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Pilot-scale study of removal of anionic surfactants with trickling filter Guo, Feng 2008

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PILOT-SCALE STUDY OF REMOVAL OF ANIONIC SURFACTANTS WITH TRICKLING FILTER  by  Feng Guo  A THESIS SUBMITTED 1N PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF  MASTER OF APPLIED SCIENCE  in The Faculty of Graduate Studies (Civil Engineering)  THE UNIVERSITY OF BRITISH COLUMBIA (VANCOUVER) September, 2008 © Feng Guo  11  ABSTRACT  Anionic surfactants are wildly used in many industrial and household applications. Because anionic surfactants are used so widely, significant attention has focused on the removal of these contaminants from wastewater. Among various treatment techniques, biofiltration, such as trickling filter technologies, has been employed in many wastewater treatment plants (WWPTs) to remove anionic surfactants. However, current knowledge of the efficacy of trickling filter to remove anionic surfactants from wastewaters is limited. The present study characterized the performance of a high rate (i.e. roughing) trickling filter to remove anionic surfactants both at lab-scale and pilot-scale. Lab-scale tests investigated the biodegradation of anionic surfactants under controllable conditions were compared with those from previous studies by others. Pilot-scale tests investigated the efficacy of a trickling filter at removing anionic surfactants from a wastewater over an extended period of time. The data from the pilot-scale tests were used to model the performance of trickling filter at removing anionic surfactants from the wastewater, using first order and modified Velz models.  The lab-scale tests indicated that high molecular weight anionic surfactants degrade faster than the low molecular weight surfactants. The biodegradation rates observed in the present study were similar to those from pervious studies by others. The pilot-scale tests indicated that roughing trickling filter could remove 11% to 29% of anionic surfactants and 4% to 22% of COD from the wastewater. Higher molecular weight anionic surfactants were more degradable.  The experimental data could be accurately modeled using the modified Velz model (R 2 value more than 0.9). The degradation rates of modified Velz model for total anionic surfactants, high molecular weight anionic surfactants and COD were 0.053±0.0057, 0.088±0.0048 and 0.119±0.0111 (mIs) ° respectively.  111  The pilot-scale test results indicated that a high rate (i.e., roughing) trickling filter was not capable of effectively removing anionic surfactants in the primary effluent at Lions Gate WWTP because a relatively large trickling filter area would be required to achieve the required surfactant removal efficiency.  iv  TABLE OF CONTENTS  ABSTRACT  .  ii  TABLE OF CONTENTS  iv  LIST OF TABLES  vi  LIST OF FIGURES  vii  LIST OF SYMBOLS  viii  ACKNOWLEDGEMENTS  x  CHAPTER 1 INTRODUCTION AND RESEARCH OBJECTIVES  1  1.1 SrFE SiTuATION AND PRoBLEMs RELATED TO MBAS 1.2 OBJ&rnvEs OF PREsENT STUDY 1.3 ORGANIzATION OF THE THEsIs  CHAPTER 2 LITERATURE REVIEW 2.1 TypEs AND USAGE OF SuiuAcTANTS 2.2 EivuO1IENTAL IMPACT OF SuRFAcTANTs 2.3 TREATMENT METHODS FOR THE REMov.i. OF ANIONIC SuIAcTANTs FROM WA5TEwAmR  2.3.1 Physical and Chemical Treatment 2.3.2 Biological Treatment 2.4 M0DELNG THE PERFoRMANcE OF TRIcI<aING FmTER  2.4.3 Knowledge Gap in Previous Studies CHAPTER 3 MATERIALS AND METHODS 3.1 L-ScALE BIODEGRADATION ExPERIMENTS 3.2 Pn.oT-ScPi.E ExPERIMENTs  3.2.1 Pilot-Scale System Setup 3.2.2 Pilot-Scale System Operation 3.2.3 Sampling Process 3.3 ANM..YTIcAL METHODS  3.3.1 MBASAnalysis 3.3.1.1 Procedure of SPE 3.3.1.2 Procedure ofMBASAnalysis 3.3.2 COD Analysis 3.3.3 TS&VS Test 3.3.4 Other Data Monitored On-Site 3.3.5 Data Analysis Methods 3.4 WAsmwATER SouRcE  3.5QAJQC  1 3 4 5 5 6 7 7 8 10 13 14 14 16 16 20 20 21  21 24 30 33 33 33 34 34 35  V  CHAPTER 4 RESULTS AND DISSCUSSIONS 4.1  .  LAB-sCALE BIoDEGIDATIoN ExPERIMENTs  4.2 PILOT-scALE ExPERIMENTs  36 40  4.2.1 MBAS Removal  40  4.2.2 COD Removal  42  CHAPTER 5 IMPLICATIONS OF RESULTS TO PROCESS ENGINEERING  45  CHAPTER 6 CONCLUSIONS  48  REFERENCES APP ENDIX A: RAW DATA  57  APPENDIX A-I LAB-SCALE ExPERIMENTAL DATA  57  APPENDIX A-Il PILOT-SCALE ExPERIMENTAL DATA  59  APPENDIX A-Ill TOTAL COD, H, DO AND TEMPERATuRE OF WASTEWATER AND TS&VS DATA  85  APPENDIX B: QA/QC  87  APPENDIX C: CALCULATION OF ADJUSTMENT OF INFLUENT AND RECYCLING FLOW RATES  89  APPENDIX D: SUBLATION TEST PROCEDURE AND RESULTS  90  APPENDIX E: TYPICAL CALIBRATION CURVE FOR MBAS APPENDIX F: TYPICAL CALIBRATION CURVE FOR COD  94  vi  LIST OF TABLES  Table 3- 1 Lab-scale experimental conditions  14  Table 3- 2 Physical properties of trickling filter media used in the present study  17  Table 3- 3 Pilot-scale experimental conditions  20  Table 3- 4 Summary of procedure of SPE  29  Table 3- 5 Summary of procedure of MBAS analysis  32  Table 3- 6 Characteristics of influent wastewater to the pilot-scale TF  35  Table 4- 1 The first order model rate coefficients from the lab-scale experiments  38  Table 4- 2 Summary of modified VezI model rate coefficients from the pilot-scale experiments  42  Table 5- 1 Summary of parameters used for calculation  45  vii  LIST OF FIGURES  Fig. 1- 1 Lions Gate WWTP site map  2  Fig. 2- 1 Chemical structure of typical surfactants  6  Fig. 2- 2 Chemical structures of typical anionic surfactants Fig. 2- 3 Biodegradation pathway of dodecylbenzene suiphonate  6  Fig. 3- 1 Pilot-scale experiment flow chart  9 17  Fig. 3- 2 Pilot-scale experimental setup  19  Fig. 3- 3 Flowchart of a). MBAS analysis; b). COD analysis procedures Fig. 3- 4 Solid phase extraction apparatus  23  Fig. 4- 1 Average removal efficiency of MBAS in lab-scale biodegradation tests  37  Fig. 4- 2 Average removal efficiency of COD in lab-scale biodegradation tests Fig. 4- 3 MBAS removal  39 41  Fig. 4-4 COD removal  43  Fig 5- 1 Fraction removed as a function of surface area (m ) for a trickling filter 2  46  Fig 5- 2 Sensitivity analysis of parameters in the modified Vezl model  47  25  viii  LIST OF SYMBOLS  C  concentration of contaminant of interest (mg/L),  =  0 = concentration in the effluent (mg/L), C Cm = concentration in the influent (mg/L), kT = first order rate constant at temperature T (hf’), 20 k ’  =  first order rate coefficient at 20°C (hf’)  hydraulic retention time (s),  =  kinetic viscosity (0.0 13 cm /s, measured by AV25OVAC viscosity meter), 2 angle of TF plate inclination from the horizontal plane,  =  acceleration of gravity (981 cm/s ), 2  g  L = length of the flow through TF (cm), q =  0  flow per unite width of TF plate (cm /cms), 3  a dimensionless temperature correction coefficient, which typically equal to 1.035,  T = wastewater temperature (°C) R  recirculation ratio, defined as the recirculation flow rate divided by the primary  =  effluent flow rate (dimensionless), 20 = modified Vezi rate coefficient at 20°C [(mIs) O.5 k A  =  media specific surface 3 /m 2 (m ) , which is 90 3 1m in this experiment, 2 m  D = media depth (m), 0  =  a dimensionless temperature correction coefficient, which typically equal to 1.035,  T = wastewater temperature (°C),  1 Q  =  trickling filter feed flux, defined as the primary effluent flow divided by the cross-sectional area of the trickling filter 2 1m 3 (m s ),  n = a dimensionless flow exponent, typically set to 0.5  ix  H  =  the head loss (m);  k = the head loss coefficient (m’); =  flow velocity (mis)  x  ACKNOWLEDGEMENTS First, I would like to convey my cordial appreciation to my supervisor, Dr. Pierre Bérubé, for his unreserved help, guidance and support during this research. He has been providing me with enjoyably atmosphere to learn, and bringing the realistic attitude and resourceful thinking to the pursuit of science.  I would also like to thank Susan Harper and Paula Parkinson for their infinite patience and advice in handling all analytical matters in the Environmental Lab, Bill Leung for designing and building the pilot-scale trickling filter system and adjusting the system at the site, as well as summer student Jean-Philippe Labliberté for his assistance sampling and performing the analysis in the lab.  In addition, I am really grateful to Rick Gallilee, Matthew Green, Gord Austron and all staffs in the Lions Gate WWTP for their assistance in sampling and obtaining site specific information.  Also, thank GVRD for funding this project.  Last but not least, I would like to thank my parents, relatives and all my friends for their support and care during the period of my study.  CHAPTER 1 INTRODUCTION AND RESEARCH OBJECTIVES  1.1 Site Situation and Problems Related to MBAS The Lions Gate Wastewater Treatment Plant (WWTP) was opened in 1961. It provides primary wastewater treatment for approximately 160,000 residents of the District of West Vancouver, the City of North Vancouver, and the District of North Vancouver. In 2006, the average daily flow to the Lions Gate WWTP was 92 MDL (GVRD website). At this plant, treatment consists of screening, aerated grit removal, sedimentation, disinfection and sludge digestion. Fig 1-1 shows the site map of the Lions Gate WWTP and the location of the pilot trickling filter used in the present project.  The Great Vancouver Regional District (GVRD) monitors the quality of the effluent from the Lions Gate WWTP using monthly rainbow trout bioassay. In 2003, two of the twelve monthly bioassays resulted in fish mortalities (GVRD, 2003).  Further investigation revealed that anionic surfactants, especially high molecular weight compounds, were a major contributor to the toxicity associated with the effluent (GVRD 2001, 2006; Bradley and Bérubé, 2008)  WfldSOOk  Lions Gate Site Map  Fig. 1- 1 Lions Gate WWTP site map  Muster St5500 I  Emrgonoy Shower’ Eyow005  13 13  —  2  3  A number of treatment approaches have been considered to remove anionic surfactants, measured as methylene blue active substances (MBAS) from the Lions Gate WWTP effluent.  •  Coagulation/flocculation followed by settling could remove approximately 50% of the MBAS from the Lions Gate WWTP (C1-T2MHILL, 2002). However, high coagulant does were required.  •  Air flotation could only remove up to 30% of MBAS from the Lions Gate WWTP effluent (Pu, 2005).  •  A screening study indicated that biological treatment was more effective than coagulation/flocculation and settling, as well as air flotation at reducing the MBAS induced toxicity associated with the Lions Gate WWTP effluent (Bradley and Bërubë, 2008).  1.2 Objectives of Present Study The present study, expanding on the previous research by the GVRD and UBC, was developed to investigate the feasibility of using a roughing trickling filter to reduce the MBAS induced toxicity associated with the primary effluent at the Lions Gate WWTP. Trickling filters were used since biological treatment was demonstrated to effectively reduce the MBAS induced toxicity associated with the Lions Gate WWTP effluent (Bradley and Bérubé, 2008), and in addition, GVRD has extensive experience with this technology (i.e. two of the WWTP operated by GVRD are based  on a trickling filter technology)  4  To investigate the feasibility of using a roughing trickling filter to remove anionic surfactants present in the Lions Gate WWTP effluent, the following tasks were performed.  1) An extensive literature review was performed to gain insight into MBAS biodegradation (e.g. biodegradation pathway, factors influencing biodegradation, biodegradation kinetics) in trickling filters.  2) A pilot-scale trickling filter was designed installed and operated at Lions Gate WWTP to quantify the extent of MBAS removal that can be achieved under different raw water conditions (e.g. raw water pH, DO and temperature) and operation conditions (loading rate and recycling ratio). The overall removal efficiencies were based on the difference of MBAS concentrations in the influent and effluent of the pilot-scale trickling filters.  3) The results from the pilot-scale trickling filter system were incorporated into trickling filter models, and the models were used to identify operating conditions that maximize the removal of MBAS and estimate the extent of MBAS removal that could be achieved using trickling filters.  1.3 Organization of the Thesis This thesis was organized into 7 chapters. Chapter 2 presents a summary of the previous published literature relevant to the present study. Chapter 3 describes the experimental methods and procedures used, while, Chapters 4 and 5 discuss the experimental and modeling results. Chapter 6 summarizes the implication of the results with respect to engineering practice. Chapter 7 presents the conclusions of the present study and offers recommendations for further research.  5  CHAPTER 2 LITERATURE REVIEW The types, uses, environmental impacts and removal of anionic surfactants are briefly discussed in this chapter.  2.1 Types and Usage of Surfactant Surfactants are widely used for domestic and industrial purposes, primarily as detergents in cleaning applications. However, surfactants are also extensively used as emulsifiers in various industrial applications (e.g. pesticides, print inks, pigments paints, and food production). The global surfactant consumption in 1998 was 9.4 million tons (TECL, 2002). Over 60% of this market was in North America, Western Europe and Japan. The Canadian market for surfactants in 1998 was estimated to be about 130 kilotonnes (TECL, 2002).  Surfactants can be divided into three subgroups based on their ionic charge: anionic, cationic and non-ionic (Fig. 2-1). Of these, anionic surfactants are the most commonly used commercially. The more extensive use of anionic surfactants is due to the fact that these compounds are highly biodegradable and as a result have less of a negative impact on the environment (Berna, 1985; Byran, 1988). Four types of anionic surfactants are available commercially (Fig. 2-2). Among these, linear alkyl or alkylbenzene sulphates (LAS) are the most widely used anionic surfactants due to their excellent cleaning properties. Common uses of anionic surfactants in domestic applications include laundering, dishwashing and shampooing. The commercial LAS alkyl chain lengths typically range from 10 to 14 carbon atoms (i.e. C 10 to ) 14 in the C U.S. and from 10 to 13 carbon atoms (i.e. C 10 to ) 13 in Europe (Terziá et a!., 1992; C Trehy et a!., 1996; Sanz eta!., 2003; Leon M.V. eta!., 2006).  6  e a. @ H---SO ——R—CH 3  Ne_(CH ) m3 —CH —2 3 b. CH 3 CH C.  _ 3 CH ) f 2 mO_(CH2_CHr_O)nCHr_CH (CH fl  Fig. 2- 1 Chemical structure of typical surfactants (a.Anionic; b. Caionic; c. Nonionic, R: alkyl groups, Source: Schwuger IM, 1997)  a. 9 —R---3 CH S 0  H°  3 CH  le  b. CH3—R— SO  e  H  H3 C.  d.  (CH 3 CH ) 2 m  H  0— (O) —0 —?SO  e2 — 3 S0 — C——R—OH CH 0  Fig. 2- 2 Chemical structures of typical anionic surfactants (a. LAS; b, Branched LAS; c. Alky Ether Suiphonate; d. Fatty Acids/Soaps, R: alkyl groups, Source: Swishe, 1987)  2.2 Environmental Impact of Surfactants The average surfactant concentration in the domestic wastewater varies from 1 to 10 mg/L (measured as methylene blue active substances, MBAS, Zhong et a!., 1999; Prats et a!., 2006), and can be as high as 21 mg/L (measured as MBAS, Gupta et a!., 2003). Surfactants in wastewater can decrease the oxygen transfer efficiency during wastewater treatment, and as a result, negatively affect the treatment performance (Qin et al., 2005). LAS can be toxic to aquatic organisms, such as, bacteria, algae, daphnia and fish, at concentration as low as 1 mg/L (measured as MBAS, Lewis 1990;  7  Gledhill et a!., 1991). LAS can also bio-accumulate in some fish, and eventually spread through ecosystems via the food chain (Werner and Kimerle, 1982; Gledhill. Et a!., 1991). LAS can also enhance eutrophication (Swisher, 1987). The toxicity of LAS is linked to the number of carbons in the alkyl chain (Zoller, 1998; CESIO, 2002). The grater the number of carbon atoms in the chain, the greater the toxicity. For example, the LC ’ of LAS with 12, 14 and 16 carbons in the alkyl chain for rice 50 fish are 5lmg/L, 5.9mg/L and 0.5Omg/L, respectively (Zoller, 1998).  Due to the negative impacts that anionic surfactants can have on aquatic organism, many environmental and public health regulatory authorities have established stringent limits, typically  1.0 mgIL, as MBAS, for anionic surfactants in wastewater  discharged to the environment (Adak et a!., 2005).  2.3 Treatment Methods for the Removal of Anionic Surfactants from Wastewater  A number of approaches have been considered for the removal of anionic surfactants from wastewater. These approaches are summarized in this section 2.3.1 Physical and Chemical Treatment  Air flotation was investigated as a means of removing MBAS from the Lions Gate WWTP effluent. Lab-scale screening study suggested that air flotation could achieve up to 70% MBAS removal (Bradley, 2004). However a subsequent pilot-scale study demonstrated that less than 30 % MBAS removal could be consistently achieved over extended period of time (Pu, 2005). More constant MBAS removal ranging from 50% to 70% has been reported when using coagulation-flocculation and settling to removal MBAS (Aboulhassan et a!., 2006, CH2MHILL, 2002). However, high coagulant concentrations (i.e. greater than 40 mg/L Al or Fe) were required. Oxidation has been reported to achieve high MBAS removal, ranging from 95% to (1)  Concentration at which less than 50% of organisms in a bioassay survive.  8  100% (Brambilla et a!., 1997; Lin et a!., 1999; Ikehata and El-Din, 2004; Amat et al., 2007). However, some studies have demonstrated that oxidation can increase the toxicity associated with the effluent from a WWTP (Monarca et a!., 2000; Bradley, 2004). Alumina and waste-activated carbon has also been reported to achieve high MBAS removal, ranging from 90% to 95% (Gupta et al., 2003; Adak et a!., 2005). However, this high removal efficiency could only be achieved when the concentration of MBAS was very high (i.e. several thousand ppm). The removal of MBAS electrochemically and by ionizing radiation has also been considered (Moraes et a!. 2004; Gu eta!., 2006; Kong eta!., 2006). Although these approaches show promise, it is currently not practically feasible to implement these technologies at full-scale.  2.3.2 Biological Treatment  Anionic surfactants are considered readily biodegradable under both aerobic and anaerobic conditions (Brich, 1991; Lee eta!., 1995; van Ginkel, 1996; Battersby eta!., 2001; Leon et a!., 2006). However, surfactants are typically degraded more rapidly under aerobic conditions (Bema eta!., 1989; Matthijs, 1997; Mohan eta!., 2006).  Since the anionic surfactants are so readily biodegradable, biological treatment is the most popular approach to remove these containments from wastewater. Conventional activated sludge systems have been documented to remove over 96% of anionic surfactants present in wastewaters. (Brich, 1991; Matthijs et a!., 1997, 1999; Feijtel, 1999; Battersby et a!., 2001; Leon et a!., 2006). Similar removal efficiencies to those observed for conventional activated sludge systems have been observed for membrane bioreactor systems (Dhouib,  ci’ a!.,  2005; Gonzalez, 2007). Trickling filter  systems have also been documented to effectively remove over 80% of anionic surfactants from water (Trehy et a!., 1996; Holt et a!., 1998). The results also indicated that with long hydraulic retention times (i.e. 4 to 8 days), the loading rates and recycling ratios do not substantially affect the efficiency of trickling filter at  9  removing anionic surfactants. Unfortunately, to date, no study has been performed to characterize and optimize the performance of trickling filters for removal of anionic surfactants from wastewater. Note that the present study focused on the use of roughing trickling filter to remove anionic surfactants for wastewater. Trickling filter are considered because the utility (i.e. GVRD) funding the research has extensive experience with the use of trickling filter systems for wastewater treatment process and the utility is interested in characterizing the performance of a high rate (roughing) trickling filter system.  In general, LAS with longer alkyl chains are more biodegradable (Terzic et al., 1992; Gledhill et al., 1995; Kiewiet et a!., 1997). The higher biodegradability of longer alkyl chains is linked to the higher tendency of these compounds onto absorb to biomass (Garcia et a!., 2002; Prats et a!., 2006). The biodegradation of anionic surfactants occurs primarily via a hydroxylation of the alkyl chain (Ginkel, 1995, 1996). Fig 2-3 illustrates the biodegradation pathway of dodecylbenzene sulphonate. As a result of biodegradation, high molecular weight anionic surfactants are converted to lower molecular weight anionic surfactants.  H,,CH, 3 SO ) 2 __<r__(CH  H_f__(CH) 3 SO O 2 CH 11 H  H__f__(CH) 3 SO CH,O 11  H 3 SO ) 2 nCOO1I __iJ__(CH  n__fJ__CH 3 SO c 2 oOH  Fig. 2- 3 Biodegradation pathway of dodecylbenzene suiphonate. (Source: Gin/ce!, 1996)  10  Higher biodegradation rates are typically observed when LAS is exposed to mixed bacterial cultures, rather than when exposed to pure cultures (Terzi5 et a!., 1992; Ginkel, 1996). Higher biodegradation rates are also typically observed at higher temperatures. Prats (2006) indicated that the positive effects of temperature on biodegradation are due to higher biomass growth rate and higher reaction rates at elevated temperatures. However, the degradation rate of LAS does not change substantially between 9 to 20 °C (Painter and Zabel, 1989), which is the temperature range that is typical observed in wastewater treatment system (Metcalf and Eddy, 2003). As a result, in conventional wastewater treatment systems, the removal efficiency of anionic surfactants is typically not affected by temperature (Brich, 1991; Battersby et a!., 2001; Leon et a!., 2006). The effects of other parameters, such as pH, dissolver oxygen, darkness and salinity, on the biodegradation of LAS, have also been investigated. However, these parameters were reported not to significantly affect the biodegradation of LAS over the ranges of pH, dissolver oxygen, darkness and salinity typically observed in wastewater (Quiroga and Sales, 1990).  The overall biodegradation of LAS typically follows a first order rate (Terziá et at., 1992; Lee et at., 1995; Zhang et a!., 1999; Baker eta!., 2000; Perales et a!., 2007). However, it should be noted that a few studies have reported that the biodegradation of LAS can also follow a zero order rate (Sales et at., 1987). In general, LAS biodegrade at a higher rate than other organic material present in wastewater (Matthijs, 1997)  2.4 Modeling the Performance of Trickling Filter A number of numerical relationships exist that can be used to model the  performance of trickling filters (Leslie-Grady et a!., 1999). Of these, the first order model and the modified VezI model are the most commonly used to simulate overall removal (i.e., absorption and biodegradation) of biodegradable containments from  11  wastewater using trickling filter (Leslie-Grady et a!., 1999; Parker & Merrill, 1984; Richard & Reinhart, 1986; Logan et a!., 1987a, b; Randall et a!., 1997; Raj & Murthy, 1999). The popularity of these models is largely due to their simplicity.  First Order Model The first order model was originally used to simulate the performance of trickling filters by Howland (1958). The first order model is presented in Equations (2-1) to (2-4). Equation (2-1) is the differential equation describing the first order biodegradation relationship. Equation (2-2) is the integrated form of Equation (2-1) with respect to the amount of anionic surfactants removed (i.e. C IC). Equation 0  (2-3) is the linear form of Equation (2-2), used to estimate the first order reaction rate coefficient, (k ’) graphically. Equation (2-4) is an estimate of the hydraulic retention 20 time in the trickling filter system. As presented, the performance of a trickling filter  is  a function of the flow rate and the geometry of the trickling filter media.  dC —=—kT.C =  (2-1)  e[_k200(T_2t1  cm  in_J cout  =  20 k ,.O(T_20).t  (2-2)  (2-3)  033  [()) C  =  (2-4) 67 (q)°  concentration of contaminant of interest (mg/L),  0 = concentration in the effluent (mg/L), C C kT 20 k ’ t  =  =  concentration in the influent (mg/L), first order rate constant at temperature T (hf ), 1 first order rate coefficient at 20 C (hf’)  hydraulic retention time (s),  12  =  kinetic viscosity (0.013 cm /s, measured by AV25OVAC viscosity meter, 2 angle of trickling filter plate inclination from the horizontal plane,  =  ), 2 g = acceleration of gravity (981 cm/s L = length of the flow through TF (cm), flow per unite width of TF plate (cm /cms), 3  qw  9  a dimensionless temperature correction coefficient, which typically equal to  =  1.035,  T = wastewater temperature (°C)  Modified VezI Model The modified VezI model was generated from the first order model, and incorporates the effects of the recireulation ratio, the media depth and the media surface area on the performance of trickling filters (Parker & Merrill, 1984; Richard & Reinhart, 1986; Logan et aL, 1987 a, b; Randall et aL, 1997; Raj & Murthy, 1999). The modified Vezi model is presented in Equations (2-5) and (2-6). Equations (2-5) and (2-6) are analogous to Equations (2-2) and (2-3) for the first order model.  cm  (2-5)  2 k 2 T .AS.D.O( 0) 0  —  (R+i)exp .(R 1 [Q  +  —R  %.D.e(T20)  R  =  recirculation ratio, defined as the recirculation flow rate divided by the primary effluent flow rate (dimensionless),  20 = modified Vezl rate coefficient at 20°C [(mIs) O.5 k =  (2-6)  media specific surface 3 1m 2 (m ) ,  D = media depth (m),  13  t Q  =  trickling filter feed flux, defined as the primary effluent flow divided by the cross-sectional area of the trickling filter 2 /m 3 (m s ),  n  =  a dimensionless flow exponent, typically set to 0.5  2.4.3 Knowledge Gap in Previous Studies  Although a number of studies have demonstrated that biological treatment can effectively degrade anionic surfactants, limited research attention has focused on the use of a roughing trickling filter to degrade anionic surfactants. As a result, the effect of different operation conditions (e.g. feed flow and recirculation ratio) on the removal of anionic surfactants from real wastewater is poorly understood. For this reason, the present study was developed to investigate the feasibility of using a roughing trickling filter to biodegrade anionic surfactants present in the primary effluent from the Lions Gate WWTP.  14  CHAPTER 3 MATERIALS AND METHODS  The experiments were designed to study the feasibility of using a roughing trickling filter to biologically remove anionic surfactants present in the Lions Gate Wastewater Treatment Plant (WWTP) effluent. Note that for all experiments, the concentration of anionic surfactants was measured as methylene blue active substances (MBAS). In this chapter, all aspects related to the experiments performed in this study are presented, including experimental setups, sample processing, preservation and storage, analytical procedures, and quality assurance and quality control procedures.  3.1 Lab-Scale Biodegradation Experiments  The purpose of conducting lab-scale biodegradation tests was to investigate the MBAS biodegradation rates at lab-scale under controllable conditions. For experimental conditions were considered during the lab-scale tests as presented in Table 3-1.  Table 3- 1 Lab-scale experimental conditions.  Experimental Temperature Duration conditions  (°C)  (hours)  1  14  1  2  14  3  3  20-22  1  4  20-22  3  The procedure for the lab-scale biodegradation tests is described below. •  To a 250mL flask, a 1 5OmL aliquot of the influent to the trickling filter at the Lions Gate WWTP was added.  15  The influent sample was stored in 200mL amber glass bottles and kept in a cooler (with ice packs) during transportation from the Lions Gate WWTP to the UBC Environmental Lab. Lab-scale biodegradation tests were performed immediately upon arrival at the lab. The glass amber bottles were rinsed three times with the influent before sample collection. Typical characteristics of the influent wastewater are presented in Section 3.4.  •  The flask was placed in an incubator shaker (Innova 4230, New Brunswick) for 45 minutes to allow the aliquot to reach a set temperature. Two temperatures were considered. 20-22°C, which corresponds to the average temperature of the Lions Gate WWTP influent wastewater during the summer, and 14°C which corresponds to the average temperature of the Lions Gate WWTP influent during the winter. The shaker stirred the flasks at a rate of 200rpm. A rotational speed of 200rpm is typical of the lab-scale tests performed to investigate the biodegradation of MBAS (Narkis and Zur, 1979; van Ginkel, 1996; Zhong et a!., 1999; Baker eta!., 2000; Prats eta!., 2006).  •  Approximate 0.1 5g of biomass collected from the top section of the pilot-scale trickling filter was then added to the aliquot, and the mixture was incubated. Two incubation times were considered: 1 hour and 3 hours. Although these durations are much lower than those typically used in other studies (e.g. 20 to 30 days), short incubation periods ranging from 1 to 3 hours are more compatible with the hydraulic retention times maintained in the pilot-scale trickling filter.  •  After incubation, 100 mL of the mixture was filtered through Glass Micro-fiber filter paper 691 and preserved with three to four drops of 1% (V/V) formalin and stored in fridge at 4°C, prior to MBAS analysis. The filter cake was discarded since only soluble MBAS (i.e., filtrate) was of interest in the present study. The remaining 50 mL of mixture was filtered through White Nylon 0.45 .tm filter paper and preserved with 2 drops of concentrated sulfate acid and stored in fridge  16  at 4°C, prior to COD analysis. The filter cake was discarded. The MBAS analysis and COD analysis were performed immediately after the lab-scale biodegradation tests.  3.2 Pilot-Scale Experiments A pilot-scale trickling filter was installed at the Lions Gate WWTP to study the feasibility of using a roughing trickling filter to remove anionic surfactants present in the Lions Gate WWTP effluent.  3.2.1 Pilot-scale System Setup  For the pilot-scale experiments, a roughing trickling filter was set up at the Lions Gate WWTP from October 2006 to June 2007. The pilot-scale experimental system consisted of a flow distribution bulkhead, trickling filter media, an effluent bulkhead, a feed line and a recirculation line, feed and recirculation pumps, a system tank, and a support structure, as illustrated in Fig. 3-1. The distribution bulkhead, trickling filter media and the effluent bulkhead were housed in a custom-made half-inch thick plastic enclosure.  The flow distribution bulkhead consisted of two distribution plates, perforated with 1cm diameter-holes distributed to spread the influent evenly over the trickling filter media. The dimensions of the trickling filter media were 60cm wide, by 60cm wide, by 120cm high. The trickling filter media was held in place in the plastic enclosure by four brackets. The trickling filter media used in the present study was cross-flow plastic media. The physical properties of trickling filter media are summarized in Table 3-2.  17  Table 3- 2 Physical properties of trickling filter media used in the present study. Trickling filter media Cross-flow plastic media  Approx.  Approx.  unit weight  specific surface area  ) 3 (Kg/rn  (rn2/m3)  65  90  Void Space  Angle from horizontal  (%)  (°)  >95  60  Source: ECOfluid Systems Inc  Flow  Recirculation Line Trickling Filter Media  Overflow Line Tank Pump  Fig. 3- 1 Pilot-scale experiment flow chart.  18  The effluent bulkhead located below the trickling filter media, was approximate 15cm in height. Openings in both the flow distribution bulkhead and the effluent bulkhead enabled sufficient air movement in the trickling filter media to ensure aerobic conditions in the system.  The dimensions of the system tank were ll5cmx95cmx 60cm (Fig. 3-2 a). The system tank collected the effluent from the trickling filter. Some of the effluent from the trickling filter was recycled to the flow distribution bulkhead to maintain a given recycling ratio, while the remainder overflowed from the system (Fig. 3-2 c). The support structure consisted of high density foam covered with a plywood frame (Fig. 3-3 c). The total liquid volume in the system tank was approximately 34.4 L (Fig. 3-2 c).  19  a  Influent and biomass sampling point  enclosure  Effluent bulkhead  Flow distribution bulkhead [lelin  • wmet Effluent sampling point  Support Structure  Recirculation  Fig. 3- 2 Pilot-scale experimental setup a: East side ofTF system; b. South side of TF system; c: Recycle pooh  20  3.2.2 Pilot-scale System Operation  Six experimental conditions were considered during the pilot-scale tests as presented in Table 3-3. These experimental conditions were selected to cover the typical range of operating conditions for a roughing trickling filter (Metcalf and Eddy, 2003). For each experimental condition, the MBAS and COD removals were monitored. The pilot-scale system was acclimatized for a period of two weeks between each set of experimental conditions. The system was operated at each experimental condition for four to six weeks.  Table 3- 3 Pilot-scale experimental conditions Experimental  Influent Flow  Recycling Flow  Condition  Rate (L/min)  Rate (L/min)  1 2  200 125  3 4  120 120  0 0 60 120  5  120  6  80  180 160  3.2.3 Sampling Process  Samples of the influent to, and the effluent from, the trickling filter were collected directly from the sampling locations illustrated in Fig. 3-2 a, b. Samples were collected at 10:30 am and 8:00pm once or twice per week. The sample collection and transportation procedures used during the pilot-scale tests are the same as those used in lab-scale tests (Section 3.1). Similarly, the sample filtration, preservation and storage procedure used, prior to MBAS and COD analysis are the same as those used in lab-scale test (Section 3.1).  Biomass was periodically collected once or twice per week from the top of the trickling filter to monitor any change in the total solids (TS) and volatile solids (VS)  21  contact of the biomass over time. Some of the collected biomass was also use for the lab-scale tests. Biomass was collected with a 1.94cm diameter plastic tube at five locations within the trickling filter media (i.e. at the four corner areas and the middle area of the top of the trickling filter-Fig. A-i). During sampling, the tube was pressed tightly onto the trickling filter surface, and then slid upward. The biomass samples were placed in a pre-weighed aluminum dish and kept in a cooler (with ice packs) during transportation to the UBC Environmental Lab. At the TS and VS analysis were performed immediately.  3.3 Analytical Methods  This section described the analytical methods used in the present study as well as the data analysis processes followed. A summary of the sequence followed for solid phase extraction (SPE) as well as MBAS and chemical oxygen demand (COD) analysis is presented in Fig. 3-3.  3.3.1 MBASAnalysis  Anionic surfactants can be measured as methylene blue active substances (MBAS), which responds to any chemical containing anionic and hydrophobic groups. Anionic surfactants combine with aqueous methylene blue to form ion-pair compounds that are blue in color. These compounds can be extracted from the water and the concentration of these compounds can be measured spectrophotometrically. The resulting measure is proportional to the concentration of anionic surfactants present in the water.  The traditional MBAS method is presented in Standard Method 5540C (APHA et a!., 1992). Based on Standard Method 5540C, Chitikela et a!. (1995) developed a modified MBAS analysis, which reduced the sampling size, eliminated the use of  22  expensive glassware and decreased the consumption of chloroform. The modified MBAS method by Chitikela et a!. (1995) was used in present study. Note that the use of cationic resins as indicated by Chitikela et a!. (1995) was not necessary to obtain accurate MBAS measurements. Therefore, cationic resins were not used in present study. Based on the sublation test results (Appendix D), the sublation step does not affect the MBAS analysis and was not performed in present study prior to MBAS analysis.  23  b  [  65% tract  a  tract1 [ 1r,  9O%tct  ‘If  ] [  TotaI  ‘if  Fig. 3- 3 Flowchart of a). MBAS analysis; b). COD analysis procedures.  24  3.3.1.1 Procedure ofSPE  Solid phase extraction (SPE) was used to fractionate the MBAS present in the collected samples based on polarity (EVS, 2003). In SPE, the samples to be analyzed are first loaded onto the SPE column packing material. Then, solvents of decreasing polarity, with increasing dissolving power, can be used to separate and elute the MBAS according to polarity which is analogous to the molecular weight, since high molecular weight MBAS is more hydrophobic. A study performed by EVS (2003) demonstrated that material eluted with solution containing 65%, 75% and 90% of methanol (V/V) in water could be used to separate MBAS into low, medium and high molecular weights, respectively. The ratio of summation of the mass of MBAS eluted with the solution containing 65%, 75% and 90% methanol, to the mass of MBAS of whole samples (i.e. unfractionated) was defined as recovery for the SPE procedure. Recoveries ranging from 80% to 120% were considered to be acceptable.  SPE consisted of four steps: activation, analyte loading, column washing and analyte elution. These were performed as recommended by the SPE supplier (Supelco, 1997). A picture of the SPE experimental system is presented in Fig. 3-4. The SPE procedure is described below and summarized in Table 3-4.  25  Fig. 3- 4 Solid phase extraction apparatus  1) Activation An SPE column (Supeiclean LC-18, Supelco) was placed on one of the ports in the vacuum box, as showed in Fig. 3-4, and a vacuum (approximately -15 Kpa) was applied to the box. Approximately lmL of 100% fresh methanol (High Performance Liquid Chromatography, HPLC grade) was added to the SPE column. The stopcock was then opened slowly to let approximately half of the methanol drain out of the SPE column. The stopcock was then closed for 1 minute, allowing enough contact time for  26  the methanol to saturate the whole packing material in the SPE column. After 1 minute, the stopcock was reopened and the vacuum was resumed to let the remaining methanol drain out of the SPE column. Another lmL of 100% methanol was then added to the column. Again, half of the methanol was drained, the remainder retained for one minute, and subsequently also drained as described above. Following the addition of methanol, 1 mL of distilled de-ionized (DDI) water (generated from Alpha-Q Ultra-Pure Water System, Millipore) was added to the column, and once again half was drained, the remainder retained for one minute, and subsequently the remainder was drained. Another lmL of DDI water was then added to the column. The DDI water was again drained; however, the stopcock was closed when 1-2mm of DDI water remained on the top of the SPE column packing material.  2) Analyte Loading A 5 OmL aliquot of the sample to be analyzed was filtered with Glass Micro-fiber Filter 691. Approximately 3mL of the filtered aliquot was directly added to the SPE column and the remaining 47mL was added into the 75mL reservoir located above the SPE column, as shown in Fig. 3-4. The stopcock was then opened and set to maintain a liquid flow rate of less than 1 .5mL per minute through the SPE column. After all of the filtered aliquot had passed through the SPE column, air was passed through the SPE column for about 30 seconds until the packing material became dry. The SPE column was then immediately washed and the analyte of interest (i.e. MBAS) eluted as described below. The liquid that flowed through the SPE column during loading was discarded.  3) Column Washing Column washing was performed to remove weakly retained and entrained material from the packing material and to ensure that any anionic surfactants that may have remained in the 75mL reservoir or the top potion of the SPE column were transferred to the column material. A 40% (V/V) methanol solution was used as the washing solution. Six 1 mL aliquot of the wash solution was poured over the wall of  27  the 75mL reservoir and passed through the SPE column. Between each aliquot addition, air was passed through the SPE column for approximately 30 seconds until the packing material become dry.  4) Elution The loaded SPE column was placed above an elution vial in the sample rack (see Fig 3-4). To the SPE column, a lmL aliquot of 65% (V/V) methanol solution in water was added. The stopcock was then opened slowly to let approximately half of the 65% elution solution to drain out of the SPE column. The stopcock was then closed for 1 minute, allowing enough contact time between the elution solution and the packing material, so that the absorbed surfactants could be released into the solution. After 1 minute, the stopcock was reopened and the vacuum was resumed to let the remaining 65% elution solution drain out of the column. Air was then passed through the SPE column for approximately 30 seconds until the packing material became dry. The procedure was then repeated with another 1 mL aliquot of 65% methanol elution solution. The SPE column was then relocated above an unused elution vial and the above procedure was repeated with 2-lmL aliquot of a solution containing 75% methanol (V/V) in water, and then 2-1 mL aliquot of a solution containing 90% methanol (V/V) in water. The 65%, 75% and 90% methanol elution solutions in vials were then transferred to flasks, and made up to 25mL, 5OmL and 25mL, respectively, by adding DDI water. The 65% and 90% elutions were only made up to 25mL, rather than 5OmL, because the IvIBAS concentration in these elutions was lower than the MBAS concentration in the 75% elution. The material fraction from the 65%, 75% and 90% solution were defined as the low, medium and high molecular weight elution fractions.  28  Noted that in the SPE used in present study, the flow rate was controlled at less than 1 .5mL/min, which was lower than the flow rate used in Bradley’s (2004) study (i.e. 5mLlmin). This allowed a longer contact time between the MBAS contained in the wastewater and the packing material in SPE column. This enabled the recovery of the extraction procedure to be improved.  29  Table 3- 4 Summary of procedure of SPE 1)  2)  Activation: •  Add 1 mL of 100% methanol to the SPE column and apply the vacuum to produce a flow rate less than 1 .5mL/min through the column;  •  Stop the vacuum for 1 minute when half of the methanol has been drawn through the SPE column. Continue the vacuum and allow the remaining methanol to be drawn though the packing material;  •  Add another lmL of 100% methanol and use vacuum to let half methanol pass through, and after 1 minute, draw through the remaining half methanol;  •  Repeat the above procedure with DDI water. For the second-i mL water, stop vacuum when 1 to 2 mm of liquid remain on the top of the packing material.  Analyte Loading: • • •  3)  Filter 5OmL aliquot if wastewater sample to be analyzed and add approximately 3mL of the aliquot to the SPE column; Place the 75mL reservoir above the column and add the remaining aliquot (47mL) into it; Apply vacuum and control the flow rate of 1 .5mL/min or less until the packing material goes to dryness.  Column Washing: • •  1 1  Apply vacuum, and in succession, over the side of reservoir with six lmL of 40% methanol solutions, and let it drain through into the SPE column; Allow the packing material to go to dryness before adding the next lmL of 40% methanol.  I4 4)  Elution: • • • • • •  Position the SPE column above an elution vial; Add lmL of 65% methanol solution into the column, and apply vacuum gently until half of the 65% methanol solution drains through the packing material; Stop vacuum for at least 1 minute, and then apply vacuum again to drain through the remaining 65% methanol solution till the column goes to dryness; Add another imL of 65% methanol solution into the column and repeat the above process; Placed the SPE column above a new elution vial and repeat the above procedure using 75% and 90% methanol solution. Make the 65%, 75% and 90% eluted solution to 25mL, 5OmL and 25mL with DDI water respectively for later MBAS extraction.  30  3.3.1.2 Procedure ofMBASAnalysis  The MBAS analysis consisted of three steps: organic extraction (fresh chloroform), aqueous back-washing and measurement. The procedure of MBAS analysis is described below.  1) Organic Extraction To a 5OmL vial (vial 1), a 5mL aliquot of the sample to be analyzed was added. Then, a drop of the phenolphthalein indicator solution (standard commercial) and 1 drop of 1 N NaOH (reagent) were added (Standard Method 5540 C, APHA et a!., 1992). The vial was shaken by hand until the solution turned to a uniform pink color. One drop of 1 N 4 S0 (reagent) was added and the vial was shaken untile the pink 2 H color of the solution changed to colorless. Two mL of fresh chloroform and 2mL of methylene blue solution (Standard Method 5540 C, APHA et a!., 1992) were then added to the vial in sequence. The vial was shaken by hand for 30 seconds and then put in a GS-6 Centrifuge (BECKMAN) at about 2000rpm for 15 minutes to separate the organic and liquid phases. The chloroform, containing the surfactant-methylene blue ion pairs at the bottom of the vial, was extracted and transferred to a second vial (vial 2) with a Pasteur pipette. The organic extraction was repeated by adding a second 2mL of fresh chloroform (HPLC grade) to vial 1 and repeating the mixing, separation and extraction procedure as described above.  2) Aqueous Back-wash To the second vial (vial 2), containing the 4mL of extracted chloroform solution, 1 OmL of a aqueous wash solution (i.e., acidic buffer solution prepared according to Standard Method 5540 C, APHA et at., 1992) was added. The vial was then shaken by hand for 30 seconds before 15-mm centrifugation (BECKMAN GS-6) at about 2000rpm. The organic phase at the bottom of the second vial was extracted and transferred to a third vial (vial 3) with a Pasteur pipette. Following the aqueous back-wash, one organic back-extraction was conducted to ensure complete recovery  31  of methylene-blue anionic surfactant ion pairs by adding 2mL of fresh chloroform to vial 2 and repeating the mixing and separation procedure described above, and extracting and transferring to the third vial (vial 3).  3) Measurement To the third vial (vial 3), fresh chloroform was added to make up a volume to 2OmL. The tie-in glass tube of the 690 Spectrophotometer (TURNER) was rinsed three times, with the chloroform solution from the third vial. The tie-in glass tube was then filled with 80% of the solution from the third vial. Then, the absorbance of the chloroform solution in the third vial was measured at 652 jim and converted to an MBAS concentration value, based on the MBAS calibration curve. The overall MBAS procedure that was followed is was summarized in Table 3-5.  During MBAS analysis, the MDL of MBAS was determined based on the Standard Method 1030 E (APHA et a!., 1992). The MDL for MBAS was 0.26mg/L (see Appendix B)  Before MBAS analysis, all glassware was soaked overnight in a solution containing 10% hydrochloric acid (V/V) in water and then washed with tap water twice. All glassware was then soaked in distilled water for two hours before being washed three times with de-ionized distilled water. Finally, the washed glassware was dried at 40°C overnight.  32  Table 3- 5 Summary of procedure of MBAS analysis 1)  Organic Extraction: •  2)  •  Place a 5mL aliquot of the sample to be analyzed in the first 5OmL vial. Add I drop of the phenolphthalein indicator solution and I drop of 1 N NaOH solution in sequence, and swirl until solution turns pink;  • • •  Add one drop of 1 N 4 S0 and swirl till solution turns colorless; 2 H Add 2mL fresh chloroform and 2mL methylene blue solution, and mix for 30 seconds; Centrifuge for 15 mm at 2000rpm;  •  Use a Pasteur pipette to take out the organic phase at the bottom of the first vial, and transfer to the second vial;  •  Add another 2mL fresh chloroform to the first vial and repeat the above process.  Aqueous Backwash: •  To the second vial, add 1 OmL wash solution and mix for 30 seconds before centrifugation for 15 mm at 2000rpm;  •  Use a Pasteur pipette to take out the organic phase at the bottom of the second vial, and transfer to the third vial;  .  Add 2mL fresh chloroform to the second vial, shaking and centrifuging as above process; Use a Pasteur pipette to take out the organic phase at the bottom of the second vial, and transfer to the third vial.  •  3)  .1  Measurement: • •  ‘1(  To the third vial, containing about 6mL extracted chloroform, make up the volume to 2OmL with fresh chloroform; Measure the absorbance of the chloroform solution at 652p.m with TUNER 690 spectrophotometer.  33  3.3.2 COD Analysis  In present study, both total and dissolved COD, in the influent and the effluent to the trickling filter, were measured. COD test was carried out based on Standard Method 5220 A and C (APHA et a!., 1992). Because of the potential interference from chloride in the samples, COD reagent with mercuric sulfate was used to digest the wastewater samples. The COD concentrations measured during the present study was from 20 to 200mg/L, and as a result, the COD reagent for low concentration COD (1 to 200mg/L) was selected (Standard Method 5220 A, APHA et a!., 1992). During the COD analysis, the MDL of COD was determined based on the Standard Method 1030 E (APHA et al., 1992). The MDL for COD was 9.43mg/L (see Appendix B)  3.3.3 TS& VS Test  The total solid (TS) and volatile solid (VS) attached on the surface of the top of trickling filter were monitored to investigate the growth of biomass. The TS and VS tests were performed based on Standard Method 2540 B and 2540 E. With the known area of the sampling surface (see Section 3.2.3), the TS and VS are expressed as density, mg/cm . The average values of TS or VS density from five sampling 2 locations (Fig. A-i) are presented as the results (Appendix A).  3.3.4 Other Data Monitored On-site  During the sampling period, the temperature, pH value (300 Series OAKTON) and dissolved oxygen (DO) (Model 57 YSI) were measured on-site, for both the influent and the effluent to the pilot-scale trickling filter (Appendix A).  34  3.3.5 Data Analysis Methods  Reported removal efficiencies are based on the difference between the influent and effluent to the trickling filter. Periodically, negative removal efficiencies (i.e., for less than 10% of results) were observed. These negative removal efficiencies were not used in subsequent numerical analysis. Any outlying removal efficiencies were also not used in subsequent numerical analysis. Any removal efficiency that was not within one standard deviation of the average removal efficiency for a given set of operating condition was defined as an outlying removal efficiency  3.4 Wastewater Source  Wastewater from the Lions Gate WWTR was used in the present study. The treatment process at the Lions Gate WWTR include screening, aerated grit removal, sedimentation, disinfection and sludge digestion (see Chapter 1). The site map and the location of pilot-scale trickling filter were shown in Fig. 1-1. The pilot-scale trickling filter was operated at the Lions Gate WWTP from October, 2006 to June, 2007. The primary effluent, before addition of chlorine, was used as the influent of the pilot-scale trickling filter. Some characteristics of the raw influent wastewater to the pilot-scale trickling filter are presented in Table 3-6.  35  Table 3- 6 Characteristics of influent wastewater to the pilot-scale TF Influent to pilot-scale TF TSS (mg/L) COD (Total) (mg/L) COD (dissolved) (mg/L) BOD (mg/L) MBAS (whole) (mg/L) DO (mg/L) pH(-) Temperature (CC)  57±1.2(2)  138±135 (10:30am) 01 173±100(20:OOpm) 58 ±63 (10:30am)’ 82 ±66(20:00pm) 1 90±5(2)  3.47±0.002 (10:30am) 7.42 ±0.48 (20:OOpm) 1 6.9±0.9(1) 7.13±0.2(1) 13± 1.7”  (1): values presented are average results obtained during the present study; (2): values presented are average results obtainedfrom the Lions Gate WWTP monthly report for the period between October 2006 and June 2007; all reported ranges correspond to the 95% confidence interval ofthe measurement.  3.5 QA/QC  During the experimental period, Quality Assurance (QA) and Quality Control (QC) procedures were followed. For all analysis, either Standard Methods for the Examination of Water and Wastewater (APHA et a!., 1992), or well-documented analytical methods (Chitikela et a! 1995; Bradley 2004) were followed. Field blanks containing analyte-free samples, (DDI water), were taken from the UBC Environmental laboratory and were exposed to the sampling environment at the sampling site. These samples were then subject to MBAS and COD analysis. Field blank results for the MBAS analysis were close to the MDL of MBAS, and for the COD analysis were lower than the MDL of COD (Appendix B). Experimental blanks containing analyte-free samples (DDI water) were subject to MBAS and COD analysis. Experimental blank for the MBAS analysis were close to MDL, and for the COD analysis were lower than MDL (Appendix B). Duplicate or triplicate analyses were performed on randomly selected samples for MBAS and COD analysis.  36  CHAPTER 4 RESULTS AND DISSCUSSIONS In the present study, lab-scale and pilot-scale experiments were conducted to investigate the feasibility of using roughing trickling filter to remove anionic surfactants measured as methylene blue active substances (MBAS) in the primary effluent from the Lions Gate Wastewater Treatment Plant (WWTP). The raw data of each individual sampling event are presented in Appendix A.  4.1 Lab-scale Biodegradation Experiments  Lab-scale experiments were performed to study the biodegradation of MBAS under controlled conditions as described in Section 3.1. Two lab-scale biodegradation tests were performed on May  th 14  2007 and June  th 12  2007. The raw data collected  during the lab-scale experiments are presented in Appendix A-I.  Note that the MBAS recoveries for the lab-scale tests, performed at 20-22°C with a 3 hour detention time, were relatively low, (i.e. 88 to 92%). For this reason, the results from this experiment are not included in the discussion below.  The MBAS removal observed during the lab-scale biodegradation experiments are presented in Figure 4-1. The results suggested that over the temperature range investigated (i.e., 14°C to 20-22°C), temperature did not significantly affect the biological removal of MBAS. This result is consistent with those observed by Painter and Zabel (1989), who reported that the biodegradation of LAS does not change substantially between 9 and 20°C.  37  80% e  40%  D14°C,lh D20C,1h  20%  020”C,3hs  -20% Total  LMW  1MW  11MW  Fig. 4- 1 Average removal efficiency of MBAS in lab-scale biodegradation tests (The total L MW I MW and H MW correspond to the whole sample, the 65% SPE column extract, the 75% SPE column extract and the 90% SPE column extract respectively; Error bars correspond to 95% confidence interval ofthe average MBAS removal efficiency.)  Other than for the low molecular weight MBAS, the extent of MBAS removal increased over time. This was expected since the removal of MBAS has typically been reported to follow a first order biodegradation rate (Terzió eta!., 1992; Lee et at., 1995; Zhang et at., 1999; Baker et at., 2000; Perales et at., 2007). As presented in Figure 4-1, the concentration of low molecular weight MBAS actually increase during the lab-scale biodegradation experiments. The increase in the concentration of low molecular weight MBAS is likely linked to the fact that during biodegradation, higher molecular weight MBAS is converted to lower molecular weight MBAS (Ginkel, 1996). This lower molecular weight MBAS can accumulated in the system since it has a relatively low biodegradation rate (Terzic et a!., 1992; Gledhill et at., 1995; Kiewiet  etaL, 1997).  Assuming that the biodegradation of MBAS follows a first order rate, as suggested by Terzié eta!., (1992), Lee et at., (1995), Zhang eta!., (1999) Baker eta!., (2000), Perales et at., (2007), the biodegradation rates for MBAS were estimated (Table 4-1). The biodegradation rate coefficient was highest for high molecular weight  38  MBAS. These results are consistent with those from previous research by others (Terzic et a!., 1992; Gledhill et a!., 1995; Kiewiet et al., 1997). The first order biodegradation rate coefficient values obtain from present study also agreed with those obtained from previous studies by others, which ranged from 0.00075 to 0.4 hf’ (Terzic et aL, 1992; Gledhill et a!., 1995; Kiewiet et at., 1997). It should be noted that the first order biodegradation rate coefficients depend on the amount of biomass used during the lab-scale biodegradation experiments. Therefore, care must be taken when comparing biodegradation rate coefficients obtained from different studies. As previously discussed, in the present study, approximately 0.1 5g of biomass was added to each of the flasks used in the lab-scale biodegradation experiments. The biodegradation rate coefficient for the low molecular weight MBAS was likely not negative. The apparent negative biodegradation rate coefficient was likely link to the fact that during the biodegradation, high molecular weight MBAS was converted to low molecular weight MBAS as previously discussed.  Table 4- 1 The first order model rate coefficients from the lab-scale experiments Component  20 value (hf’) k’  Total MBAS  -0.13±0.037  HMW MBAS  -0.53±0.24  1MW MBAS  -0.10±0.11  LMW MBAS  0.027±0.042  COD  -0.22±0.16  (The total, LMJ 1MW and HMW correspond to the whole sample, the 65% SPE column extract; the 75% SPE column extract and the 90% SPE column extract respectively,• ± correspond to 95% confidence interval of estimated rates; k’ 20 estimated using a temperature correction coefficient of 1.035)  The COD removal observed during the lab-scale biodegradation experiments are presented in Fig. 4-2. As observed for MBAS, over the range of temperature (i.e. 14’C to 22 ‘C), temperature did not significantly affect the removal of COD. However, unlikely for MBAS, the extent of COD removal did not increase over time.  39  Unfortunately, based on the data, it was not possible to determine why the extent of COD removal did not increase with time. The first order biodegradation rate coefficients for COD estimated from the present study are consistent with those reported in literature by others, which ranged from 0.03 to 1.0 hr’ with high activated sludge concentrations (i.e. approximately 120 to 500 mg/L; Ginestet et a!., 2002; Coulibaly et at., 2006; Yildiz et a!., 2008). As previously discussed, the first order biodegradation rate coefficients depend on the amount of biomass used during the lab-scale biodegradation experiments, and therefore, care should be taken when comparing biodegradation rate coefficients obtained from different studied.  40%  30% D14C  20%  D20°C  :32.65•  E  2691 22.02  10%  0%  —  —  1 hour  —  —  —  3 hours  Incubation time (h)  Fig. 4- 2 Average removal efficiency of COD in lab-scale biodegradation tests (Error bars correspond to the highest and lowest values of COD removal efficiencies)  The overall biodegradation rate of the MBAS was slightly lower than that of the COD (Table 4-1, i.e. not significantly different based on a 95% confidence interval), which is different from the results obtained from previous studies by others (Terzic et a!., 1992; Gledhill et at., 1995; Kiewiet eta!., 1997). This difference is likely linked to the fact that mixtures of various MBAS were present in the wastewater used in the lab-scale experiments and some of the MBAS compounds, such as the lower molecular weight MBAS, likely had a biodegradation rates that were lower than that  40  for COD. On the other hand, the biodegradation rates of the high molecular MBAS  was similar to that of the COD (i.e. not significantly different based on a 95% confidence interval), which is in agreement with the results from previous studies by others (Berna et aL, 1989).  4.2 Pilot-scale Experiments Pilot-scale experiments were performed to study the feasibility using a roughing trickling filter to remove MBAS in the primary effluent at the Lions Gate WWTP under different operating conditions (Section 3.2.2). The pilot-scale experiments were performed over the period from October 2006 to June 2007. The raw data collected during the pilot-scale experiments are presented in Appendix A-TI.  4.2.1 MBAS Removal  The removal of biodegradable material in a trickling filter is a function of the contact time between the wastewater being treated, as well as the amount and activity of biomass attached to the trickling filter. Two relationships are commonly used to model the removal of contaminants in a trickling filter: The first order model and the modified Vezl model. In the first order model, the contact time is estimated based on the overall flow through the trickling filter (Section 2.4.1). For the modified Vezl model, the contact time is estimated based on the overall flow through the trickling filter as well as the recycling flow (Section 2.4.2).  The removal of MBAS for different experimental conditions was incorporated into the first order model and the modified Vezl model, as presented in Figure 4-3. For both the total MBAS, as well as for the different molecular weight fractions, better agreement (i.e. high R ) was observed between the experimental data and the 2 modified Vezi model, than between the experimental data and the first order model.  41  This was expected since the first order model does not consider the effect of the recycling ratio on the contact time between the wastewater being treated and the biomass attached to the trickling filter. For this reason, the modified Vezl model was used to interpret the data obtained during the pilot-scale experiments. 0.30 0.25 — —  0.20  2 (R  =  0.97)  • HMW  2 (R  =  0.82)  =  a)  0.95)  El Total ALMW )I( 1MW  2O58)  0.15  • 0.10 0.05 0.00 1  0  4  3  2 t 20 1.O35°  0.20  )t( 1MW  (R = 2 0.91) 2 = 0.98) (R 2 = 0.98) (R  • HMW  2 (R  —ElTotal 0.15  — —  —  -—  A LMW  =  b)  0.99)  0.10 U  ci 0.05  0.00 0  200  400  600  800  1000  1200  5 AsD/[Qj(R+1)J° 20 1.O35°  Fig. 4-3 MBAS removal a). First order model; b). Modified Vezi model (The total, LM 1MW and HMW correspond to the whole sample, the 65% SPE column extract, the 75% SPE column extract and the 90% SPE column extract respectively)  42  The modified Vezl model rate coefficient at 20°C (k ) for MBAS estimated form 20 the data collected for all experimental conditions is presented in Table 4-2. In general, the high molecular weight MBAS was the most biodegradable, followed by the intermediate molecular weight MBAS and the low molecular weight MBAS. Under the pilot-scale experimental conditions, approximately 11.75% to 29.09% of high molecular weight MBAS, 0.8 1% to 17.36% of the intermediate molecular weight MBAS and 2.18%-8.89% of the low molecular weight MBAS was removed. When considering all molecular weight fractions, the total MBAS removal efficiency was 6.15% to 10.73%. However, it should be noted that the difference between the modified Vezl model rate coefficient at 20°C for the high molecular weight and intermediate molecular weight MBAS was not statistically significant. Studies by others have also reported that high molecular weight MBAS are the more biodegradable than lower molecular weight MBAS (Terzic et al., 1992; Gledhill et al., 1995; Kiewiet eta!., 1997).  Table 4- 2 Summary of modified Vezl model rate coefficients from the pilot-scale experiments Components  3 20 value ([rn/si 0.5) x10 k  Total MBAS  -0.0533±0.0057  FIMW MBAS  -0.0884±0.0048  1MW MBAS  -0.0767±0.011  LMW MBAS  -0.0601±0.0030  COD  -0.12±0.011  (All ranges correspond to 95% confidence ofestimated rate coefficients; 20 estimated using a temperature correction coefficient of 1.035) Ic  4.2.2 COD Removal  Under the pilot-scale experimental conditions, approximately 4.87% to 22.98% of COD was removed. The removal of COD for different experimental conditions was incorporated into the first order model and the modified Vezl model, as presented in  43  Figure 4-4. As presented in Fig. 4-4, both first order model and modified Vezl model showed good agreement with experimental data (i.e., R =O.95 for first order model 2 and R =O.96 for modified Vezl model). Since the modified Vezi model was used to 2 ) was observed 2 interpret the MBAS data, and slightly better agreement (i.e. higher R between the experimental data and the modified Vezl model, than between the experimental data and the first order model, the modified Vezi model was also used to interpret the COD data.  0.30  0.20 L) U  0.10  0.00  o  2.5  1.5  1  0.5  (T-20) 1035  0.20  0.15 +  -  0.10  0.05  0.00 0  200  400  600  )AsD/[Q ,(R+ 20 1 .035(T  800  1000  )]O5 1  Fig. 4-4 COD removal a). First order model; b). Modified Vezl model  1200  44  The overall COD biodegradation rate (i.e., the modified Vezl rate coefficient at 20CC) observed in the present study is approximately two to five times less than those reported in literature (Park and Merrill, 1984; Raj and Murthy, 1999). However, in the present study, the system was operated as a high rate roughing trickling filter with organic loading rates ranging from 13.3 to 53.2 kgCOD/m .d, while the trickling 3 filters used in studies by others were operated at much lower organic loading rates ranging from 0.54 to 4.45 kgCOD/m .d (Raj and Murthy, 1999). For typical 3 wastewater, overall COD removal efficiencies ranging from 50 to 90% can typically be achieved with trickling filters with organic loading rate ranging from 0.4 to 2.4 .d, while the overall COD removal efficiency that can typically be 3 kgCOD/m achieved in a high rate roughing trickling filter are less than 20% (Metcalf and Eddy, 2003).  As observed during the lab-scale experiments, the overall biodegradation rate of MBAS (i.e. total MBAS) was lower than that of COD (Table 4-2). As observed for the lab-scale experiments, this was likely linked to the fact that mixture of various MBAS were present in the wastewater used in the pilot-scale experiments, and some of the MBAS compounds, such as lower molecular weight MBAS likely had biodegradation rates that were lower than that of COD. Unlike for the lab-scale experiments, the biodegradation rate of the high molecular weight MBAS was lower than that of COD (i.e. recall that the biodegradation rates estimated during the lab-scale experiments for HMW MBAS and COD were relatively similar). However, the biodegradation rates for the high molecular weight MBAS and COD were in the same order of magnitude. The results from both lab and pilot scale experiments suggested that the extent of removal of high molecular weight MBAS, which is the most toxic MBAS fraction, should be comparable to the extent to which COD can be removed in a high rate trickling filter.  45  CHAPTER 5 IMPLICATIONS OF RESULTS TO PROCESS ENGINEERING  Using the results from the pilot-scale experiments, the modified Vezl model was used to estimate the size of a trickling filter that is needed to achieve a given removal efficiency for anionic surfactants in the primary effluent from the Lions Gate WWTP. The parameters used to calculate the estimated size are presented in Table 5-1. Typical operation conditions (i.e., depth and recycling ratio) for a high rate trickling were selected to estimate the size of the trickling filter (Metcalf and Eddy, 2003). Trickling filter sizes were estimated to achieve a given removal efficiency for high molecular weight MBAS, total MBAS and COD (Figure 5-1).  Table 5- 1 Summary of parameters used for calculation Variables  Values  Description  R  Recycling ratio  1.5  A  Media specific surface 3 /m 2 (m )  90  D  Depth of trickling filter (m)  4  0  dimensionless temperature correction coefficient  1.035  T  Wastewater temperature (°(D)  I 5•5(1)  Q  Primary effluent flow (m /s) 3  1 .0648’ HMW MBAS  20 k  modified Vezl model coefficient at 20t [(mis) O.5j  Total MBAS COD  =  =  =  Concentration of contaminant of interest in the influent and effluent from the trickling filter 1 C Modified Vezl model  In  + R  C R+  .D.O(T20) =  1  (1): average values at Lions Gate WWTP in 2006 (GVRD, 2006)  0.0000533  0.000 12  0 C  20 k [Q(R +  1)1°  0.0000884  46  In the present pilot-scale experiments, COD removals of 4.87% to 22.98% were achieved. This is consistent with the COD removal range that can typically be achieved using a roughing trickling filter (Metcalf and Eddy, 2003). For the pilot-scale experiments, the total MBAS and high molecular weight MBAS removal ranged from 6.15% to 10.73% and 11.75% to 29.09%, respectively. To achieve comparable removal efficiencies when treating all of the primary effluent from the Lions Gate WWTP would require a trickling filter with a surface area of approximately 100 m . To achieve high removal efficiencies, say the removal of 50% 2 of most toxic fraction of MBAS (i.e. high molecular weight MBAS), the surface area of trickling filter required would be approximately 400m 2 (Figure 5-1).  60  -4o  0  100  200  300  400  500  600  700  ) 2 Trickling filter surface area (m ) for a trickling filter 2 Fig 5- 1 Fraction removed as a function of surface area (m  Based on the modified Vezl model, seven parameters, recycling ratio, trickling filter media specific surface, depth of trickling filter, flow rate, wastewater temperature, modified Vezl model rate coefficient and temperature correction coefficient; can affect the required trickling filter surface area that is needed to achieve a desired MBAS removal efficiency. Figure 5-2 presents how each parameter can affect the required trickling filter surface area needed to achieve a removal of 50%  47  of the most toxic fraction of IvIBAS. Figure 5-2 indicates that increasing in recycling ratio, wastewater temperature, modified VezI model rate coefficient, trickling filter media specific surface and depth, or decreasing in flow rate and temperature correction coefficient would reduce the area of trickling filter that needed to remove the MBAS. Among all the parameters in modified Vezi model, temperature correction coefficient, the trickling filter media specific surface and the depth of the filter media have the greatest effect on the trickling filter surface area that is needed to achieve a desired MBAS removal efficiency.  500  .\/ t4:3  -o—Q —*-—As, Dor k 20 —*E---  T  0  -100 -60  -30  0  30  60  Change in parameters of interest (%)  Fig 5- 2 Sensitivity analysis of parameters in the modified Vezi model.  Due to the relatively large trickling filter surface area required to remove a substantial amount of the MBAS (e.g. 50%) present in the primary effluent from the Lions Gate WWTP and the lack of land available in the vicinity of the Lions Gate WWTP it does not appear that a trickling filter is a feasibility option to address the MBAS included toxicity associated with the Lions Gate WWTP effluent.  48  CHAPTER 6 CONCLUSIONS  1) The lab-scale experiments demonstrated that high molecular weight MBAS was more biodegradable than the low molecular weight MBAS.  2) The lab-scale experiments suggest that during the biodegradation, the molecular weight of MBAS decreases.  3) The pilot-scale experiments demonstrate that the MBAS removal efficiencies increase with increasing recirculation ratio and decreasing flow rate. The overall removal of total IvIBAS that could be achieved with the roughing trickling filter ranged from 6.15% to 10.73%. The high molecular weight MBAS was the most biodegradable MBAS fraction, achieving 11.75% to 29.09% removal.  4) The data collected from the pilot-scale experiments could be effectively modeled using the modified Vezl relationship. The modified Vezi rate coefficients for the total MBAS, high MW MBAS, intermediate MW MBAS and low MW MBAS were 0.000053 3, 0.0000884, 0.0000767, 0.000060 1 [mIs] 0.5 respectively.  5) Although a roughing trickling filter can remove MBAS, a relatively large trickling filter area would be required to achieve a relatively high MBAS removal efficiency. 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Zhong C. L., Valsaraj T. K., Constant W. D. and Roy D., Aerobic Biodegradation Kinetics of Four Anionic and Nonionic Surfactants at Sub- and Supra-critical Micelle Concentrations (CMCs), Water Research, Vol. 33, No. 1, pp. 115-124, 1999. Zoller U. Handbook of Detergents Part B: Environmental Impact. Surfactant Science Series 121. Marcel Dekker, Inc. New York, 1998.  65.4 26.91%  65.4  63.0  65.4  60.5  86.2  Dissolved COD  105.38% 107.89%  106.47%  102.79%  101.44%  Recovery rate  0.50 0.45  3.40  3.94  7.44  0.36 mg/L 42.86%  0.48  0.48  0.47  0.84  90%  3.65  7.22  3.69  3.68  3.93  3.42  3.91  75%  -3.23%  -0.1 3mg/L  8.62%  0.72mg/L  2#  0.24mg/L 5.88%  3.84  3.82  3.85  3.72  65%  7.63  7.73  7.53  8.35  1#  (mgfL) 2#  (mg/L)  (mg/L)  (mg/L) 1#  Incubation at 20 C  Average Removal  Average  Incubation at 14 C  Influent  whole  MBAS  Incubation test for 1 hour (8pm)  Table A-i Lab-scale experimental results on May 15, 2007  Appendix A-I Lab-scale Experimental Data  APPENDIX A: RAW DATA  65.4  0.48  3.54  3.80  24.13%  0.36 mg/L 41.67%  0.37 mg/L 9.46%  -0.O8mg/L -2.15%  1.02 mg/L 12.22%  (mg/L)  7.33  Average Removal  Average  57  83.7  108.1  Dissolved COD  84.9  22.02%  76.4  109.84% 107.98%  92.35%  88.02%  95.08%  Recovery rate 84.3  0.41  0.47  0.51 mg/L 39.23%  0.79  0.75  0.82  1.30  90%  2.67  1.00 mg/L 25.58%  2.91  3.00  2.82  3.91  75%  69.1  2.52  2.33  2.27  2.53  2.46  2.14  65%  -0.36mg/L -16.82%  6.80  6.93  7.73  4.88  2#  2.50  1#  (mg/L)  Incubation at 20 C  5.01  (mg/L) 0.86 mg/L 11.12%  Average Removal  Average  6.87  2#  Incubation at 14 C (mg/L)  whole  (mg/L)  Influent  Incubation test for 3 hours (1pm)  Table A-2 Lab-scale experimental results on June 12, 2007  72.8  0.44  2.60  2.30  4.95  Average (mg/L)  Average  32.65%  0.86 mgIL 66.15%  1.31 mg/L 33.50%  -0.l6mg/L -7.48%  2.78 mg/L 35.96%  Removal  58  59  Appendix A-Il Pilot-scale Experimental Data:  Table A-3 MBAS and COD analysis results on 17 Nov 2006 Sampling date: 17 Nov, 2006, 11:00am Flow rate: 197.4LImin, 284.3m 1d 3 Hydraulic loading 2 1 3 (m . d): m 7.31 Organic loading (kgBOD/m .d): 17.4 3 Air temperature: 9.5CC Raining No circulation DO (mg/L) pH Temperature(t)  Influent Effluent 6.2 6.8 7.01  7.19  13.5  13.5  COD concentration (mg/L) Influent Effluent Removal rate Total Dissolved  146.0  179.5  52.9  57.7  -22.94% -9.07%  MBAS concentration (mgfL) Influent Effluent Removal rate Whole  2.58  2.38  65% 75% 90%  1.07 1.34  1.08 1.37 0.43  Recovery rate  0.59 116.3% 121.0%  7.75% -0.93% -2.24% 27.12%  60  Table A-4 MBAS and COD analysis results on 05 Dec 2006 Sampling time: 05 Dcc, 2006, 11:00 am  Sampling time: 05 Dec, 2006, 8:30 pm  Flow rate: 201.3 L/min, 290m /d 3 Hydraulic loading 2 1 3 (m . d): m 7.46  290m 1 d Flow rate: 201.3 L/min, 3 Hydraulic loading 2 /d): 3 (m . m 7.46  Organic loading (kgBOD/m .d): 26.6 3 Air temperature: 7.2 C  Air temperature: 9 0  No raining  No raining  No circulation  No circulation  DO (mg/L) pH Temperature(°C)  Influent Effluent 7.2 7.4 7.19 7.35 13  Organic loading (kgBOD/m .d): 26.6 3  DO (mg/L)  pH  13  Temperature( C)  Influent Effluent 7.1 6.8 7.26 7.11 13  13  COD concentration (mgIL) Influent Effluent Removal rate Total  169.9  Dissolved  72  193.8 -14.06%±8.01% 81.6  -13.33%±7.97%  Total Dissolved  Influent Effluent Removal rate -6.27% 191.4 203.4 86.3  88.7  -2.78%  MBAS concentration (mg/L) Whole 65% 75% 90% Recovery rate  Influent Effluent Removal rate 3.16 3.36 5.95%±2.48% 1.68 1.52 9.52%±5.87% 1.34  1.28  4.48%±3.80%  0.39  0.42  -7.69%±5.08%  101.5% 101.9%  Whole 65% 75% 90% Recovery rate  Influent Effluent Removal rate 7.9% 6.18 6.71 1.14% 2.63 2.6 3.24 0.86  3.29  -1.54%  0.58  32.56%  100.3% 104.7%  61  Table A-5 MBAS and COD analysis results on 12 Dec 2006 Sampling time: 12 Dcc, 2006, 10:30 am Flow rate: 105.4 L/min, 151.8 m /d 3 Hydraulic loading 2 /d): 3 (m . m 3.9 Organic loading (kgBOD/m .d): 15.6 3  Sampling time: 12 Dec, 2006, 8:30 pm Flow rate: 210.8 L/min, 303.6 m /d 3 Hydraulic loading 2 1 3 (m . d): m 7.81 Organic loading (kgBOD/m .d): 31.1 3  Air temperature: 9 C No raining  Air temperature: 9.2 C No raining  No circulation  No circulation Influent Effluent  Influent Effluent  DO (mg/L)  6.4  6.7  DO (mg/L)  6.5  6.8  pH  7.22  7.31  pH  7.2  7.28  Temperature(°C)  11.5  11.5  Temperature(t)  11.5  11.5  Total Dissolved  COD concentration (mgIL) Influent Effluent Removal rate 215.5 166.7 22.6% Total 86.2  71.5  17.1%  Dissolved  Influent Effluent Removal rate -14.4% 186.2 213.1 -18.8% 108.1 91  MBAS concentration (mg/L) Whole 65%  Influent Effluent Removal rate 3.33 3.24 2.7% 1.30 1.31 -0.7%  Whole 65%  Influent Effluent Removal rate 3.26% 5.94 6.14 -1.00% 2.05 2.03  75%  2.05  2.00  2.4%  75%  3.53  3.44  90%  0.58  0.58  0.00%  90%  1.34  0.97  Recovery rate  118.0% 119.8%  Recovery rate  112.4% 108.8%  2.55% 27.6%  62  Table A-6 MBAS and COD analysis results on 3 Jan 2007 Sampling time: 3 Jan 2007, 10:30 am Flow rate: 133.4 L/min, 192.1 m /d 3 Hydraulic loading 2 1 3 (m . d): m 4.94  Sampling time: 3 Jan 2007, 8:30 pm /d 3 Flow rate: 133.4 L/min, 192.1 m 1 3 (m . d): m 4.94 Elydraulic loading 2  Organic loading (kgBOD/m .d): 17.3 3 Air temperature: 11 ‘C No raining  Organic loading (kgBOD/m .d): 17.3 3  No circulation  No circulation  ir temperature: 9.5 °C ‘o raining Influent Effluent  Influent Effluent DO (mg/L)  7.8 7.04  8  DO (mg/L)  7  7.3  pH  7.18  pH  6.91  7.09  Temperature(t)  11  11  Temperature(t)  11.5  11.5  Total Dissolved  COD concentration (mgfL) Influent Effluent Removal rate 159.4 149.6 6.15%±5.43% Total 59.3  78.8  -32.88%±ll.42%  Dissolved  Influent Effluent Removal rate 5.21% 186.2 176.5 -5.11% 100.8 95.9  MBAS concentration (mg/L) Influent Effluent Whole  2.63  2.32  65%  1.2  75% 90%  1.06 0.44  Removal rate Whole  1.13  11.79%±2.78% 5.83%±2.05%  1.19 0.33  -12.26%±2.06% 25.00%±8.25%  75% 90%  Recovery rate 102.7% 114.2%  65%  Recovery rate  Influent Effluent Removal rate 6.08% 5.72 6.09 6.3% 2.43 2.28 2.85 0.95  3.09 0.66  -8.42% 30.53%  102.3% 105.4%  Table A-7 TS and VS analysis results on 3 Jan 2007 Sampling area: 5.912 cm 2  Locations TS (mg) VS (mg) VS/TS  1 16.5 15.2 92.12%  2 19.8 17.4  3 21.2 18.9  87.88%  89.15%  4 21.3  5 25.1  19.3 90.61%  22.3 88.84%  Average (mg)  Standard deviation  Density (mgI cm ) 2  20.8 18.6  3.1 2.6  3.52  89.61%  3.15  63  Table A-8 MBAS and COD analysis results on 17 Jan 2007 Sampling time: 17 Jan 2007, 10:30 am Flow rate: 133.4 L/min, 192.1 m /d 3 Hydraulic loading 2 /d): 3 (m . m 4.94  Sampling time: 17 Jan 2007, 8:00 pm Id 3 ‘low rate: 133.4 Llmin, 192.1 m lydraulic loading 2 1 3 (m . d): m 4.94  Organic loading (kgBOD/m .d): 15.1 3 Air temperature: 9 C  )rganic loading (kgBOD/m .d): 15.1 3 \ir temperature: 7 C  No raining  ‘To raining  No circulation  ‘To circulation  DO (mg/L)  Influent Effluent 6.2 7  Influent Effluent DO (mg/L)  6.5  6.8  pH  7.29  7.38  pH  7.19  7.38  Temperature(°C)  11.5  11.5  Temperature(°C)  12  12  COD concentration (mg/L) Influent Effluent Removal rate 110.6 120.3 -8.77%±5.43%  Total Dissolved  56.9  52.0  8.61%±11.42%  Influent Effluent Removal rate 169.1 9.18% 186.2  Total Dissolved  76.4  78.8  3.05%  MBAS concentration (mgfL) Influent Effluent Removal rate 3.27 3.2 2.14%±2.78%  Whole  Influent Effluent Removal rate 3.24% 7.46 7.71  Whole  65% 75%  1.77  1.56  11.86%±2.05%  65%  2.6  2.45  1.39  1.50  75%  4.08  4.13  90%  0.33  0.3  -7.91%±2.06% 9.1%±8.25%  5.77% -1.22%  90%  1.46  0.93  36.3%  Recovery rate  106.7% 114.2%  Recovery rate  105.6% 100.7%  Table A-9 TS and VS analysis results on 17 Jan 2007 Sampling area: 5.912 cm 2 Locations TS (mg) VS (mg) VS/TS  1 26.8 23.3 86.94%  2 27.3 22.7 83.15%  3 28.5 23.4 82.11%  4 22.4 19.5 87.05%  5 29.6 25.4 85.81%  Average  Standard  (mg)  deviation  26.9  2.75 2.14  22.9 84.92%  Density cm ) (mgI 2 4.55 3.87  64  Table A-i0 MBAS and COD analysis results on 23 Jan 2007 Sampling time: 23 Jan 2007, 10:30 am Flow rate: 123 L/min, 177.1 m /d 3 Hydraulic loading 2 1 3 (m . d): m 4.56 Organic loading (kgBOD/m .d): 8.4 3 Air temperature: 11.5 C Raining  Sampling time: 23 Jan 2007, 8:00 pm low rate: 123 Llmin, 177.1 m Id 3  No circulation  ‘o circulation  /d): 3 (m . m 4.56 lydraulic loading 2 Organic loading (kgBOD/m .d): 8.4 3 ir temperature: 9 C ot raining  Influent Effluent 8.5 8.8  DO (mg/L)  Influent Effluent 8.4 8.8 6.84 7.03  DO (mg/L)  pH  6.89  7.00  pH  Temperature(t)  9.5  9.5  Temperature(t)  9.5  9.5  COD concentration (mg/L) Influent Effluent Total  88.6  Dissolved  37.3  86.2  Removal rate 2.71%±5.43%  Total  42.2  -13.14%±11.42%  Dissolved  Influent Effluent Removal rate 108.1 -5.98% 102 44.7  35.6  20.36%  MBAS concentration (mg/L) Influent Effluent  Influent Effluent Removal rate  Removal rate  Whole  2.80  2.49  11.07%±2.78%  Whole  4.90  4.35  11.22%  65%  1.13  1.07  5.31%±2.05%  65%  1.68  6.55%  75% 90%  1.46  -7.53%±2.06% 20.00%±8.25%  75% 90%  2.25  -7.11%  0.40  1.57 0.32  1.57 2.41  0.88  0.75  14.77%  Recovery rate 106.8% 118.9%  Recovery rate  98.2% 108.7%  Table A-il TS and VS analysis results on 23 Jan 2007 Sampling area: 5.912 cm 2 Locations  1  TS (mg) VS (mg) VSITS  18.6 15.9 85.48%  2 34.3 28.5 83.09%  3 28.8 24.4 84.72%  4 22.5 18.9 84.00%  5 29.3 25.4 86.69%  Average  Standard  (mg)  deviation  Density ) 2 (mgI cm  26.7 22.6 84.72%  6.17 5.11  4.52 3.82  65  Table A-12 MBAS and COD analysis results on 29 Jan 2007 Sampling time: 29 Jan 2007, 10:30 am Flow rate: 110.7 L/min, 159.4 m Id 3 Hydraulic loading 2 /d): 3 (m . m 4.1  Sampling time: 29 Jan 2007, 8:00 pm /d 3 Flow rate: 110.7 L/min, 159.4 m Flydraulic loading 2 1 3 (m . d): m 4.1 Organic loading (kgBOD/m .d): 15.2 3  Organic loading (kgBOD/m .d): 15.2 3 Air temperature: 5 C No raining  ir temperature: 8 C ‘o raining  No circulation  o circulation Influent Effluent  Influent Effluent 7.5 7.0  DO (mg/L)  6.8  7.5  DO (mg/L)  pH  7.15  7.24  pH  7.07  7.22  Temperature(C)  11  11  Temperature( C)  11  11  Influent Effluent  COD concentration (mg/L) Removal rate  Total  139.9  154.5  -10.44%±5.43%  Total  Dissolved  59.3  70.3  -21.61%±11.42%  Dissolved  Influent Effluent Removal rate 166.7 9.3% 183.8 105.7  105.7  0%  MBAS concentration (mg/L) Influent Effluent Whole 65%  3.51 1.26  3.27 1.16  Removal rate 6.84%±2.78% 7.94%±2.05%  Whole 65%  75% 90%  2.00 0.44  2.14 0.32  -7.00%+2.06% 27.27%±8.25%  75% 90%  Recovery rate 105.4% 110.7%  Influent Effluent Removal rate 2.02% 8.41 8.24 13.33% 2.55 2.21 4.17 2.01  Recovery rate  4.55 1.82  -9.11% 9.45%  103.6% 104.3%  Table A-13 TS and VS analysis results on 29 Jan 2007 Sampling area: 5.912 cm 2 Locations TS (mg) VS (mg) VS/TS  1 28.0 25.4 90.71%  2 23.9 20.2 84.51%  3 36.8 31.1 84.51%  4 25.8 22.5 87.21%  5 27.7 24.3 87.73%  Average (mg)  Standard deviation  Density ) 2 (mgI cm  28.4 24.7 86.85%  4.80 4.18  4.80 4.18  66  Table A-14 MBAS and COD analysis results on 20 Feb 2007 Sampling time: 20 Feb 2007, 10:30 am Flow rate: 123 L/min, 177.1 m Id 3  ;ampling time: 20 Feb 2007, 8:00 pm low rate: 123 L/min, 177.1 m /d 3  Hydraulic loading 2 /d): 3 (m . m 4.56 Organic loading (kgBODfm .d): 6.66 3 Air temperature: 7.5 ,C  /d): 3 (m . m 4.56 lydraulic loading 2 .d): 6.66 3 )rganic loading (kgBOD/m ir temperature: 7 °C  No raining  ‘o raining  Circulation rate: 0.5  Dirculation rate: 0.5  Influent Effluent  Influent Effluent 7.4 7.9  DO (mg/L)  7.2  7.6  DO (mg/L)  pH  7.18  7.21  pH  7.24  7.31  Temperature(t)  11  11  Temperature(t)  11  11  COD concentration (mgIL) Influent Effluent Removal rate 100.8 105.7 -4.86%±5.55% Total  Total Dissolved  32.5  22.8%±8.94%  25.1  Influent Effluent Removal rate -1.69% 142.3 144.7  Dissolved  32.5  30.0  7.69%  MBAS concentration (mg/L) Influent Effluent Removal rate 7.52% 5.41 5.85 16.43% 2.13 1.78  Influent Effluent Removal rate Whole  2.52  65%  2.60 1.29  75%  1.26  1.15  90%  0.31  0.32  Recovery rate  1.21  3.08%±3.48% 6.20%±2.93%  Whole  8.73%±4.07% -3.23%±2.22%  75%  3.11  2.74  11.90%  90%  0.92  0.85  7.61%  110.0% 106.3%  65%  Recovery rate  105.3% 99.3%  Table A- 15 TS and VS analysis results on 20 Feb 2007 Sampling area: 5.912 cm 2  Average (mg)  Locations TS (mg)  1 32.9  2 27.4  VS (mg) VS/TS  29.1 88.20%  24.1 87.96%  3 29.8 26.0 87.25%  4 36.8 32.2 87.50%  5 39.4 33.9 86.04%  33.3 29.1 87.37%  Standard deviation  Density (mg! cm ) 2  4.92 4.1  5.63 4.92  67  Table A-16 MBAS and COD analysis results on 27 Feb 2007 Sampling time: 27 Feb 2007, 10:30 am Flow rate: 123 L/min, 177.1 m /d 3  Sampling time: 27 Feb 2007, 8:00 pm /d 3 Flow rate: 123 L/min, 177.1 m  Hydraulic loading 2 /d): 3 (m . m 4.56 Organic loading (kgBOD/m .d): 14.2 3  lydraulic loading 2 1 3 (m . d): m 4.56 .d): 14.2 3 Organic loading (kgBOD/m ir temperature: 5 C  Air temperature: 6 C No raining  ‘io raining  Circulation rate: 0.5 DO (mg/L)  irculation rate: 0.5  Influent Effluent 6.2 7.2  Influent Effluent 7.0 6.5  DO (mg/L)  pH  7.12  7.21  pH  7.09  7.23  Temperature(C)  11  11  Temperature( C)  10  10  COD concentration (mgIL) Influent Effluent Removal rate 115.4 98.4 14.73%±5.55% Total  Total Dissolved  47.1  27.6  41.40%+8.94%  Influent Effluent Removal rate 15.74% 186.2 156.9 32.20% 61.7 91.0  Dissolved  MBAS concentration (mgfL) Influent Effluent Removal rate 3.11 2.94 5.47%±3.48% 1.35 1.31 2.96%±2.93%  Whole 65% 75%  1.68  1.63  3.00%±4.07%  90%  0.37  0.31  16.22%±2.22%  Recovery rate  109.3% 110.5%  Influent Effluent Removal rate 8.65% 5.81 6.36  Whole 65%  2.02  1.77  75% 90%  3.58 1.18  2.74  12.38% 23.46%  1.07  9.32%  Recovery rate  106.6% 96.0%  Table A-i 7 TS and VS analysis results on 27 Feb 2007 Sampling area: 5.912 cm 2 Locations TS (mg) VS (mg) VS/TS  1 32.2 28.4 88.20%  2 30.8 27.7 89.94%  3 27.6 24.6  4 30.1 26.7  89.13%  88.70%  5 34.3 30.8 89.80%  Average (mg)  Standard deviation  Density (mgI cm ) 2  31.0 27.6 89.16%  2.45 2.27  5.24 4.67  68  Table A- 18 MBAS and COD analysis results on 05 Mar 2007 Sampling time: 05 Mar 2007, 10:30 am Flow rate: 123 L/min, 177.1 m /d 3 Hydraulic loading 2 1 3 (m . d): m 4.56  ampling time: 05 Mar 2007, 8:00 pm Flow rate: 123 L/min, 177.1 m Id 3 Flydraulic loading 2 /d): 3 (m . m 4.56  Organic loading (kgBOD/m .d): 17.9 3 Air temperature: 11.5 C  Organic loading (kgBOD/m .d): 17.9 3  Raining  ‘o raining  Circulation rate: 0.5  Circulation rate: 0.5  DO (mg/L)  \ir temperature: 9.8 °C  Influent Effluent 6.3 7.1  Influent Effluent 7.2 6.3  DO (mg/L)  pH  7.11  7.25  pH  6.89  7.18  Temperature(t)  12  12  Temperature(C)  11.5  11.5  COD concentration (mgIL) Influent Effluent Removal rate 164.3 152.1 7.43%±5.55% Total 69.1 64.2 7.09%±8.94% Dissolved  Total Dissolved  Influent Effluent Removal rate -6.82% 178.9 191.1 105.7  88.6  16.18%  MBAS concentration (mgfL) Influent Effluent Removal rate 3.71 3.55 4.31%±3.48%  Whole  Influent Effluent Removal rate 7.62 3.05% 7.86  Whole  65%  1.37  1.27  7.30%*2.93%  65%  2.29  2.19  4.37%  75%  1.94 0.45  1.74  10.31%±4.07%  75%  3.55  5.33%  0.40  11.11%±2.22%  90%  3.75 1.56  1.37  12.18%  Recovery rate  96.7%  93.3%  90% Recovery rate  101.1% 85.9%  Table A-19 TS and VS analysis results on 05 Mar 2007 Sampling area: 5.912 cm 2  Average (mg)  Locations TS (mg)  1 37.0  2 35.9  3 28.4  VS (mg) VS/TS  32.6 88.11%  31.8 88.58%  25.0 88.03%  4 29.7 26.9  5 22.3 19.8  90.57%  88.79%  30.7 27.2 88.78%  Standard deviation  Density ) 2 (mg/ cm  5.99 5.24  5.19 4.60  69  Table A-20 MBAS and COD analysis results on 08 Mar 2007 Sampling time: 08 Mar 2007, 10:30 am  Sampling time: 08 Mar 2007, 8:00 pm /d 3 Flow rate: 123 L/min, 177.1 m  Flow rate: 123 L/min, 177.1 m Id 3 Hydraulic loading 2 1 3 (m . d): m 4.56  1 3 (m . d): m 4.56 lydraulic loading 2 .d): 21.2 3 )rganic loading (kgBOD/m  Organic loading (kgBOD/m .d): 21.2 3 Air temperature: 9 C  ir temperature: 10.5 °C  Raining  aining  Circulation rate: 0.5 DO (mgIL)  irculation rate: 0.5  Influent Effluent 7.1 6.4  Influent Effluent 7.2 6.8  DO (mgfL)  pH  7.05  7.29  pH  7.02  7.18  Temperature(t)  11  11  Temperature(C)  11.5  11.5  COD concentration (mg/L) Influent Effluent Removal rate 176.5 156.9 11.1O%±5.55%  Total Dissolved  78.8  88.6  11.06%±8.94%  Influent Effluent Removal rate -1.52% 239.9 236.3  Total  117.9  Dissolved  MBAS concentration (mg/L) Influent Effluent Removal rate 3.86 3.55 Whole 8.03%±3.48% 1.36 1.50 9.33%±2.93% 65% 1.32 1.19 75% 9.85%±4.07%  Whole 65% 75% 90%  0.50  0.43  Recovery rate  86.0%  83.9%  14.00%±2.22%  113.0  4.16%  Influent Effluent Removal rate 19.02% 6.47 7.99 2.15  1.95 3.13  90%  3.53 1.05  9.30% 11.33%  0.87  17.14%  Recovery rate  96.7%  92.0%  Table A-2 1 TS and VS analysis results on 08 Mar 2007 Sampling area: 5.912 cm 2 Locations TS (mg) VS (mg) VS/TS  1 27.6 24.3 88.04%  Average (mg) 2  38.7 34.4 88.89%  3 23.0 20.2 87.83%  4 28.5 25.4 89.12%  5 39.0 34.1 87.44%  31.4 27.7 88.27%  Standard  Density  deviation  (mgI cm ) 2  7.15 6.30  5.31 4.69  70  Table A-22 MBAS and COD analysis results on 26 Mar 2007 Sampling time: 26 Mar 2007, 10:30 am Flow rate: 123 L/min, 177.1 m /d 3  Sampling time: 26 Mar 2007, 8:00 pm /d 3 ‘low rate: 123 L/min, 177.1 m [lydrauiic loading 2 /d): 3 (m . m 4.56  Hydraulic loading 2 /d): 3 (m . m 4.56 Organic loading (kgBOD/m .d): 12.7 3 Air temperature: 12.5 t  .d): 12.7 3 Organic loading (kgBOD/m  Not raining  ot raining  Circulation rate: 1  Dirculation rate: 1  iir temperature: 9.5 ‘C  Influent Effluent 7.2 7.5  DO (mg/L)  Influent Effluent DO (mg/L)  7.3  8.0  pH  6.84  7.05  pH  6.90  6.99  Temperature(°C)  12  12  Temperature(°C)  12  12  COD concentration (mgIL) Influent Effluent Removal rate 93.5 87.4 6.52%±6.06% Total  Total Dissolved  25.1  22.7  9.56%±10.61%  Influent Effluent Removal rate 3.82% 191.1 183.8  98.4  Dissolved  71.5  27.34%  MBAS concentration (mgfL) Influent Effluent Removal rate 4.02% 6.21 6.47 5.33% 1.69 1.60  Influent Effluent Removal rate Whole 65%  3.33 1.37  3.11 1.21  6.61%±l.77%  Whole  11.68%±2.22%  65%  75% 90%  1.83 0.42  1.63 0.37  10.93%±2.39% 11.90%±3.41%  90%  Recovery rate  108.7% 103.2%  75%  3.80 1.47  Recovery rate  3.53 1.34  7.11% 8.84%  107.6% 104.2%  Table A-23 TS and VS analysis results on 26 Mar 2007 Sampling area: 5.912 cm 2 Locations TS (mg) VS (mg) VS/TS  1 26.6 23.5 88.35%  2  3  35.5 31.6 89.01%  25.5  22.4 87.84%  4 31.8 28.1 88.36%  5 33.7 29.7 88.13%  Average  Standard  (mg)  deviation  30.6 27.1 88.37%  4.39 3.97  Density (mg/ cm ) 2 5.18 4.58  71  Table A-24 MBAS and COD analysis results on 29 Mar 2007 Sampling time: 29 Mar 2007, 10:30 am Flow rate: 123 L/min, 177.1 m /d 3 Hydraulic loading 2 1 3 (m . d): m 4.56  Sampling time: 29 Mar 2007, 8:00 pm  Organic loading (kgBOD/m .d): 13.4 3 Air temperature: 14.5 C Not raining  .d): 13.4 3 Organic loading (kgBOD/m Air temperature: 11 C  Flow rate: 123 L/min, 177.1 3 m I d Elydraulic loading 2 /d): 3 (m . m 4.56  ‘iot raining  Circulation rate: 1  Dirculation rate: 1  Influent Effluent  Influent Effluent  DO (mg/L)  7.1  7.4  DO (mg/L)  7.0  7.5  pH  7.09  7.25  pH  7.13  7.22  Temperature(°C)  13  13  Temperature( C)  12  12  COD concentration (mgfL) Influent Effluent  Removal rate  Total  122.8  130.1  -5.94%±6.06%  Total  Dissolved  59.3  66.6  -12.31%±10.61%  Dissolved  Influent Effluent Removal rate 152.1 6.00% 161.8 71.5  71.5  0%  MBAS concentration (mg/L) Influent Effluent Whole 65%  4.08 1.52 2.38  75% 90%  3.71 1.40 2.00 0.51  0.50  Recovery rate  Removal rate 9.07%±1.77% 7.89%±2.22% 15.97%±2.39% -2.00%±3.41%  107.8% 105.4%  Whole 65% 75% 90% Recovery rate  Influent Effluent Removal rate 10.09% 8.72 7.84 3.16% 2.53 2.45 8.92% 4.26 3.88 19.29% 1.40 1.13 93.92% 95.15%  Table A-25 TS and VS analysis results on 29 Mar 2007 Sampling area: 5.912 cm 2 Locations TS (mg) VS (mg) VS/TS  1 33.4 28.2 84.43%  (mg)  Standard deviation  Density ) 2 (mg/ cm  37.8  4.92  32.1 84.96%  3.97  6.39 5.43  Average 2 45.5  37.8 83.07%  3 33.7 28.5 84.57%  4 38.9 33.6 86.38%  5 37.3 32.3 86.60%  72  Table A-26 MBAS and COD analysis results on 02 Apr 2007 Sampling time: 02 Apr 2007, 10:30 am Flow rate: 123 L/min, 177.1 m Id 3  Sampling time: 02 Apr 2007, 8:00 pm /d 3 E’low rate: 123 L/min, 177.1 m Elydraulic loading 2 /d): 3 (m . m 4.56  Hydraulic loading 2 1 3 (m . d): m 4.56 Organic loading (kgBOD/m .d): 9.7 3  Organic loading (kgBOD/m .d): 9.7 3 ir temperature: 8 ‘C  Air temperature: 9 °C Not raining  ‘Tot raining  Circulation rate: 1  Circulation rate: 1  Influent Effluent  Influent Effluent 7.3 6.8  DO (mg/L)  6.9  7.3  DO (mg/L)  pH  7.16  7.31  pH  7.07  7.22  Temperature(t)  13  13  Temperature(t)  12  12  COD concentration (mgIL) Influent Effluent Removal rate 98.4 105.7 -7.42%+6.06% Total 39.8 44.7 -12.31%±10.61% Dissolved  Total Dissolved  Influent Effluent Removal rate 139.9 10.83% 156.9 54.4  59.3  -9.01%  MBAS concentration (mg/L) Influent Effluent  Influent Effluent Removal rate  Removal rate  Whole 65%  4.15  3.71  10.60%±1.77%  Whole  1.73  1.61  6.94%±2.22%  65%  75%  2.07  1.87  75%  0.46  0.40  9.66%±2.39% 13.04%±3.41%  90% Recovery rate  102.6% 104.6%  90% Recovery rate  7.51 3.19  7.07 2.76  3.40 3.60 1.08 0.93 104.8% 100.3%  5.86% 13.48% 5.56% 13.89%  Table A-27 TS and VS analysis results on 02 Apr 2007 Sampling area: 5.912 cm 2 Locations TS (mg) VS (mg)  1 31.3 26.9  2 29.1  3 32.8  4 36.3  25.4  29.1  VS/TS  85.94%  87.29%  88.72%  Average (mg)  Standard deviation  Density ) 2 (mg/ cm  31.4  3.41 2.83  5.31 4.58  30.7  5 27.5 23.6  27.1  84.57%  86.60%  86.43%  73  Table A-28 MBAS and COD analysis results on 05 Apr 2007 Sampling time: 05 Apr 2007, 10:30 am Flow rate: 123 L/min, 177.1 m Id 3 Hydraulic loading 2 1 3 (m . d): m 4.56 Organic loading (kgBOD/m .d): 13.7 3 Air temperature: 14 C Not raining Circulation rate: 1  Sampling time: 05 Apr 2007, 8:00 pm Flow rate: 123 L/min, 177.1 m Id 3 Elydraulic loading 2 1 3 (m . d): m 4.56 Organic loading (kgBOD/m .d): 13.7 3 ir temperature: 12 C ‘tot raining :Dirculation rate: 1  Influent Effluent DO (mg/L)  Influent Effluent  6.5 7.12  6.8  DO (mg/L)  6.4  pH  7.25  pH  7.03  7.0 7.15  Temperature(t)  14  14  Temperature(t)  13  13  Total Dissolved  COD concentration (mg/L) Influent Effluent Removal rate 122.8 108.1 11.97%±6.06% Total 42.2 37.3 11.61%±10.61% Dissolved  MBAS concentration (mgIL) Influent Effluent Removal rate Whole 3.11 2.91 6.43%±1.77% Whole 65% 1.69 1.55 8.28%±2.22% 65% 75% 1.65 1.50 9.01%±2.39% 75% 90% 0.39 20.51%±3.4l% 0.31 90% Recovery rate 110.3% 115.5% Recovery rate  Influent Effluent Removal rate -12.23% 159.4 178.9 91.0  69.1  24.07%  Influent Effluent Removal rate 7.04 3.69% 7.31 6.90% 3.19 2.97 3.80 0.85  3.24  14.74%  0.76  10.59%  106.6% 99.01%  Table A-29 TS and VS analysis results on 05 Apr 2007 Sampling area: 5.912 cm 2 Locations TS (mg) VS (mg) VS/TS  1 36.3  2 39.4  31.6  33.8  3 37.3 32.6  4 34.8 29.5  Average (mg)  Standard deviation  Density (mgI cm ) 2  37.5 32.3  2.02 1.89  6.34  5  39.5 34.2  87.05%__85.79%__87.40%__84.77%__86.58%__86.33%  5.46  74  Table A-30 MBAS and COD analysis results on 16 Apr 2007 Sampling time: 16 Apr 2007, 10:30 am Flow rate: 123 L/min, 177.1 m Id 3  ampling time: 16 Apr 2007, 8:00 pm /d 3 low rate: 123 Llmin, 177.1 m /d): 3 (m . m 4.56 4ydraulic loading 2  Hydraulic loading 2 /d): 3 (m . m 4.56 Organic loading (kgBOD/m .d): 6.65 3 Air temperature: 13 C  .d): 6.65 3 )rganic loading (kgBOD/m  Raining  ot raining  ir temperature: 10 C  Circulation rate: 1.5  irculation rate: 1.5  Influent Effluent 7.2 6.8  DO (mg/L)  Influent Effluent 7.2 6.5  DO (mg/L)  pH  7.32  7.34  pH  7.19  7.23  Temperature(C)  14  14  Temperature(t)  13.5  13.5  COD concentration (mg/L) Influent Effluent Removal rate 135.0 122.8 9.04%±12.74% Total 37.3 27.6 26.Ol%±5.33% Dissolved  Total Dissolved  Influent Effluent Removal rate 5.34% 120.3 114.2 27.6  22.7  17.75%  MBAS concentration (mg/L) Influent Effluent Removal rate 3.36 2.98 11.31%±1.92% 1.74 1.57 9.77%±l.74% 1.52 1.10 27.63%±5.74%  Whole 65% 75% 90%  0.41  Recovery rate  0.31  24.39%±5.90%  109.2% 100.0%  Influent Effluent Removal rate Whole 65% 75% 90% Recovery rate  7.80 2.48  7.13  8.59%  2.34  5.65%  4.57  4.08  1.07  1.02  10.72% 4.67%  104.1% 104.3%  Table A-3 I TS and VS analysis results on 16 Apr 2007 Sampling area: 5.912 cm 2 Locations TS (mg)  1 35.6  VS (mg) VS/TS  31.4 88.20%  2 31.5 27.8 88.25%  3 33.7 29.8 88.430%  4 33.0 29.1 88.18%  5 34.3 30.7 89.50%  Average  Standard  Density  (mg)  deviation  (mgI cm ) 2  33.6 29.8 88.52%  1.52  5.68 5.04  1.40  75  Table A-32 MBAS and COD analysis results on 19 Apr 2007 Sampling time: 19 Apr 2007, 10:30 am Flow rate: 123 L/min, 177.1 m /d 3  Sampling time: 19 Apr 2007, 8:00 pm  Hydraulic loading . 2 1 3 (m d): m 4.56 Organic loading (kgBOD/m .d): 17.9 3 Air temperature: 14 ‘C  Elydraulic loading 2 1 3 (m . d): m 4.56 .d): 17.9 3 )rganic loading (kgBOD/m  Flow rate: 123 L/min, 177.1 m /d 3  Not raining  ir temperature: 11 C “ot raining  Circulation rate: 1.5  Dirculation rate: 1.5  Influent Effluent DO (mg/L)  Influent Effluent 7.1 6.8  7.0  DO (mg/L)  pH  6.5 7.32  7.36  pH  7.21  7.24  Temperature(t)  14.5  14.5  Temperature(t)  13  13  Influent Effluent  COD concentration (mg/L) Removal rate  Total  210.6  169.1  19.71%±12.74%  Total  Dissolved  88.6  64.2  27.54%±5.33%  Dissolved  Influent Effluent Removal rate -7.45% 196.0 210.6 86.2  69.1  19.84%  MBAS concentration (mgfL) Influent Effluent  Removal rate  Whole 65%  3.42 1.90  3.05 1.77  10.82%±1.92% 6.84%±1.74%  75% 90%  1.32 0.36  1.01 0.32  23.48%±5.74% 11.11%+5.90%  Recovery rate  104.7% 101.6%  Whole 65% 75% 90% Recovery rate  Influent Effluent Removal rate 5.85% 7.18 6.76 10.87% 2.30 2.05 3.71 1.31  3.22 1.22  13.21% 6.87%  101.9% 96.01%  Table A-33 TS and VS analysis results on 19 Apr 2007 Sampling area: 5.912 cm 2 Locations TS (mg) VS (mg) VS/TS  1 40.3 34.3 85.11%  Average (mg) 2 45.7  39.5 86.43%  3 36.9 33.0 89.430%  4 38.8 34.1 87.89%  5 34.2 29.2 85.38%  39.2 34.0 86.83%  Standard  Density  deviation  (mg/ cm ) 2  4.30  6.63  3.69  5.75  76  Table A-34 MBAS and COD analysis results on 24 Apr 2007 Sampling time: 24 Apr 2007, 10:30 am Flow rate: 123 L/min, 177.1 m /d 3  ampling time: 24 Apr 2007, 8:00 pm /d 3 Flow rate: 123 L/min, 177.1 m Elydraulic loading 2 /d): 3 (m . m 4.56 Organic loading (kgBOD/m .d): 18.7 3  Hydraulic loading 2 1 3 (m . d): m 4.56 Organic loading (kgBOD/m .d): 18.7 3 Air temperature: 13 ‘C Raining  ir temperature: 11 ‘C “ot raining  Circulation rate: 1.5  Circulation rate: 1.5  Influent Effluent  Influent Effluent  DO (mg/L)  7.0  7.4  DO (mg/L)  6.8  7.1  pH  7.33  7.43  pH  7.24  7.28  Temperature(’C)  14  14  Temperature( ‘C)  13  13  Total  86.2  COD concentration (mg/L) Removal rate 105.7 -22.62%±12.74% Total  Dissolved  66.6  49.5  Influent Effluent  25.68%+5.33%  Dissolved  Influent Effluent Removal rate 147.2 11.70% 166.7 115.4  103.2  10.57%  MBAS concentration (mg/L)  Influent Effluent Whole 65%  3.49 1.59  10.89%±1.92% 10.06%±1.74% 18.03%±5.74% 8.33%±5.90%  75%  1.83  1.50  90%  0.36  0.33  Recovery rate  Removal rate  3.11 1.43  108.3% 104.8%  Whole 65%  Influent Effluent Removal rate 6.75% 7.04 7.55 10.16% 2.74 3.05  75%  3.60  3.20  11.11%  90%  1.19  1.01  15.13%  Recovery rate  103.8% 98.7%  Table A-35 TS and VS analysis results on 24 Apr 2007 Sampling area: 5.912 cm 2 Locations  1  TS (mg)  46.7  2 31.9  VS (mg) VS/TS  41.0 87.79%  28.3 88.71%  3 34.6 30.4 87.860%  4  28.9 25.6 88.58%  5 24.5 21.4 87.35%  Average (mg)  Standard deviation  Density (mgI cm ) 2  33.3 29.3  8.37 7.34  5.63 4.96  88.06%  77  Table A-36 MBAS and COD analysis results on 21 May 2007 Sampling time: 21 May 2007, 10:30 am Flow rate: 80 L/min, 115.2 m /d 3  Sampling time: 21 May 2007, 8:00 pm Flow rate: 80 L/min, 115.2 m /d 3 Hydraulic loading 2 1 3 (m . d): m 2.96  Hydraulic loading 2 1 3 (m . d): m 2.96 Organic loading (kgBOD/m .d): 14.7 3 Air temperature: 12 C  .d): 14.7 3 )rganic loading (kgBOD/m \ir temperature: 15 C  Not raining  ‘Tot raining  Circulation rate: 2  ircuIation rate: 2  DO (mg/L) pH  Influent Effluent 7.9 8.0 7.11 7.16  Temperature(C)  14  DO (mg/L) pH  14  Temperature(t)  COD concentration (mg/L) Influent Effluent Removal rate  Total Dissolved  106.9 56.9  83.7 45.9  Influent Effluent 7.4 7.8 7.11 7.05  21.70% 19.33%  Total Dissolved  16  16  Influent Effluent Removal rate 196.0 164.3  196.0 86.2  0% 47.53%  MBAS concentration (mg/L) Iniluent Effluent Removal rate 2.18 2.56 -17.43% 1.61 1.22 24.22%  Whole 65% 75% 90%  0.92  0.99 0.32  0.39  Recovery rate  -7.61%  Whole 65% 75% 90%  17.95%  133.9% 98.8%  Recovery rate  Influent Effluent Removal rate 1.47% 9.36 9.50 5.17% 2.90 2.75 5.61 2.14  5.63 2.25  -3.57% -5.14%  112.1% 113.6%  Table A-37 TS and VS analysis results on 21 May 2007 Sampling area: 5.912 cm 2  Average (mg)  Locations TS (mg)  1 40.9  2 25.6  VS (mg) VS/TS  36.2 88.51%  23.0 89.84%  3 28.0 25.7 91.79%  4 34.8 30.8 88.51%  5 36.1 31.6 87.53%  33.1 29.5 89.12%  Standard deviation  Density (mg/ cm ) 2  6.22 5.19  5.60 4.99  78  Table A-38 MBAS and COD analysis results on 24 May 2007 Sampling time: 24 May 2007, 10:30 am Flow rate: 80 L/min, 115.2 m /d 3 Hydraulic loading 2 1 3 (m . d): m 2.96  Sampling time: 24 May 2007, 8:00 pm Flow rate: 80 L/min, 115.2 m Id 3 lydraulic loading 2 /d): 3 (m . m 2.96 )rganic loading (kgBOD/m .d): 8.7 3  Organic loading 3 (kgBOD/m . d): 8.7 Air temperature: 17 ‘C Not raining  &ir temperature: 20 t ‘tot raining  Circulation rate: 2  Dirculation rate: 2 Influent Effluent 6.2 6.1  Influent Effluent DO (mg/L)  6.8  6.7  pH  7.54  7.59  pH  7.29  7.22  Temperature(°C)  16  16  Temperature( C)  17  17  DO (mg/L)  COD concentration (mg/L) Influent Effluent Removal rate 127.6 142.3 -11.52% Total  Total Dissolved  47.1  64.2  -36.31%  Dissolved  Influent Effluent Removal rate 152.1 8.76% 166.7 81.3  63.0  22.51%  MBAS concentration (mgIL) Influent Effluent Removal rate 2.69 3.00 -11.52%  Whole  Whole  Influent Effluent Removal rate -7.67% 6.18 5.74  65%  1.58  1.60  -1.27%  65%  2.95  3.10  -5.08%  75%  1.28  1.26  0.37  0.29  75% 90%  3.69  90%  1.56% 21.62%  3.73 0.74  -1.08% -12.12%  Recovery rate  120.1% 105.0%  Recovery rate  0.66  127.2% 122.5%  Table A-39 TS and VS analysis results on 24 May 2007 Sampling area: 5.912 cm 2  Average (mg)  Locations TS (mg)  1 22.0  2 24.4  3 24.9  VS (mg) VS/TS  19.6 89.09%  22.0 90.16%  22.4 89.96%  4 15.4 13.8 89.61%  Standard deviation  Density ) 2 (mgI cm  5 29.8  23.3  5.20  3.94  25.8 86.58%  20.7 88.84%  4.50  3.50  79  Table A-40 MBAS and COD analysis results on 28 May 2007 Sampling time: 28 May 2007, 10:30 am Flow rate: 80 L/min, 115.2 m /d 3  Sampling time: 28 May 2007, 8:00 pm /d 3 Flow rate: 80 L/min, 115.2 m Elydraulic loading 2 1 3 (m . d): m 2.96  Hydraulic loading 2 1 3 (m . d): m 2.96 Organic loading (kgBOD/m .d): 9.0 3  )rganic loading (kgBOD/m .d): 9.0 3  Air temperature: 16 C Not raining  ‘tot raining  Circulation rate: 2  :Dirculation rate: 2  temperature: 20 C  Influent Effluent 6.5 6.8  Influent Effluent  DO (mg/L)  6.6  6.7  pH  7.47  7.37  pH  7.16  7.25  Temperature(t)  16  16  Temperature( C)  17  17  DO (mg/L)  COD concentration (mgfL) Influent Effluent Removal rate 105.7 137.4 -29.99% Total  Total Dissolved  67.9  52.0  23.42%  Dissolved  Influent Effluent Removal rate 9.69% 159.4 176.5 67.8  110.6  -63.13%  MBAS concentration (mgfL) Influent Effluent Removal rate 3.51 4.77 -35.90% 1.74 1.42 18.39%  Whole 65% 75% 90%  1.76 0.48  Recovery rate  2.10 0.36  -19.32% 25.00%  113.4% 81.3%  Whole 65% 75% 90% Recovery rate  Influent Effluent Removal rate 10.76% 8.79 9.85 2.80 6.35% 2.99 4.42 1.22  5.43  87.6%  104.4%  0.95  -22.85% 22.13%  Table A-41 TS and VS analysis results on 28 May 2007 Sampling area: 5.912 cm 2 Locations TS (mg) VS (mg) VS/TS  1 23.4 20.8 88.89%  2 75.6 66.2 87.57%  3 29.4 26.1 88.78%  4 28.4 24.2 85.21%  5 16.4 14.4 87.80%  Average  Standard  Density  (mg)  deviation  (mg/ cm ) 2  34.6 30.3 87.57%  2.35 2.05  5.85 5.13  80  Table A-42 MBAS and COD analysis results on 31 May 2007 Sampling time: 31 May 2007, 10:30 am Flow rate: 80 L/min, 115.2 m /d 3  ampling time: 31 May 2007, 8:00 pm /d 3 Flow rate: 80 L/min, 115.2 m 1 3 (m . d): m 2.96 lydraulic loading 2  Hydraulic loading 2 1 3 (m . d): m 2.96 Organic loading (kgBOD/m .d): 10.8 3 Air temperature: 21 C Not raining  .d): 10.8 3 )rganic loading (kgBOD/m ir temperature: 23 C ot raining  Circulation rate: 2  irculation rate: 2 Influent Effluent  Influent Effluent 7.4 7.2  DO (mg/L)  7.1  7.4  pH  7.38  7.43  pH  7.06  7.19  Temperature(t)  18  18  Temperature( C)  18  18  DO (mg/L)  COD concentration (mgIL) Influent Effluent Removal rate 142.3 144.7 -1.69% Total  Total Dissolved  59.3  76.4  -28.84%  Dissolved  Influent Effluent Removal rate 159.4  171.6  -7.65%  102.0  88.6  13.14%  MBAS concentration (mgfL) Influent Effluent Removal rate 4.19 5.61 -33.89% 2.29 2.37 -3.49%  Whole 65% 75%  1.70 0.50  90% Recovery rate  2.01  -18.24%  0.56  -12.00%  107.2% 88.1%  Whole 65%  Influent Effluent Removal rate 6.87% 8.41 9.03 13.85% 3.36 3.90  75% 90%  4.04 0.78  4.11 0.64  Recovery rate  96.6%  96.4%  -1.73% 17.95%  Table A-43 TS and VS analysis results on 31 May 2007 Sampling area: 5.912 cm 2 Locations TS (mg) VS (mg) VS/TS  1 45.4 40.5 89.21%  2 31.9 28.7 89.97%  3 30.8 27.9 90.58%  4 22.5 19.8 88.00%  5 30.9 27.4 88.67%  Average (mg)  Standard deviation  Density ) 2 (mgI cm  32.3  8.25 7.43  4.89  28.9 89.47%  5.46  81  Table A-44 MBAS  and COD analysis results on 4 June 2007  Sampling time: 4 June 2007, 10:30 am Flow rate: 80 L/min, 115.2 m /d 3 Hydraulic loading 2 /d): 3 (m . m 2.96  /d 3 Flow rate: 80 L/min, 115.2 m Elydraulic loading 2 1 3 (m . d): m 2.96  Organic loading (kgBOD/m .d): 12.0 3 Air temperature: 23  )rganic loading (kgBODIm .d): 12.0 3 ir temperature: 19 ‘C  Not raining  Eaining (not very much)  ampling time: 4 June 2007, 8:00 pm  Circulation rate: 2  irculation rate: 2 Influent Effluent  Influent Effluent 6.7 6.9  DO (mg/L)  7.1 7.44  7.3 7.52  DO (mg/L)  pH  pH  7.19  7.22  Temperature(t)  18.5  18.5  Temperature(’C)  18.5  18.5  COD concentration (mgfL) Influent Effluent Removal rate 171.6 169.1 1.46%  Total Dissolved  95.9  105.7  -10.22%  Total Dissolved  Influent Effluent Removal rate -4.08% 186.2 178.9 83.7  93.5  -11.71%  MBAS concentration (mgIL) Influent Effluent Removal rate Whole 65%  4.97 1.43 2.43  4.26 1.66  14.29% -16.08%  Whole  0.40  2.05 0.45  15.68% -12.50%  75% 90%  85.7%  97.7%  75% 90% Recovery rate  65%  Recovery rate  Inf.luent Effluent Removal rate 9.20% 9.78 8.88 12.40% 3.18 3.63 4.95  4.66 1.56  1.37  5.86% -13.87%  101.7% 105.9%  Table A-45 TS and VS analysis results on 4 June 2007 Sampling area: 5.912 cm 2 Locations TS (mg) VS (mg) VS/TS  1 28.8 26.0 90.28%  2 30.2 26.7 88.41%  3 19.3 17.5 90.67%  4 21.7 19.4 89.40%  5 31.1 27.0 86.82%  Density  Average (mg)  Standard deviation  (mgI cm ) 2  26.2 23.3 88.93%  5.35 4.51  4.43 3.94  82  Table A-46 MBAS and COD analysis results on 7 June 2007 Sampling time: 7 June 2007, 10:30 am Flow rate: 80 L/min, 115.2 m /d 3 Hydraulic loading 2 /d): 3 (m . m 2.96  Sampling time: 7 June 2007, 8:00 pm Flow rate: 80 Llmin, 115.2 m Id 3 Flydraulic loading 2 1 3 (m . d): m 2.96  Organic loading (kgBOD/m .d): 8.6 3 Air temperature: 16 °C  Organic loading (kgBODIm .d): 8.6 3  Not raining  ir temperature: 18 b4ot raining  **  Circulation rate: 2  Dirculation rate: 2 Influent Effluent  Influent Effluent 7.2 6.8  DO (mg/L)  6.8  7.1  DO (mg/L)  pH  7.46  7.54  pH  7.31  7.38  Temperature(°C)  17  17  Temperature( C)  17.5  17.5  COD concentration (mg/L) Influent Effluent Removal rate 139.9 125.2 10.51% Total  Total Dissolved  60.5  53.2  12.07%  Dissolved  Influent Effluent Removal rate 1.48% 159.4 161.8 69.1  247.24  -257.80%  MBAS concentration (mg/L) Influent Effluent Removal rate 4.13 3.66 11.38% 1.64 1.45 11.59%  Whole 65%  75%  1.99  90%  0.45  1.79 0.43  10.05%  Recovery rate  98.8%  100.3%  Whole 65% 75%  4.44%  Influent Effluent Removal rate 6.26% 8.24 8.79 3.14% 3.18 3.08 4.00  3.82  4.50% 18.10%  90%  1.05  0.86  Recovery rate  93.6%  94.1%  Table A-47 TS and VS analysis results on 7 June 2007 Sampling area: 5.912 cm 2 Locations TS(mg) VS (mg) VS/TS  1 20.1 18.4 91.54%  2 22.2 19.8 89.19%  3 15.5 14.2 91.61%  4 30.7 26.3  5 21.5 18.5  85.67%  86.05%  Density  Average (mg)  Standard deviation  ) 2 (mg/ cm  22.0  5.52 4.38  3.72 3.28  19.4 88.18%  83  Table A-48 MBAS and COD analysis results on 18 June 2007 Sampling time: 18 June 2007, 10:30 am Flow rate: 80 L/min, 115.2 m /d 3  ampling time: 18 June 2007, 8:30 pm Plow rate: 80 Llmin, 115.2 3 m / d [-lydraulic loading 2 /d): 3 (m . m 2.96  Hydraulic loading 2 /d): 3 (m . m 2.96 Organic loading (kgBOD/m .d): 13.4 3  )rganic loading (kgBOD/m .d): 13.4 3 &iir temperature: 18.5 °C  Air temperature: 13 C Not raining **  “ot raining  Circulation rate: 2 DO (mgIL)  circulation rate: 2 Influent Effluent 7.2 6.9  Influent Effluent DO (mg/L)  6.8  pH  7.57  7.65  pH  7.42  7.0 7.41  Temperature(°C)  16.5  16.5  Temperature(C)  17.5  17.5  COD concentration (mg/L) Influent Effluent Removal rate Total  159.4  183.8  -15.31%  Total  Dissolved  95.9  74.0  22.84%  Dissolved  Influent Effluent Removal rate -1.16% 218.0 215.5 105.7  103.2  2.37%  MBAS concentration (mgfL) Influent Effluent Removal rate  Influent Effluent Removal rate 5.97% 8.35 8.88  Whole  4.15  3.62  12.77%  Whole  65%  1.72  1.51  12.21%  65%  2.63  2.56  2.66%  75% 90%  1.96 0.43  1.87 0.35  4.59% 18.60%  75% 90%  4.79 2.00  4.68 1.93  2.30% 3.50%  Recovery rate  99.0%  103.0%  Recovery rate  106.1% 109.8%  84  Table A-49 MBAS and COD analysis results on 21 June 2007 Sampling time: 21 June 2007, 10:45 am Flow rate: 80 L/min, 115.2 m /d 3  Sampling time: 18 June 2007, 8:30 pm Flow rate: 80 Llmin, 115.2 m /d 3 Elydraulic loading 2 1 3 (m . d): m 2.96  Hydraulic loading 2 1 3 (m . d): m 2.96 Organic loading (kgBOD/m .d): 12.0 3  )rganic loading (kgBOD/m .d): 12.0 3  Air temperature: 20.5 ‘C Not raining  ir temperature: 21.5 ‘C  Circulation rate: 2  Dirculation rate: 2  cot raining  Influent Effluent  Influent Effluent  DO (mg/L)  6.8  7.1  DO (mg!L)  pH  7.55  7.60  pH  6.8 7.35  7.37  Temperature(t)  18  18  Temperature( ‘C)  18  18  Total Dissolved  COD concentration (mg/L) Influent Effluent Removal rate 193.5 183.8 5.01% Total 86.2  91.0  -5.57%  Dissolved  7.0  Influent Effluent Removal rate 0.00% 227.7 227.7 115.4  117.9  -2.17%  MBAS concentration (mg/L) Whole 65% 75% 90% Recovery rate  Influent Effluent Removal rate 4.95 4.72 4.65% 1.87 2.63 0.62  Whole  Influent Effluent Removal rate 10.03% 10.07 9.06 14.33% 2.63 3.07  1.75  6.42%  65%  2.71 0.47  -3.04% 24.19%  75% 90%  4.57  4.53  1.71  1.49  Recovery rate  92.9%  95.5%  103.4% 104.4%  0.88% 12.87%  Note: resultsfrom 21 May 2007 to 21 June 2007 were performed by Jean-Philzpe Laliberté.  85  Appendix A-Ill Total COD, pH, DO and Temperature of wastewater and TS&VS Data  Throughout the experimental period (October, 2006 to June, 2007), pH, DO and temperature of the influent and the effluent of the pilot-scale trickling filterdid not vary significantly. The total COD, pH, DO and temperature were summarized in Table A-50. The TS&VS sampling location and the TS&VS densities throughout the experimental period are presented in Fig. A-i. and Fig. A-2.  Table A-50 Summary of total COD, pH, DO and temperature of wastewater Total COD  pH  DO  Influent  138± 135(10:3Oam) 173±100(20:OOpm)  7.13±0.2  6.9±0.9  Effluent  135±80(10:3Oam) 174± 108(20:OOpm)  7.22±0.16  Temperature  13±1.7 7.4±0.8  (All ranges correspond to 95% confidence)  4  5  3 1  2  Fig A-i Top-view of trickling filter indicating sampling locations for TS and VS tests at the top of pilot-scale trickling filter  86  . 2  C TS 7  Qvs  6  2  3  S  S  C  ininnnnn$nrt  F F F F#’t’’’t’ t  Fig A-2 TS and VS density  87  APPENDIX B: QAIQC A)MDL:  ,%SD=2.821 xSD 9 MDL=t  Table B-i MDL of MBAS (Sep 10, 2006) Absorption  Concentration (mg/L)  Standard Deviation (SD)  MDL (mg/L)  0.019  0.607  0.093062  0.263  0.012 0.017 0.011  0.429 0.556 0.403 0.581  0.018 0.010  0.378 0.454  0.013 0.012  0.429  0.017 0.020  0.556 0.632  Table B-2 MDL of COD (Dec 6, 2006) .  Absorption 0.009 0.012 0.009 0.008 0.010 0.008 0.009 0.010 0.007 0.009  Concentration (mgIL)  Standard Deviation (SD)  MDL (mg/L)  20.26 27.58 20.26 17.82 22.70 17.82 20.26  3.34  9.43  22.70 15.37 20.26  88 B) Blank Tests:  Table B-3 Blank tests for MBAS Filed Blank  Experimental Blank Date 29 Jun, 2006 05 Dee, 2006 05 Mar, 2007  Absorption 0.007 0.005 0.009  Concentration  Date  (mgfL) 0.35 0.31 0.39  12 Dee, 2006 05 Mar, 2007  Absorption  Concentration (mg/L) 0.31  0.005 0.006  0.33  Table B-4 Blank tests for COD Experimental Blank Date 05 Dee, 2006 12 Dee, 2006 23 Jan, 2007 05 Mar, 2007  Filed Blank  Absorption  Concentration (mgfL)  Date  0.003  5.61  12 Dee, 2006  0.003  0.003 0.004 0.004  5.61 8.05 8.05  05 Mar, 2007  0.003  Absorption  Concentration (mgfL) 5.61 8.05  89  APPENDIX C: CALCULATION OF ADJUSTMENT OF INFLUENT AND RECYCLING FLOW RATES An F 430 flowmeter was used to set the influent flow rate and the recycling flow rate to the desired setting by adjusting the opening of the influent flow and recycling flow control valves. However, during operation, the flow meter was removed from the influent and recycling flow lines. Because of the head loss imparted by the flowmeter, the actual flow during operation was slightly higher than that when the flow was being set. Using an estimate of head loss coefficient from the flowmeter, which was, measured experimentally, the actual operating influent and recycle flow rates were estimated. For the actual operating influent and recycling flow rates of 60, 80, 120,125, 160, 180 and 200 Limin, the control value setting were adjusted to achieve flows of influent and recycling flow rates were set to 55, 70, 110, 115, 145, 160 and 180 Limin, respectively. The calculation of the adjustment of influent and recycling flow rates are presented as follow.  The calculation of head loss coefficient is based on Equation C-i (Qasim, 1985). In the equation, H was the head loss (m); k was the head loss coefficient (m’); u was flow velocity (mis) and g was the acceleration of gravity (9.8m1s ). Equation C-i is 2 used to adjust the operating influent and recycling flow rates. The calculation processed is summarized in Table C-i. 2 H= k•— 2g  (C-I)  Table C-i The calculation of head loss coefficient k. Reading flow rate form flowmeter  180 L/min  Actual flow rate when removing the flowmeter Diameter of the flowmeter  200 L/min 3.78 cm  Calculated k value  0.236  90  APPENDIX D: SUBLATION TEST PROCEDURE AND RESULTS Depending on the solution of interest, sublation test can be used to isolate and purifi MBAS contained in liquid samples. Sublation is accomplished by bubbling a stream of nitrogen gas up through a column containing a liquid sample (i.e., MBAS) and an overlaying layer of ethyl acetate (Standard method 5440B). During sublation, MBAS tends to adsorb onto the water-gas interface. When bubbles ascended and past into the ethyl acetate layer, they escaped into the atmosphere leaving behind the MBAS in the ethyl acetate layer.  The following sublation test was performed to determine if sublation would improve the analysis of MBAS. The question needed to address here was: does sublation improve MBAS analysis. Wastewater from UBC Pilot Plant was used in the sublation tests. Characteristics of the wastewater from the UBC Pilot Plant presented in Table D-1.  Table D- 1 Characteristics of the wastewater from UBC Pilot Plant (all value range with 95% confidence) TSS (mg/L) COD (Total) (mg/L) COD (dissolved) (mg/L) BOD (mg/L) MBAS (whole) (mg/L)  110±50(1) 330± 100 ± 90’ 8.40 ±2.21(2)  DO (mg/L) pH  (-)  Temperature (‘C)  7.3 ±0.3(1) 21 ±2(1)  (1): The average results over the periodfrom February 2003 June 2004 (Geng, 2006); (2): The average results of four sampling events on 21/Jun/2006, 28/Jun/2006, 4/Jul/2006 and 12/Jul/2007. —  91  Procedure of Sublation test: The sublation test process followed the Standard Method 5540 B (APHA et al., 1992), except that a chromatography column with fitted disk (CCFD) rather than a sublator was used. Wastewater was collected form UBC Pilot Plant, stored in amber glass bottles and transferred in a cooler back to the UBC Environmental Lab. The sublation was conducted immediately after arrived the lab (i.e., within 30 minutes of collection). The experimental setup was showed in Fig. D- 1.  Fig. D-1 Experimental setup of sublation test  92  Note that the sample size was selected based on the volume of COFD column, which meant that the upper ethyl acetate solution could be conveniently collected with a Pasteur pipette. In addition, the volume ratio of ethyl acetate to wastewater samples was kept at 1:10. Also note that a air flow meter was not used in the sublation tests as recommended in the Standard Method 5540 B (APHA et al., 1992). Alternatively, the gas flow rate was controlled manually and was set to minimize any disruption between the sample and ethyl acetate inter-face.  Results of Sublation test: Two individual sublation tests were performed on wastewater samples collected from UBC Pilot Plant (i.e., on 28/Jun!2006 and on 4IJul/2006). Both sublated and unsublated samples collected on these dates were analyzed for MBAS. The results were shown in Table D-2. A pairwise statistical comparison of MBAS concentration with and without sub lation indicated that there was not significant difference of total MBAS concentrations between sublated and unsublated samples. Therefore, sublation was not performed in present study prior to MBAS analysis.  Table D-2 Summary of sublation tests results (All values in mg/L of MBAS concentration except specified) First Sublation Test (28/Jun/2006)  Total 65% 75% 90% Recovery rate  With  Without  With:without  9.14 3.80 5.00 1.38 111.38%  8.46*  108.04%  4.12 3.05 0.77 93.85%  Second Sublation Test (04/Jul/2006) Whole 65% 75% 90% Recovery rate *:  7.59 2.49 4.21 1.32 105.94%  Average value ofduplicates.  7.16’ 3.34 3.26 0.44 98.32%  106.01%  93  APPENDIX E: TYPICAL CALIBRATION CURVE FOR MBAS  MBAS calibration tests were carried out with 0, 2, 4, 8 and 10 mg/L standard dodecylbenzenesulfonic acid sodium salt (HPLC) solutions, as representative anionic surfactants. All curves resulting from the calibration were similar. A typical calibration curve for MBAS is presented in Fig. E- 1.  MBAS standard curve 12.00 10.00  1* C  8.00 6.00 4.00 2.00 0.00 0.00  0.10  0.20  0.30  0.40  Absorbance  Fig E-1 Typical calibration curve for MBAS  0.50  94  APPENDIX F: TYPICAL CALIBRATION CURVE FOR COD  The COD calibration tests were conducted four times with 0, 20, 40, 100 and 200 mg!L potassium hydrogen phthalate (HPLC) standard solutions. All curves resulting from the calibration were similar. A typical calibration curve for COD is presented in Fig. F-i.  COD Standard Curve 250 200 150 I  100 50  0 0  0.02  0.04  0.06  0.08  Abs orbance  Fig F-i Typical calibration curve for COD  0.1  

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