin11 is the concentration just downstream from the end of the system.
F. Model Application

The model will be applied to simulate Dissolved oxygen, Biochemical Oxygen Demand,

Nitrite, Nitrate, Orthophosphate, Ammonia, Organic Nitrogen and Temperature in the

Pinacanauan River.

The number of stations, rate of flow, velocity, and the cross-section area will be identified

depending on the data given by Environmental Management Bureau. The number of reaches

will be identified and each reach will be divided into several computation elements, having

their own hydraulic physical, chemical, and biological characteristics. The input data for model

validation are topographical and hydraulic data and water quality in the sampling site.

Topographical data are river cross-section that will be measured at all sampling sites. Required

hydraulic data are: flow rates, water depth and velocity. River branches between the stations

will be inputed to the model as an incremental flow. The temperature of the stream will be

measured directly in the field.

The main data required for this model are as flows:

 Number of major station

 Geometric and hydraulic characteristics of the stations

 Qualitative parameters measured at the first station

 Length between the major stations

 Number of the branches leading to main river with the geometric and hydraulic

characteristics

 Distance to the other stations

 Temperature at the stations

 Location of the intersection point of the sewage and the main river with hydraulic and

qualitative characteristics
  Roughness coefficient for the length of the river

The hydraulic, hydrodynamic, qualitative coefficients and the concentration will be

calculated and simulated in the model. Also the model will draw and compare the profiles of

the simulated and measured concentration of the constituents in a diagram.