DETERMINATION OF BOD KINETIC PARAMETERS AND EVALUATION OF ALTERNATE METHODS

A Thesis submitted to THAPAR INSTITUTE OF ENGINEERING & TECHNOLOGY, PATIALA in partial fulfillment of the requirements for the award of degree of MASTER OF ENGINEERING in ENVIRONMENTAL ENGINEERING by BALWINDER SINGH Under the supervision of

Dr. ANITA RAJOR

Dr. A. S. REDDY

DEPARTMENT OF BIOTECHNOLOGY & ENVIRONMENTAL SCIENCES THAPAR INSTITUTE OF ENGINEERING & TECHNOLOGY (DEEMED UNIVERSITY) PATIALA 147 004 June, 2004

CERTIFICATE

This is to certify that the thesis entitled, Determination of BOD Kinetic Parameters And Evaluation of Alternate Methods submitted by Balwinder Singh in partial fulfillment of the requirements for the award of Degree of MASTER OF ENGINEERING in ENVIRONMENTAL ENGINEERING to Thapar Institute of Engineering & Technology (Deemed University), Patiala, is a record of students own work carried out by him under our supervision and guidance. The report has not been submitted for the award of any other degree or certificate in this or any other university or institute.

(Dr. Anita Rajor) Department of Biotech. & Env. Sciences, Thapar Institute of Engg. & Tech., Patiala 147004

(Dr. A. S. Reddy) Lecturer (Selection Grade) Department of Biotech. & Env. Sciences, Thapar Institute of Engg. & Tech., Patiala 147004

(Dr. Sunil Khanna) Professor & Head, Department of Biotech. & Env. Sciences, Thapar Institute of Engg. & Tech., Patiala 147004

(Dr. D. S. Bawa) Dean (Academic Affairs), Thapar Institute of Engg. & Tech., Patiala 147004

DECLARATION

I here by declare, that the thesis report entitled, Determination of BOD Kinetic Parameters And Evaluation of Alternate Methods written and submitted by me to Thapar Institute of Engineering & Technology (Deemed University), Patiala, in partial fulfillment of the requirements for the degree of MASTER OF ENGINEERING in ENVIRONMENTAL ENGINEERING. This is my original work & conclusions drawn are based on the material collected by me.

I further declare that this work has not been submitted to this or any other university for the award of any other degree, diploma or equivalent course.

BALWINDER SINGH

ACKNOWLEDGEMENT
I wish to express my deep gratitude to Dr. A. S. Reddy, Lecturer (Selection Grade), Department of Biotech. & Environmental Sciences, Thapar Institute of Engg. & Technology, Patiala for his invaluable guidance, inspiration, valuable suggestions, encouragement during the entire period of present study. I will not hesitate to express sincere thanks to Dr. Anita Rajor for providing the constant encouragement and making the lab work possible under her able guidance.

I am highly thankful to Dr. Sunil Khanna, Head, Department of Biotech. & Environmental Science for granting permission for the use of departmental labs.

Lastly, I am thankful to my colleagues, friends and family members for bearing with me and providing me all moral help during the entire period of my work.

BALWINDER SINGH

CONTENTS

CONTENTS Certificate Acknowledgement Declaration List of tables List of Figures Chapter: 1 Introduction 1.1 Background information and objectives of the study 1.2 Overview of the contents of the report 1.3 Importance of the study Chapter: 2 Literature Review Chapter: 3 Materials and Methods 3.1 Introduction 3.2 Sampling 3.3 Serial BOD testing 3.4 Estimation of BOD kinetic parameters 3.4.1 Method of Moments 3.4.2 Least Squares Methods 3.4.3 Thomas Graphical Method 3.4.5 Iteration Method 3.4.6 Fujimoto Method 3.5 comparison of different methods of estimation

PAGE. NO. i ii iii iv v 15

6 11 12 33

CONTENTS Chapter: 4 Results & Discussion 4.1 Introduction 4.2 Results 4.3 Evaluation of methods 4.4 Discussion 4.5 Conclusion

PAGE. NO. 34 - 61

Chapter: 5 Conclusion References

62 - 63 64 - 66

LIST OF TABLES

Table 2.1 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.10 4.11 4.12 4.13 4.14 4.15 4.16

Name Typical values of k and L0 of various waters BOD results of River Satluj sample (SAT-7) BOD results of East Bein River (EB-4) BOD results of Treated Municipal Sewage BOD results of Treated Distillery Effluents BOD results of Treated Dairy Effluents BOD results of Treated Textile Effluents Duration of lag observed in serial BOD test BOD kinetic parameters values for SAT-7 BOD kinetic parameters values for EB-4 BOD kinetic parameters values for Treated Municipal Sewage BOD kinetic parameters values for Treated Distillery Effluents BOD kinetic parameters values for Treated Dairy Effluents BOD kinetic parameters values for Treated Textile Effluents Sum of absolute differences between observed and expected BOD values Results discarded from the method evaluation Suitability of methods for different samples

Page No. 9 35 35 36 36 37 37 38 40 41 42 43 44 45 47 49 50

LIST OF FIGURES

Figure No. 1.1 3.2 3.3 3.4 3.5 4.1 - 4.4 4.5 - 4.8 4.9 - 4.11 4.12 - 4.14 4.15 - 4.17 4.18 - 4.20

Name Fate of biodegradable organic matter, during BOD test Moores diagram for n=7 days Thomas method for SAT-7 (IV) Daily Difference method for SAT-7 (IV) Fujimoto method for SAT-7 (IV) Method comparison for SAT-7 (sample I IV) Method comparison for EB-4 (sample I IV) Method comparison for Sewage (sample I III) Method comparison for Distillery Effluent (sample I III) Method comparison for Dairy Effluent (sample I III) Method comparison for Textile Effluent (sample I III)

Page No. 2 18 24 27 32 52 53 54 55 56 57 57 58 59 60 60 - 61

CHAPTER: 1
Introduction

1.1 Background information and objectives of the study: Biodegradable organic matter is one of the important pollution parameter for water and wastewater. Being heterogeneous (suspended colloidal and dissolved forms) and being composed of a wide variety of compounds, it is very difficult to have a single direct method for estimating its organic matter concentration in any water or wastewater sample. Because of this reason, indirect methods, like BOD, COD, etc. are dependent upon for the measurement of organic matter concentration. These methods measure the organic matter concentration through estimating the amount of oxygen required for its complete oxidation. Methods like COD are quite accurate and take very less time for estimating the organic matter concentration. But they cannot differentiate biodegradable organic matter from non-biodegradable organic matter. Further, COD is not capable of accurately estimating volatile organic matter and organic matter with nitrogen bases. Because of these reasons, BOD is preferred over COD. In the BOD test microorganisms are used for bio-oxidation of the organic matter in the presence of oxygen. The amount of oxygen utilized in the bio-oxidation process is measured and expressed as organic matter concentration in terms of oxygen. This method actually estimates the amount of biodegradable organic matter rather than the total organic matter present in water or wastewater sample. In this method, the sample is diluted to appropriate level, seeded with sufficiently acclimatized microbial populations, aerated and then filled in the air proof BOD bottles and incubated under favaourable conditions. Through measuring the initial and final dissolved oxygen present in the incubated sample, the amount of oxygen consumed in the bio-oxidation process is estimated. Fig.1.1 shows the fate of biodegradable organic matter during the incubation in the BOD test.

O2

CO2 + H2O + Metabolic energy

on ati d xi -o o Bi
Bi os yn th es is

Organic Matter

Microorganism Biodegradable Organic Matter

O2

Non-Biodegradable Organic Matter

CO2+H2O+NH3+Metabolic Synthesized energy microbial biomass Auto oxidation by microorganisms

Microorganisms

O2

Residual biomass

NO3

Fig. (1.1): Fate of the biodegradable organic matter, during incubation in the BOD test.

The bio-oxidation process is rather slow and complete bio-oxidation takes a quite long time (over 25 days). This necessitates incubation of the sample for quite long time for getting the total biodegradable organic matter concentration. In practice, incubating the sample, for such a long time, is not feasible and even if feasible, since the results cannot be real time measurements; their utility is very limited. To avoid this long incubation period a compromising approach is followed. In this approach the sample is incubated for relatively short period of 5 days for getting major portion of the organic matter bio-oxidized. The obtained results are extrapolated through using a mathematical model [BOD kinetics model, y = L0 (1-e-kt)]. Use of this BOD kinetics model requires prior knowledge of the BOD kinetic parameters (k & L0). The required kinetic parameters for the water or wastewater in question are obtained through laboratory experimentation (through conducting serial BOD test, wherein the BOD exerted of the incubated sample is measured at regular intervals). Results of the serial BOD test are used in estimating kinetics parameters with the help of one of the multitude methods available. Accuracy and reproducibility of BOD testing is not very satisfactory. Hence estimation of the kinetic parameters which uses serial BOD test results is prone to become much more inaccurate. For getting satisfactory results selection of appropriate method of calculation of kinetic parameters is very important. Present study is actually concerned with evaluation of the commonly used alternative methods of kinetic parameters estimation. In the present study the following six methods have actually been evaluated: 1. Method of Moments 2. Method of Least Squares 3. Thomas Graphical Method 4. Daily Difference Method 5. Iteration Method

6. Fujimoto Method For evaluating these methods, results are obtained from serial BOD testing for 7 days, of the following samples have been used: 1. Satluj river water sample 2. East Bein river water sample 3. Treated Municipal sewage sample 4. Treated Distillery effluent 5. Treated Dairy effluent 6. Treated Textile effluent 1.2 Overview of the contents of the report: This M.E. dissertation includes five chapters. Chapter 1 is introduction. In this chapter after giving brief background information on BOD and BOD kinetics, objective of the study is introduced. This chapter also includes overview of the contents of the thesis and importance of the present study. In Chapter 2, review of published literature on BOD, BOD kinetics and methods for BOD kinetic parameters estimation is presented. In the Chapter 3, the approach followed for achieving the objective of the study is presented. In addition to this, this chapter also includes a brief overview on the commonly used methods of BOD kinetic parameters estimation. Chapter 4 includes the results of the study and discussion. The results mainly include three components, the serial BOD test results, the estimated BOD kinetic parameters, and results of evaluation of the alternate methods of kinetic parameters estimation. In the discussion, it has been shown, which of the method is most appropriate and why.

The report concludes with Chapter 5, wherein the study is summarized, limitations of the study are highlighted and scope for further study is brought forward. 1.3 Importance of the study: Design, operation and control of biological treatment units require knowledge of ultimate BOD whereas the BOD test gives 5 days BOD value or 3 days BOD value. BOD tests are usually conducted at 20C, whereas temperature in the biological treatment units can be different. These situations make BOD kinetics and BOD kinetic parameters estimation very important. Very few laboratories actually perform BOD kinetic parameters studies and ultimate BOD is found through thumb rules, which is undesirable. In the light of these, the present study proves very important. The study brings about the fact that all methods of kinetic parameters estimation cannot be appropriate for all conditions. One has to sensibly select appropriate methods for estimating the kinetic parameters.

CHAPTER: 2
Literature Review

An attempt has been made to review the available literature on BOD, BOD kinetics and available methods for kinetic parameters estimation. In the nineteenth century the performance of sewage treatment plants was measured mainly by the chemical analysis related to the determination of various forms of nitrogen; as an index of the state and progress of the oxidation of organic matter. Frankland, 1868 as referred by William (1971) first observed that depletion of dissolved oxygen in the wastewater containing organic matter was due to chemical reactions. He observed that depletion of oxygen was dependent on the time of storage. Dupret 1884 as referred by William (1971) recognized that oxygen depletions were due to the activity of microorganisms. The classical equation for expressing the BOD process is: Substrate + bacteria + O2 + growth factors &22 . H2O + increased

bacteria + energy -------------------------------------------------------------(2.1) The royal commission on Sewage Disposal, 1912, chose an incubation period of five days for the BOD test because that is the longest flow time of any British river to the open sea. An incubation temperature of 20oC was chosen because the long-term average summer temperature in Britain was 18.3oC (Nesarathnam,1998).

Adeney 1928 as referred by Jenkins (1960) defined the absolute strength of sewage as the amount of dissolved oxygen required for its complete biochemical oxidation. Winklers method was mostly used to determine the dissolved oxygen content in water (Standard Method 1995). Bruce et.al, (1993) suggested headspace biochemical oxygen demand (HBOD) test having three main advantages: the test does not require sample dilution, oxygen demand determined with in a shorter period of time (2436hrs) that can be used predict 5-day BOD value and the experimental conditions used in the HBOD test, more accurately reproduce the hydrodynamic and culture

conditions. Booki et.al, (2004) suggested the use of fibre optic probe to obtain oxygen demands in 2 or 3 days in respirometric tests, and then 5-day BOD can be predicted from the results. While a standard BOD test procedure developed for certain effluents has been widely accepted, disagreements regarding the basic mechanisms and kinetics of the test continue to persist. In fact, a review of the history of the BOD test and the related mathematical procedures leads to the conclusion that the only universally accepted concept is that the basic reactions involved are biochemical in nature. The controversies about BOD kinetics arises largely due to the fact that the distinction between BOD as a test and BOD as a microbial metabolic process is frequently overlooked. (The term process is used to refer to the series of cellular enzymatic reactions, which bring about the conversion of given reactants to final products under the constraints of the prevalent environmental constraints and factors)(William E.1971). Phelps (1953) has presented the developmental history of BOD test and its kinetics. He after studying the simplified reaction system associated with eq. 2.1 suggested that the velocity of the reaction varied directly as the concentration of the bacterial food supply (substrate). The concentration of the substrate was rated in terms of oxygen equivalents as indicated by the test. Nonetheless, Phelps realized the limitations of his empirical monomolecular law and delineated them quite clearly. In essence, he concluded that though there was no actual reason why BOD reaction should be monomolecular, the approximation was sufficient for practical applications. He also noted that there were instances where the approach was not applicable. Despite its stochastic nature, the first order approach has been applicable under some circumstances, and it is apparently an acceptable approximation of a more general deterministic expression or expressions. The BOD test is designed to determine the quantity of oxygen required by the biota of the system to completely oxidize the biologically available organic material William, (1971). The quantity of oxygen required is the sum of oxygen consumed by:

1. The bacteria of the ecosystem with in the confines of the BOD bottle as they utilize the organic material (substrate) to support synthesis and respiration. 2. The consumers (protozoa) as they ingest the bacteria as a food source to support their growth and respiration. 3. The process of auto destruction of bacterial and protozoan biomass produced as a result of the preceding two processes. During the initial phase of the BOD process, substrate is assimilated by bacteria under aerobic conditions and a major portion of the substrate is converted to biomass. When bacterial production has reached a maximum, i.e. when the substrate concentration has been reduced to essentially zero concentration, the bacteria will either enter the auto destruction phase, or if protozoa are present, they will start utilizing the bacteria as a food source. When essentially all the bacteria have been so consumed the protozoa will enter an auto destruction phase. Conceptually then, the BOD test is terminated when the concentration of bacteria and protozoa have returned to their respective concentration which prevailed at the start of the test. Gaudy (1972), Le Blanc (1974), Stones (1981) and Shrivastava (1982) have also reviewed the BOD test. Studies of streeter and Phelps, 1925 as referred by Gaudy (1972) led to the following first order equation (BOD kinetic model). dL/dt = In integrated form Lt = L0 e-kt = L0(1 e-kt) -------------------------------------------(2.2) - kL

In other form BODt Where,

BODt = Lt =

BOD exerted in t days of incubation. BOD exerted at any time t

L0

Oxygen demand yet to be exerted at t=0 i.e. ultimate BOD.

k t

= =

BOD reaction rate constant and its units are time-1. Time of incubation.

Analysis of the above first order equation indicates two variables, rate constant k and ultimate BOD, L0 are dependent on each other. If the rate of biochemical oxidation is very high, the value BOD5 is essentially equal to the ultimate BOD. (Ramallho, 1983). Maity and Ganguly (2002) observed that experimental k value is always greater than the theoretical k value by 18% and 24%, when the sample is tested at 20oC and at 27oC respectively. Shrivastava (2000) studied the effect of sewage and indigenous seed on BOD exertion and found that with indigenous seed the BOD values are observed more and kinetic study revealed that with indigenous seed the ultimate BOD is more and value of rate constant is higher in both first order and second order equations with sewage seed. Typical values of k and L0 are listed in table 2.1 (Peavy, 1985) Table: 2.1 Typical values of k & L0 for various waters. K (Day-1) <0.1 0.1 0.23 0.35 0.40 0.12 0.23 L0 (mg/l) 0 1 1 30 150 250 10 30

Water Type Tap water Surface water Weak municipal waste water Strong municipal waste water Treated effluent

Reddy reported that kinetics of BOD exertion pattern involves the following: (i) Mathematical modeling of the oxygen demand pattern of the sample being incubated (ii) Using such a mathematical model for extrapolating the results obtain and finding out the rate constant and ultimate BOD. There are different methods of estimation of kinetic parameters k & L0. Before an estimate of k & L0 can be made a set of progressive long-term (10 to 15 days) BOD data must be obtained (Merske et.al, 1972). The work of Berthouex et.al, (1971) showed that the estimation of BOD constants is most accurate when longer BOD test data, with the addition of nitrification inhibitors, are considered. To calculate k & L0 from given series of BOD measurements is fundamentally a curve-fitting problem. Reed et.al, (1931) published a paper on the statistical treatment of velocity data, that is recognized as the most comprehensive and accurate approach to the estimation of the velocity constants of the first order model for the BOD kinetics. However as this method requires laborious calculations and therefore one is discouraged from estimating k & L0 (Merske et.al, 1972). Fair (1936) proposed the log-difference method for the solution of the BOD equation, but was difficult to be solved. The method involved the plotting of daily difference between the BOD values versus time. Thomas (1937) developed the slope method (graphical) and for many years this was the most used method for computing the kinetics parameters. Thomas (1950) proposed a simple graphical approximation for evaluation of the constants of BOD curve, which is based on similarity function. Moor et.al, (1950) developed the method of moments, which became the most used technique of solving BOD kinetics parameters. The method involves constructing of Moore s diagram of BOD/L0 versus k and BOD/BOD.t versus k for the particular number of days for which the BOD data is available. Remo Navone (1960) published a new method for calculating BOD constant for sewage. This method simplified the calculation of these parameters. The least squares method involves

fitting a curve through a set of data points, so that sum of the squares of the difference between the observed value and the value of the fitted curve must be minimum (Metcalf & Eddy, 2003). Fujimoto (1961), suggested an arithmetic plot between BODt+1 versus BODt, and the intersection of this plot with line of slope 1 corresponds to the ultimate BOD(L0). Gurjar (1994) suggested a new simple method to determine first stage BOD constants (k & L0). Guillermo Cutrera et.al, (1999), compared the three methods (non linear fitting, linear fitting & Thomas method) for estimation of k & L0 and found that nonlinear method of least squares results in smallest error. Rai (2000) suggested a simplified method for determination of BOD constants. He suggested the iteration method for estimation of k & L0. Riefler and Smets. (2003) compared the type curve method with least square error method to estimate biofilm kinetic parameters & observed that more accurate and precise estimates were obtained with least square error method.

CHAPTER: 3
Materials And Methods

3.1 Introduction In the study, serial BOD testing for BOD kinetics was conducted on six different types of samples (treated municipal sewage, treated distillery effluent, treated textile effluent, treated dairy effluent, water sample collected from river Satluj near village Sangowal and water sample collected from river East Bein, a tributary to river satluj, at Malsian village). The experiments were conducted in triplicate. Samples of the river Satluj and the river East Bein were analyzed for BOD kinetics, during June to Sept. 2003, and the samples from other four sources were studied during Oct. to Dec. 2003. Results of the serial BOD tests were used in evaluating different methods used for estimating the BOD kinetics parameters (k and L0). Evaluation of the methods was done through calculating and comparing the sum of the absolute differences between the observed BOD and exerted BOD. 3.2 Sampling Grab samples were collected from each of the six sources, once a month for three months. In case of river water samples the sampling was done for four months. The collected samples were brought to the laboratory in an insulated box. For avoiding deterioration of the samples during transportation, the box containing the sample was filled with ice cubes. In the laboratory the samples were retained in a refrigerator and used in the BOD kinetics experimentation within 2 days time from the day of collection.

3.2 serial BOD testing For estimating the BOD kinetics parameters, k and Lo, serial BOD measurements for the first 7 days were made for the prepared samples incubated at 20C. That is, BOD1, BOD2, ---and BOD7 were measured for the sample in question. BOD bottle method described in Standard Method, 1995 Method No. 5210B, was used for these measurements. 24 BOD bottles were used in the experiment for facilitating daily DO measurement in triplicate, as a part of the BOD test. Dilution factor approximating to COD/6 was used for diluting the sample. Aerated distilled water containing 1 ml per liter each of ferric chloride solution, magnesium sulphate solution, phosphate buffer solution and calcium chloride solution was used as dilution water. These solutions and the solutions used in COD measurements and DO measurements were prepared as per the procedure and strengths indicated in the Standard Method, 1995 under the corresponding methods. In case of industrial effluents 1 ml per liter of acclimatized seed was also added to this dilution water. Supernatant of settled secondary sludge from the ETP of the same industry was used as acclimatized seed. The sample in question was first tested for COD using the method given in Standard Method, 1995 Method No. 5220-C. On the basis of the COD dilution factor was found out and used in the preparation of the diluted sample for serial BOD test. 12 liter of diluted sample was prepared and after sufficient aeration the sample was transfered into the 24 BOD bottles. While analyzing 3 of the bottles for initial DO, rest of the bottles were incubated in a BOD incubator at 20oC for 7 days. Every day 3 of the incubated bottles were taken out and tested for DO while using the technique given in Standard Method, 1995 Method No. 4500-O.C. BOD of the sample was estimated by using the following expressions: BODt at 20oC = DF [(DOis-DOfs)-(DOib-Dofb)(1-1/DF)]-----------------(3.1)

Where, BODt = DOis = BOD exerted in t days of incubation. DO of the diluted sample immediately after preparation, mg/l. DOfs = DO of the diluted sample at particular day of incubation, mg/l. DOib DOfb DF = = = DO of seed control before incubation, mg/l. DO of seed control after incubation, mg/l. Dilution factor.

3.4 Estimation of BOD kinetic Parameters: Using the results obtained from serial BOD test, BOD and time were plotted and through extending the smooth curve passing through the data points to the x-axis time lag involved in the test was estimated (fig. 3.1). On the basis of the lag obtained the first order BOD kinetic equation was corrected as below: BODt = L0 (1-e-k . (t-lag time))

The corrected kinetics equation was used in all the calculations, except in case of method of moments, the original BOD kinetic equation and nomograph for n = 7days was used. Using the results obtained from the serial BOD tests, BOD kinetics parameters (k and L0) were estimated by the following six different methods, which are commonly used: (i) (ii) (iii) Method of Moments (Ramallho, 1983) Least Squares Method (Metcalf Eddy, 2003) Thomas Graphical Method (McGhee, 1991)

(iv) (v) (vi)

Daily Difference Method (Ramallho, 1983) Iteration Method (Rai, R.K., 2000) Fujimoto Method (Metcalf Eddy, 2003)

4000

3500

3000

2500

BOD(mg/l)

2000

1500

1000

500

0 0 1 2 3 4 5 6 7 8

Time(days)

Fig. 3.1: Lag of 0.9 day in Textile sample-III

3.4.1 Method of moments (Ramallho, 1983): This method involves use of Moore s diagram which is actually a nomograph showing relationship between k , BOD/L0 and BOD/BOD.t. From the series of BOD measurements for 7-days, BOD/BOD.t was calculated and k value and BOD/L0 value corresponding to this BOD/BOD.t value were read from the Moore s diagram specific to 7-days. From the BOD/L0 value obtained, L0 was calculated. Moore s diagrams (fig. 3.2) are constructed through the following equations: BOD/L0 = n [10-k(10-nk 1)/(10-k-1)] ------------------------------------------(3.2)

BOD/BOD.t =

n [10 k (10 nk 1) /(10 k 1)] -----------------------------(3.3) i-n i-n ik i = 1i i = 1i 10

Where, BODt = n k L0 = = = BOD exerted in time t days of incubation. No. of days of incubation for the serial BOD test. BOD rate constant Ultimate BOD.

The above expressions have been used for calculating BOD/L0 and BOD/BOD.t values for n = 7 days. These calculated values have been used for constructing the required Moore s diagram.

0.258

6 0.238

3 0.218 2

BOD/Lo BOD/BOD.t
0.198 0 0.4 0.8 1.2 1.6 2

k(day-1)

Fig. 3.2 : Moores diagram for n=7 days

BOD/BOD.t

BOD/L0

Sample calculation: The kinetic parameters k and L0 of the River Satluj s fourth sample [SAT-7 (IV)] were calculated as given below. Step:1 Determination of BOD and BOD/BOD.t values: Dilution factor: 1:2 Incubation time (days) 0 1 2 3 4 5 6 7 8.2 7.4 6.7 6.27 5.83 5.63 4.77 4.33 --1.6 3.0 3.86 4.74 5.14 6.86 7.74 BOD=32.94 BOD/BOD.t = 0.207 Step:2 Reading k value and BOD/L0 value corresponding to the BOD/BOD.t value from the Nomograph. k BOD/L0 = = 0.05/day 2.465 --1.6 6.0 11.58 18.96 25.7 41.16 54.18 BOD.t=159.18 Incubation period:7days DO (mg/l) Incubation temperature:20oC BOD . t

BODt (mg/l)

Step 3: Estimation of L0 value L0 = BOD/(BOD/L0) = 2.465/32.94 = 13.36 mg/l 3.4.2 Least Squares Method (Metcalf Eddy 2003): According to first order kinetics dL/dt where, Lt yt dy/dt dy/dt = = = = L0 - yt BODt k (L0 yt) kL0 kyt = - kLt

This is a linear equation. Through use of least squares method k & L0 values in the above linear equation can be found out. In the calculations the following equation are used:Sxx Sxy Slope (-k) = = = n yt2 ( y)2 -----------------------------------------------(3.4)

nyt(dy/dt) (yt) (dy/dt) ---------------------------------(3.5) Sxy / Sxx ---------------------------------------------------------(3.6)

Intercept (kL0) = (dy/dt)/n + k(yt)/n -----------------------------------------------(3.7) L0 = Intercept/(-slope) ----------------------------------------------(3.8)

Sample calculation: The kinetic parameters k & L0 of the river Satluj s fourth sample [SAT-7(IV)] were estimated as follows:

Step 1: Constructing the following table: Time 1 2 3 4 5 6 7 Sums yt 1.60 3.00 3.86 4.74 5.14 6.86 7.74* 25.20 6.50 122.42 26.55 dy/dt = (yt+1 yt-1)/2W 1.50 1.13 0.87 0.63 1.07 1.30 yt2 2.56 9.00 14.90 22.47 26.42 47.06 yt.dy/dt 2.40 27.0 3.34 4.88 5.50 8.92

* Value not included in total and n = 6 is used. Step 2: Substituted the value computed in Step 1 in eq. (3.4) and (3.5). Sxx = 99.48 Sxy = - 4.5 Step 3: Calculated k and L0 by using eq. (3.6), (3.7) and (3.8). k = 0.045/day L0 = 28.17 mg/l

3.4.3 Thomas Graphical Method (McGhee 1991): This is an approximate method. It is based on the following equation: (t/y)1/3 = 1/(2.3 kL0)1/3 + [(2.3 k)2/3/6 L01/3] . t --------------------------(3.9)

Plot of (t/y)1/3 versus t gives slope as (2.3 k)2/3/6 L01/3 and intercept as 1/(2.3 kL0)1/3. The kinetics parameters are calculated as follows: k L0 = = 2.61(slope/intercept) - -------------------------------------------------- (3.10) 1/(2.3 k. intercept3) ----------------------------------------------------- (3.11)

Sample calculation: The kinetic parameters k & L0 of the river Satluj s fourth sample [SAT-7 (IV)] were estimated as follows: Step 1: Constructing the following table: Time (t) 0 1 2 3 4 5 6 7 BODt (y) 0.00 1.60 3.0 3.86 4.74 5.14 6.86 7.74 (t/y)1/3 --0.855 0.873 0.919 0.945 0.991 0.956 0.967

Step 2: Plotted (t/y)1/3 versus t (fig. 3.3) and found slope and intercept as given below: Slope = 0.0205 Intercept = 0.8474 Step 3: From equation (3.10) and (3.11), obtained k and L0: k = 0.063/day L0 = 11.34 mg/l

y = 0.0205x + 0.8474
1 0.98 0.96 0.94 0.92

(t/y)1/3

0.9 0.88 0.86 0.84 0.82 0.8 0 1 2 3 4 5 6 7 8

Days

Fig. 3.3: Thomas Method for SAT-7(IV)

3.4.4 Daily Difference Method (Ramallho,1983): According to first order equation: y dy/dt log(dy/dt) = = = L0 (1- 10-kt) L0 (-10-kt )(ln10)(-k) log(2.303 kL0) kt -----------------------------(3.12)

Plotting log (dy/dt) versus time (midinterval value of t ) gives slope as k and intercept as log(2.303 kL0). Ultimate BOD (L0) can then be obtained by the following equation: L0 Sample calculation: The kinetic parameters k & L0 of the river Satluj s fourth sample [SAT-7 (IV)] were estimated as follows: Step 1: Constructing the following table: Time (t) 0 1 2 3 4 5 6 7 y (mg/l) 0 1.60 3.00 3.86 4.74 5.14 6.86 7.74 dy/dt --1.60 1.40 0.86 0.88 0.40 1.72 0.88 log dy/dt --0.204 0.146 - 0.066 - 1.056 - 0.398 0.236 - 1.056 Midinterval value of t --0.50 1.50 2.50 3.50 4.50 5.50 6.50 = 10(intercept) / 2.303 (k). -----------------------------(3.13)

Step 2: Plotted Log (dy/dt) versus midinterval of time as shown in fig. (3.4) and obtained slope and interval as follows: Slope Intercept Step 3: Calculated k and L0: k L0 = = - slope = 0.033 = 17.12 mg/l = = - 0.033 0.1182

10(intercept)/ 2.303 (k)

0.3

y = -0.0333x + 0.1182

0.2

0.1

log (dy/dt)

0 -0.1

-0.2

-0.3

-0.4

-0.5

Time (Days)

Fig. 3.4: Daily difference method for Sat-7(IV)

3.4.5 Iteration Method: R.K. Rai (2000) suggested an iteration method for the analysis of time series of BOD data and found the results very close to that of least squares method. Procedure: (i) (ii) Assumed the ultimate BOD (L0) equal to the last BOD value. Calculated k from first order equation y = L0(1 e-kt) -----------------------------------------------------(3.14)

Using L0 as in step (i) and using first BOD data (y and t). (iii) (iv) Calculated L0 from equation using k from step (ii). Calculate k from equation using L0 from step (iii). Repeated the calculation of k using just calculated value of L0 and the given BOD data from start and L0 using just calculated value of k and the given BOD data from last till all the given data are used up. The values of k & L0 obtained in the last step are their correct values. Sample calculation: The kinetic parameters k & L0 of the river Satluj s fourth sample [SAT-7 (IV)] were estimated as follows: Step 1: Assumed L0 = 7.73 mg/l Step 2: Substituted L0 = 7.73 mg/l, y = 1.6 mg/l and t = 1 day in equation 3.13 obtained k = 0.232/day

Step 3: Substituted k = 0. 232/day, y = 7.73 mg/l and t = 7 in equation 3.13 obtained L0 = 9.628 mg/l Step 4: Substituted L0 = 9.628 mg/l, y = 3.0 mg/l and t = 2 days in equation 3.13 obtained k = 0.187/day Step 5: Substituted k =0.187/day, y = 6.87 mg/l and t = 6 days in equation 3.13 obtained L0 = 10.19 mg/l Step 6: Substituted L0 = 10.19 mg/l, y = 3.87 mg/l and t = 3 days in equation 3.13 obtained k = 0.159/day. Step 7: Substituted k = 0.159/day, y = 5.13 and t = days in equation 3.13 obtained L0 = 9.35mg/l Step 8: Substituted L0 = 9.35mg/l, y = 4.73mg/l and t = 4 days in equation 3.13 obtained k = 0.176/day

Step 9: The values of BOD constants are, therefore L0 = 9.35mg/l and k = 0.176/day 3.4.6 Fujimoto method (Metcalf Eddy 2003): Using this method an arithmetic plot was prepared of BODt+1 versus BODt. The value at the intersection of the plot with a line of slope 1 corresponds to the ultimate BOD. The rate constant k was determined from the following equation: BODt Where, BODt = L0 t Sample calculation: The kinetic parameters k & L0 of the river Satluj s fourth sample [SAT-7 (IV)] were estimated as follows: Step 1: Prepared and arithmetic plot of BODt+1 versus BODt (fig. 3.5) using the following table: Sr.No. BODt (mg/l) BODt+1 (mg/l) 3.00 3.86 4.74 5.14 6.86 7.74 1 1.60 2 3.00 3 3.86 4 4.74 5 5.14 6 6.86 = = BOD exerted in time t days of incubation. Ultimate BOD time (days) = L0 (1-e-kt)--------------------------------------------- (3.15)

Step 2: Drew a line with slope of 1 on the same plot as constructed in step 1. The value at the intersection of the two lines corresponds to ultimate BOD, L0 = 27 mg/l. Step 3: Determined the k value for 5th day data using equation 3.14. BOD5 = 5.14 = 27 (1-e-5k) k = 0.042/day

50 45 40 35 30

BODt+1

25 20 15 10 5 0 0 5 10 15 20 25 30 35 40 45 50

BODt

Fig. 5: Fujimoto Method For SAT7-IV

3.5 Comparison of different methods of estimation: The methods are compared by plotting observed BOD values and expected BOD values during 7 days for six different methods against time. Evaluation of different methods was done by calculating the sum of absolute differences between the observed and expected BOD values as follows: D = (oi ei) /ei

Where, oi and ei are the observed BOD and expected BOD values calculated by using estimated kinetic parameters by each method.

CHAPTER: 4
Results and Discussion

4.1 Introduction This chapter includes, the results obtained from the serial BOD tests, the BOD kinetic parameters estimation by different methods and the evaluation of different methods of BOD kinetic parameters estimation through sum of the absolute differences between the observed and expected BOD values during 7 days. Further, the results obtained are discussed to indicate how far the BOD kinetic parameters estimation methods are reliable and which of the methods has proved most appropriate in the present study. 4.2 Results Results obtained from the serial BOD tests for 7 days of incubation and from the COD tests on the following six different types of samples are presented in the tables 4.1 to 4.6. 1) Satluj river water sample 2) East Bein river water sample 3) Treated Municipal sewage sample 4) Treated Distillery effluent 5) Treated Dairy effluent 6) Treated Textile effluent

Table: 4.1 BOD results of River Satluj (SAT-7). Days Sample I 1 2 3 4 5 6 7 COD (mg/l) Table: 4.2 BOD results of East Bein river (EB-4). Days Sample I 1 2 3 4 5 6 7 COD (mg/l) 6.60 15.20 28.20 35.00 44.60 49.33 62.00 176.00 Sample II 2.60 13.30 23.60 28.60 33.30 37.00 39.30 115.00 BODt(mg/l) Sample III 5.50 23.25 31.75 38.25 49.25 57.50 62.50 350.00 Sample IV 10.00 21.50 51.50 61.50 71.50 88.50 95.00 727.00 1.02 2.70 3.80 4.00 4.42 4.80 6.56 16.00 Sample II 0.20 0.74 2.54 2.94 3.54 4.20 4.60 21.00 BODt(mg/l) Sample III 0.77 1.80 2.43 2.83 3.48 3.70 4.17 9.00 Sample IV 1.60 3.00 3.86 4.74 5.14 6.86 7.74 25.00

Table: 4.3 BOD results of treated municipal sewage. Days Sample-1 1 2 3 4 5 6 7 COD (mg/l) Table: 4.4 Days Sample-1 1 2 3 4 5 6 7 COD (mg/l) 1400 2130 2570 3200 3600 4250 4650 5000 BOD results of treated Distillery effluent. BODt (mg/l) Sample-2 812.50 1125.00 1687.50 1875.00 1937.50 2000.00 2062.00 10000 Sample-3 3500 6400 8700 10400 12400 13900 14900 13760 16.38 23.73 27.30 30.45 35.70 36.75 37.80 125.00 BODt(mg/l) Sample-2 73.60 117.00 155.60 162.60 175.00 183.00 188.00 160.00 Sample-3 27.30 55.90 83.20 106.60 140.40 154.70 183.30 180.00

Table: 4.5 Days

BOD results of treated Dairy effluent. BODt (mg/l) Sample-1 Sample-2 13.39 28.60 44.20 57.20 70.85 79.69 82.00 100.00 Sample-3 10.20 16.80 22.20 28.20 36.60 37.50 38.20 80.00 45.50 70.00 96.25 127.00 143.50 164.50 178.50 200.00

1 2 3 4 5 6 7 COD (mg/l) Table: 4.6 Days

BOD results of treated Textile effluent. BODt (mg/l) Sample-1 Sample-2 777.51 1282.81 1527.31 1625.11 1646.30 1680.53 1693.57 1300.00 Sample-3 135 2040 2535 2925 3255 3510 3795 2000.00 12.00 18.00 24.00 30.00 30.00 36.00 38.40 720.00

1 2 3 4 5 6 7 COD (mg/l)

The results obtained, from serial BOD tests were checked for involvement of any lag phase and wherever there is a lag phase its duration was measured. Duration of lag, obtained in serial BOD tests is given in table 4.7. Table: 4.7 Duration of lag observed in serial BOD test. Lag Values (day) Samples River Satluj (SAT-7) East Bein River (EB-4) Treated Municipal Sewage Treated Distillery Effluent Treated Dairy Effluent Treated Textile Effluent Nil Nil 0.9 ---Nil 0.20 Nil ---Nil Nil Nil ---Nil Nil Nil ---Nil 0.80 0.75 Nil Sample I 0.5 Sample II 0.85 Sample III 0.35 Sample IV Nil

BOD kinetics parameters (k and L0) calculated from the serial BOD test results using the following six different methods of BOD kinetic parameters estimation, for each of the samples on which serial BOD tests were conducted, are presented in the tables 4.8 to 4.13: 1) Method of moments 2) Least squares method 3) Thomas method 4) Daily difference method 5) Iteration method 6) Fujimoto method COD values and BOD5 /COD values at 20oC are included in these tables.

Kinetic Parameters Values Methods K Moments* Least squares Thomas* Daily Difference* Iteration Fujimoto COD (mg/l) BOD5/COD 0.067 0.221 0.146 0.051 0.414 0.172 Sample I L0 9.27 7.36 6.39 9.4 5.25 8.2 16.0 0.276 K 0.00002 0.037 0.049 0.027 0.160 0.170 Sample II L0 14430 21.83 9.44 18.46 7.42 7.00 21.0 0.169 Sample III K 0.067 0.195 0.421 0.082 0.248 0.256 L0 6.51 5.54 2.45 5.38 4.75 5.00 9.0 0.395 K 0.05 0.045 0.063 0.033 0.176 0.042 Sample IV L0 13.36 28.17 11.34 17.12 9.35 27.0 25.0 0.206

Table: 4.8 BOD Kinetic Parameters Values for the Satluj River water (SAT-7) * k values are to base 10.

Table: 4.9 BOD kinetic parameters values for the East Bein River water (EB-4): BOD Kinetic Parameters Values for the East Bein River water Methods K Moments* Least squares Thomas* Daily Difference Iteration Fujimoto COD (mg/l) BOD5/COD * k values are to base 10. 0.0001 0.023 0.031 0.007 0.071 0.022 Sample I L0 38000 405.48 100.40 490.58 142.85 430.0 176.0 0.254 K 0.018 0.147 0.119 0.134 0.315 0.282 Sample II L0 91.88 64.87 49.35 46.0 45.18 48.0 115.0 0.290 Sample III K 0.018 0.095 0.127 0.073 0.231 0.208 L0 266 135.75 71.51 89.74 72.51 84.0 350.0 0.141 K 0.000 0.047 0.042 0.025 0.074 0.136 Sample IV L0 25372 358.14 113.9 264.65 241.0 145.0 727.0 0.098

Table: 4.10 BOD kinetic parameters values for the treated Municipal sewage: Kinetic Parameters Values Methods Sample I K Method of moments* Least squares Thomas* Daily difference* Iteration Fujimoto 0.206 0.444 0.192 0.182 0.335 0.524 L0 38.50 39.29 40.81 37.26 41.22 38.5 K 0.212 0.475 0.186 0.195 0.499 0.485 Sewage Sample II L0 193.43 196.64 207.70 183.45 188.16 192 K 0.014 0.044 0.009 0.016 0.092 0.049 Sample III L0 917 683.10 1365.26 785.57 346 640

COD(mg/l) BOD5/COD * k values are to base 10.

125 0.286

160 1.094

180 0.78

Table: 4.11 BOD kinetic parameters values for the treated Distillery Effluent: Kinetic Parameters Values Methods Sample I K Method of moments* Least squares Thomas* Daily difference* Iteration Fujimoto 0.1 0.157 0.117 0.063 0.227 0.082 L0 5578.30 6839.22 5200.84 6897.90 5356.47 10700 K 0.192 0.412 0.173 0.204 0.521 0.447 Distellery Sample II L0 2183.13 2230.28 2327 1998.10 2141.98 2170 K 0.078 0.175 0.077 0.081 0.196 0.172 Sample III L0 21384.83 21264.28 21239.71 20391.90 19166.45 21500.00

COD(mg/l) BOD5/COD * k values are to base 10.

5000 0.72

10000 0.194

13760 0.901

Table: 4.12 BOD kinetic parameters values for the treated Dairy Effluent: Kinetic Parameters Values Methods Sample I K Method of moments* Least squares Thomas* Daily difference* Iteration Fujimoto 0.072 0.081 0.070 0.045 0.141 0.094 L0 267.0 410.53 257.60 290.80 293.88 38.20 K 0.083 0.114 0.069 0.047 0.146 0.186 Dairy Sample II L0 109.70 157.39 137.56 174.64 134.0 120.0 K 0.083 0.186 0.087 0.180 0.170 0.455 Sample III L0 55.35 54.59 53.0 39.0 57.26 3850.0

COD(mg/l) BOD5/COD * k values are to base 10.

200 0.718

100 0.708

80 0.458

Table: 4.13 BOD kinetic parameters values for the treated Textile Effluent: Kinetic Parameters Values Methods Sample I K Method of moments* Least squares Thomas* Daily difference* Iteration Fujimoto 0.124 0.228 0.125 0.071 0.329 0.151 L0 43.56 47.81 43.41 64.98 41.00 56.50 K 0.283 0.703 0.231 0.312 0.83 0.096 Textile Sample II L0 1730.13 1731.0 1916.46 1686.38 1686.36 4300.0 K 0.058 0.259 0.179 0.145 0.528 0.455 Sample III L0 6648.20 4706.95 4232 3832.11 3631.11 3850.0

COD(mg/l) BOD5/COD * k values are to base 10.

720 0.042

1300 1.266

2000 1.628

4.3 Evaluation of Methods For evaluating the methods used for estimating the BOD kinetic parameters, expected BOD values against each of the observed BOD values were calculated with the help of the first order BOD kinetics equation given below: BODt = L0 (1-exp-kt) In the above equation the BOD kinetic parameters (k and L0) estimated by the method in question are used for calculating the expected BOD values. While using the observed and expected BOD values, the sum of the absolute differences between the observed and expected BOD values, while using the following equation: D=

i = 1

(oi ei) /ei

Where, D = sum of the absolute differences between the observed and expected BOD values oi ei k = = = is the observed BOD is the expected BOD is the number of terms in the formula

The observed BOD values and expected BOD values for the six different methods have been plotted against time (t) and shown in Figures 4.1 to 4.20. The chi-square statistic obtained for each of the methods of BOD kinetic parameters estimation are given in table 4.14, and are also indicated in the above figures.

Table: 4.14 Sum of absolute differences of observed and expected BOD values:
Methods Sample SAT-7 (I) SAT-7 (II) SAT-7 (III) SAT-7 (IV) 0.83 0.15 0.37 0.44

Moments

Least Squares 1.13 0.18 0.52 0.78

Thomas 0.62 0.37 2.33 0.41

Daily difference 2.98 0.17 0.93 0.93

Iteration 0.64 0.30 0.47 0.50

Fujimoto 1.59 2.59 0.19 1.43

EB-4 (I) EB-4 (II) EB-4 (III) EB-4 (IV)

0.55 6.07 0.75 0.99

0.63 1.34 1.72 0.92

2.50 0.17 0.45 3.70

0.99 0.19 1.27 1.24

0.72 0.21 1.05 0.94

0.62 0.12 0.66 1.07

Sewage-I Sewage-II Sewage-III Distillery-I Distillery-II Distillery-III Dairy - I Dairy II Dairy III Textile-I Textile-II Textile-III

0.32 0.16 0.22 0.49 0.28 0.15 0.38 0.71 0.38 0.41 0.15 1.47

0.34 0.19 0.22 0.64 0.33 0.09 0.86 0.25 0.36 0.54 0.18 1.37

0.40 0.26 0.14 0.47 0.38 0.08 0.32 0.70 0.36 0.42 0.37 0.74

0.67 0.60 0.16 0.96 0.59 0.07 2.03 0.35 0.93 0.82 0.17 1.74

0.73 0.15 0.41 0.57 0.32 0.20 0.35 0.31 0.37 0.42 0.30 0.73

0.31 0.11 0.36 1.18 0.27 0.10 0.52 0.56 0.95 1.09 2.59 0.69

4.4 Discussion For evaluating the methods used for estimating the BOD kinetics parameters, the following criterion has been used: Criterion-1: The method, for which the sum of absolute difference between the observed and estimated BODs (through using first order BOD kinetics equation and estimated BOD kinetic parameters) is minimum, should be the best method for BOD kinetic parameters estimation. That is, if this sum is less than or equal to 0.35, then one can say that the observed values are within the range of 0.95xBODexpected to 1.05xBODexpected. Criterion-2: Criterion-1 for comparison has however not been applied on:
1.

all those cases for which the calculated ultimate BOD (L0) is less than the observed BOD7

2. all those cases for which the observed COD is less than the observed BOD7 or calculated ultimate BOD (L0). Details of the results rejected on the basis of the second criterion are indicated in the table 4.15.

Table-4.15: Results discarded from the methods evaluation Sample Satluj river water sample-1 Satluj river water sample-2 Satluj river water sample-3 Satluj river water sample-4 East Bein river water sample-1 East Bein river water Sample-4 Treated municipal sewage sample-1 Treated municipal sewage sample-2 Treated municipal sewage sample-3 Treated distillery effluent sample-1 Treated distillery effluent sample-2 Treated distillery effluent sample-3 Treated dairy effluents sample-1 Treated dairy effluents sample-2 Treated dairy effluent sample-3 Treated textile effluent sample-2 Treated textile effluent sample-3 Methods Thomas method and Iteration method Moments method and Least Squares method Thomas method Least Squares method and Fujimoto method Moments method, Least Squares methods, Daily difference method and Fujimoto method Moments method Daily difference method All the six method All the six method All the six methods Daily difference method All the six methods All the six methods All the six methods Fujimoto method All the six methods All the six methods

Method of Moments, Thomas method and Daily Difference method have used log to base 10 in the estimations of BOD kinetics parameters. Hence the BOD reaction rate constant (k) obtained by these methods need correction by multiplying with 2.303 in order to make them comparable with the k values calculated by other methods.

After evaluating the methods according to the criterion-1 given earlier, suitability of methods for different samples obtained is shown in the table-4.16. Table: 4.16 Suitability of methods for different samples:
Sample Satluj river water (4 samples) East bein river water (4 samples) Treated municipal sewage samples) Treated distillery effluent samples) Level of Moments Significance 95% 90% 80% 95% 90% 80% 95% (3 90% 80% 95% (3 90% 80% 95% 90% 80% 95% 90% 80% None of 3 2 of 3 1 of 3 None of 2 1 of 2 None of 2 1 of 1 ------1 of 1 ------None of 1 1 of 1 ---None of 1 1 of 1 ---Least Squares None of 2 1 of 2 1 of 2 None of 3 None of 3 2 of 3 1 of 1 ------1 of 1 ------None of 1 1 of 1 ---None of 1 1 of 1 ---Thomas None of 2 2 of 2 ---1 of 4 1 of 4 None of 4 None of 1 1 of 1 ---None of 1 1 of 1 ---None of 1 1 of 1 ---None of 1 1 of 1 ---Daily Iteration difference 1 of 4 None of 4 2 of 4 1 of 3 None of 3 2 of 3 ------------------None of 1 None of 1 1 of 1 None of 1 None of 1 1 of 1 1 of3 2 of 3 ---1 of 4 1 of 4 2 of 4 None of 1 1 of 1 ---1 of 1 ------None of 1 1 of 1 ---None of 1 1 of 1 ---Fujimoto 1 of 3 None of 3 None of 3 1 of 3 1 of 3 1 of 3 1 of 1 ------1 of 1 ---------------None of 1 None of 1 1 of 1

Treated Dairy effluent (3 samples) Treated Textile effluent

The results indicate that iteration method is best for estimating the BOD kinetic parameters from the serial BOD test results. Daily difference method is worst of all.

4.5 Conclusions Method of moments has been found erroneous under the following two different conditions: When there is a lag phase in the serial BOD test (lag phase reduces the t value (from 7 to 7-lag period) where as the nomogram used is specific for t=7 days) When the sample is a river water sample or when it is thoroughly treated effluent sample k value obtained by Method of Moments has been very low and the L0 value very high (consistently higher than the sample s COD) Results of the serial BOD tests have been observed to be not of that high accuracy and dependable. Accurate results might have made the study much more useful. The evaluation approach followed in this study has indicated that Iteration method is the best and daily difference method the worst among the methods evaluated for estimating BOD kinetics parameters from the serial BOD test results.

Observed BOD Moments(0.83)

7 6
BOD(mg/l)

Least squares(1.13) Thomas(0.62) Daily diff.(2.98) Iteration(0.64) Fujimoto(1.59) BOD = 6.56 mg/l COD = 16 mg/l

5 4 3 2 1 0 0 1 2 3 4
Days

Fig: 4.1 Method comparison for SAT-7(I)

7 6 5
BOD (mg/l) Observed BOD Moments(0.15) Least squares(0.18) Thomas(0.37) Daily diff.(0.17) Iteration(0.30) Fujimoto(2.59) BOD = 4.60 mg/l COD = 21.0 mg/l

4 3 2 1 0 0 1 2 3 4
Days

Fig: 4.2 Method comparison for SAT-7 (II)

5 4.5 4 3.5 3 2.5 2 1.5 1 0.5 0 0 1 2 3 4

Days

Observed BOD Moments(0.37) Least squares(0.52) Thomas(2.33) Daily diff.(0.93) Iteration(0.47) Fujimoto(0.19) BOD = 4.17 mg/l COD = 9.0 mg/l

BOD (mg/l)

Fig: 4.3 Method comparison for SAT-7 (III)

9 8 7 6 5 4 3 2 1 0 0 1 2 3 4
Days

Observed BOD Moments(0.44) Least squares(0.78) Thomas(0.41) Daily diff.(0.93) Iteration(0.50) Fujimoto(1.43) BOD = 7.74mg/l COD = 25.0 mg/l

BOD (mg/l)

Fig: 4.4 Method comparison for SAT-7 (IV)

70 60
BOD (mg/l)

Observed BOD Moments(0.55) Least squares(0.63) Thomas(2.50) Daily diff.(0.99) Iteration(0.72) Fujimoto(0.62)

50 40 30 20 10 0 0 1 2 3 4
Days

BOD = 62.0 mg/l COD = 176.0 mg/l

Fig: 4.5 Method comparison for EB-4 (I)

45 40 35 30 25 20 15 10 5 0 0 1 2 3 4 5 6 7

Observed BOD Moments(6.07) Least squares(1.34) Thomas(0.17) Daily diff.(0.19) Iteration(0.21) Fujimoto(0.12)

BOD (mg/l)

BOD = 39.4 mg/l COD = 115.0 mg/l

Days

Fig: 4.6 Method comparison for EB-4 (II)

70 60 BOD (mg/l) 50 40 30 20 10 0 0 1 2 3 4 Days 5 6 7 8

Observed BOD Moments(0.75) Least squares(1.72) Thomas(0.45) Daily diff.(1.27) Iteration(1.05) Fujimoto(0.66)
BOD = 62.50 mg/l COD = 350.0 mg/l

Fig: 4.7 Method comparison for EB-4 (III)

Observed BOD Moment(0.99)

120 100 BOD (mg/l) 80 60 40 20 0 0 1 2 3 4 5 6 7 8

Least squares(0.92) Thomas(3.70) Daily diff.(1.24) Iteration(0.94) Fujimoto(1.07) BOD = 95.0 mg/l COD = 727.0 mg/l

Days

Fig: 4.8 Method comparison for EB-4 (IV)

Observed BOD

50 40
BOD(mg/l)

Moments(0.32) Least squares(0.34) Thomas(0.40) Daily diff.(0.67) Iteration(0.73) Fujimoto(0.31)

BOD = 37.8 mg/l COD = 125.0 mg/l

30 20 10 0 0 1 2 3 4
Days

Fig. 4.9 Method comparison for sewage-I

Observed BOD Moments(0.16) Least squares(0.19)

250 200
BOD(mg/l)

Thomas(0.26) Daily diff.(0.60) Iteration(0.15) Fujimoto(0.11) BOD = 188.0 mg/l COD = 160.0 mg/l

150 100 50 0 0 1 2 3 4
Days

Fig: 4.10 Method comparison for Sewage - II

200 180 160 140 120 100 80 60 40 20 0 0 1 2 3 4 Days 5 6 7 8

Observed BOD Moments(0.22) Least squares(0.22) Thomas(0.14) Daily diff.(0.16) Iteration(0.41) Fujimoto(0.36)
BOD = 183.0 mg/l COD = 180.0 mg/l

BOD(mg/l)

Fig: 4.11 Method comparison for Sewage-III

BOD(mg/l)

5000 4500 4000 3500 3000 2500 2000 1500 1000 500 0 0 1 2 3 4
Days

Observed BOD Moments(0.49) Least squares(0.64) Thomas(0.47) Daily diff.(0.96) Iteration(0.57) Fujimoto(1.18)

BOD = 4650.0 mg/l COD = 5000.0 mg/l

Fig. 4.12 Method comparison for Distillery-I

2500 2000
BOD(mg/l)

Observed BOD Moments(0.28) Least squares(0.33) Thomas(0.38) Daily diff.(0.59) Iteration(0.32) Fujimoto(0.27)

1500 1000 500 0 0 1 2 3 4

Days

BOD = 2062.0 mg/l COD = 10000.0 mg/l

Fig: 4.13 Method comparison for Distillery II

18000 16000 14000 12000 10000 8000 6000 4000 2000 0 0 1 2 3 4

Days

Oserved BOD Moments(0.15) Least squares(0.09) Thomas(0.06) Daily diff.(0.07) Iteration(0.20) Fujimoto(0.10)

BOD(mg/l)

BOD = 14900.0 mg/l COD = 13760.0 mg/l

Fig: 4.14 Method comparison for Distillery-III

Observed BOD Moments(0.38) Least squares(0.86) Thomas(0.32) Daily diff.(2.03) Iteration(0.35) Fujimoto(0.52) BOD = 178.5 mg/l COD = 200.0 mg/l

200 180 160 140 120 100 80 60 40 20 0 0 1 2 3 4

Days

BOD(mg/l)

Fig: 4.15 Method comparison for Dairy-I

100 90 80 70 60 50 40 30 20 10 0 0 1 2 3 4
Days

Observed BOD Moments(0.71) Least squares(0.25) Thomas(0.70) Daily diff.(0.35) Iteration(0.31) Fujimoto(0.56)

BOD(mg/l)

BOD = 82.0 mg/l COD = 100.0 mg/l

Fig: 4.16 Method comparison for Dairy-II

45 40 35 30 25 20 15 10 5 0 0 1 2 3 4
Days

Observed BOD Moments(0.38) Least squares(0.36) Thomas(0.36) Daily diff.(0.93) Iteration(0.37) Fujimoto(0.95)

BOD(mg/l)

BOD = 38.2 mg/l COD = 80.0 mg/l

Fig: 4.17 Method comparison for Dairy-III

50 45 40 35 30 25 20 15 10 5 0 0 1 2 3 4
Days

Observed BOD Moments(0.41) Least squares(0.54) Thomas(0.42) Daily diff.(0.82) Iteration(0.42) Fujimoto(1.09) BOD = 38.4 mg/l COD = 720.0 mg/l

BOD(mg/l)

Fig: 4.18 Method comparison for Textile-I

2500 2000
BOD(mg/l)

Observed BOD Moments(0.15) Least squares(0.18) Thomas(0.37) Daily diff.(0.17) Iteration(0.30) Fujimoto(2.59) BOD = 1693.6 mg/l COD = 1300.0 mg/l

1500 1000 500 0 0 1 2 3 4

Days

Fig: 4.19 Method comparison for Textile-II

Observed BOD Moments(1.47) 4500 4000 3500 3000

BOD(mg/l)

Least squares(1.37) Thomas(0.74) Daily diff.(1.74) Iteration(0.73) Fujimoto(0.69)

BOD = 3795.0 mg/l COD = 2000.0 mg/l

2500 2000 1500 1000 500 0 -500 0 1 2 3 4

Days

Fig: 4.20 Method comparison for Textile-III

CHAPTER: 5
Conclusions

The present study on the evaluation of six different methods for BOD kinetic parameters estimation, while using the serial BOD test results for treated industrial effluents and river waters, has indicated that Iteration method is the best and Daily difference method is the worst. This conclusion should be seen in the light of the following limitations of the present study: 1. BOD and COD results indicate that some of the samples used in the study are not in real sense treated effluents (at the time sampling the treatment plant might not been working satisfactorily) (sewage samples 2 and 3, distillery effluent sample 3 and textile effluent sample 2 and 3). 2. In quite a few cases the testing has indicated that their BOD7 is greater than COD this indicates that the testing of the samples has not been that accurate. For making the evaluation process acceptable the results of all such samples whose BOD7 was obtained greater than the COD have not been considered. 3. In some of the cases in the serial BOD test, an initial lag phase was observed (indicating that the seed used was not sufficiently acclimatized). For taking care of this problem the BOD kinetic equation used has been appropriately modified. But this modification has brought in certain errors affecting the evaluation process. 4. Treated effluent samples have been used and for properly treated effluents k values, as expected, have been found to be very low and wherever very low k values are encountered the L0 was found to be higher than COD. Samples with such cases have also been not considered in the evaluation process. For the selection of appropriate method for BOD kinetic parameters, study has indicated that the following aspects may be given due consideration:

Serial BOD test may be conducted accurately while using properly acclimatized seed and the results may be crosschecked with COD test.

For each type of wastewater or water samples the methods may be separately evaluated and selected on the basis of statistically significant number of serial BOD tests (at least 7 samples may be tested).

Incubation period for serial BOD test was chosen as 7 days and this may be followed because it can allow bio-oxidation of significant fraction of the organic matter and nitrogenous BOD exertion may still not be significant. However in case of treated effluent samples for avoiding nitrogenous BOD exertion appropriate inhibitors may be used.

The present study has clearly indicated that Moments Method of kinetic parameters estimation is not good for samples from surface water bodies and for thoroughly treated secondary effluents. Keeping this in mind further work may be planned for answering the question which method is most appropriate under what conditions?

REFERENCES 1. APHA, AWWA and WPCF (1995), Standard Methods for Estimation of Water & Waste Water, 19th addition, 1995, Jointly edited by Eaton, Andrew D.; Clesceri, Lenore S. and Greenberg, Arnold E.. 2. Berthouex, P. M. and Hunter, W.G. (1971), Problems associated with planning BOD experiments. J. San. Eng. Div. Amer. Soc. Civil Engr., 97 (SA4), p. 393407. 3. Booki Min; David Kohlar; Bruce E. Logan (2004), A Simplified HBOD Test Protocol Based on Oxygen Measurement using a fiber optic Probe, Water Environmental Research, Vol. 76(1), p. 29-36. 4. Bruce E. Logan; Gretchen A. Wagenseller (1993),The HBOD Test: A New Method for Determining Biochemical Oxygen Demand, Water Environmental Research, Vol. 65(7), p. 862. 5. Fair, G.M. (1936) The Log Difference Method of Estimating the Constants of the First Stage BOD Curve Sewage Works Journ., Vol. 8, p. 430 434. 6. Fujimoto, Y (1961), Graphical use of first stage BOD equation, J. Water Pollution Control, Vol. 36(1), p. 69. 7. Gaudy, A.F. Jr. (1972) Biochemical Oxygen Demand in water Pollution Microbiology Ed. Ralph Mitchell, Wiley Interscience N. Y. London, p. 305. 8. Guillermo Cutrera; Liliana Manfredi; Carlos E del Valle and Froilan Gonzalez, J. (1999), On the determination of the kinetic parameters for the BOD Test, Water SA, Vol. 25 No. 3, p. 377-379. 9. Gurjar, B. R. (1994), Formulation of a Simple New Method to Determine First Stage BOD Constants, (K & L) , Indian J. Environmental Protection, Vol. 14, No. 6, p. 440-442.

10. Jenkins, D. (1960) The use of Manometric Methods in the Study of Sewage and Trade Wastes , in Waste Treatment Ed. P.C.G. Issac., p.319. 11. Le Blanc, P.J. (1974) Review of Rapid BOD Test Methods , J. Water Pollution Control Federation. Vol. 46, p. 2202. 12. Maiti, S.K. and Ganguly Sangeeta (2002) Errors in the Performance of BOD327 and BOD520 test and its Effect on Determination of Rate Constant Indian J. Environmental Protection, Vol. 22 (10), p. 1113 1119. 13. Marske, D.M. and L.B. Polkowski (1972), Evaluation of methods for estimating biochemical oxygen demand parameters. J. Water Poll. Cont. Fed., 44 (10), p. 1987-2000. 14. McGhee, T.J. (1991) Water Supply and Sewrage 6th edition McGraw Hill, Tokyo. 15. Metcalf Eddy (2003), Wastewater Engineering, Tata McGraw Hill Publication, New Delhi. 16. Moore, E. W.; Thomas; H. A., and Snow, W.B. (1950), Simplified Method for analysis of BOD data, Sew. Ind. Wastes. 22 (10). 17. Nesarattnam Suresh (1998), Effluent Treatment, Pira Environmental Guide Series, published by Pira International UK. 18. Phelps, E.B. (1953) Stream Sanitation , Wiley, New York. 19. Peavy H.S., Donal R. Rowe, George Tchobanoglous (1985) Environmental Engineering McGraw Hill, New York p. 43 20. Rai, R. K. (2000), Simplified method for Determination of BOD Constants , Indian J. Environmental Protection, Vol. 20, No. 4, p. 263-267. 21. Rai, R. K. (2000), Iteration Method For The Analysis Of BOD Data , Indian J. Environmental Health. Vol. 42. No. 1 p. 25-27.

22. Ramallho, R. S. (1983), Introduction to Wastewater Treatment Process , Academic Publication, (Second Edition), New York. 23. Reddy, A. S., BOD and BOD kinetics , Under Publication. 24. Reed, L.J. and Theriault, E.J. (1931), The statistical treatment of reaction . Velocity data II. J. Phys. Chem., p. 35 950. 25. Remo Navone (1960), A new method for calculating k and L for sewage , Water and Sewage Works, p. 285-286. 26. Shrivastava, A.K. (1982) Analytical and Experimental Investigations of BOD Kinetics in an Aquatic Eco-systems Ph. D. Thesis submitted to University of Roorkee, Roorkee. 27. Shrivastva, A.K.: Swaroop Jyoti and Jain Neeraj (2000), Effect of Indigenous Seed on Kinetic Equations , Indian J. Environmental health, Vol.22(2), p. 7578. 28. Stone, T. (1981), A resume of the Kinetics of BOD Test, Water Pollution Control 80(4), p. 513-520. 29. Thomas, Jr. H.A. (1937) The Slope Method of Evaluating the Constants of the First Stage BOD Curve Sewage Works J., Vol. 9, p. 425. 30. Thomas, H.A. (1950), Graphical determination of BOD curve constants , Water & Sewage works, Vol. 97, p. 123. 31. William, E. Gates and Sambhunath Ghosh (1971) Biokinetic Evaluation of BOD Concepts and Data J. Sanitary Engineering Division, SA-3, p. 287 307.