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Extant Biodegradation Testing With Linear Alkylbenzene Sulfonate in Laboratory and Field Activated Sludge Systems Xiaohong Huang1, Timothy G. Ellis1, and Sandra K. Kaiser2

Dept. of Civil and Construction Engineering, Iowa State University, Ames, IA 50011-3232 2 The Procter and Gamble Company, Cincinnati, OH 45253-8707

ABSTRACT Two 1-L porous pot (65 µ stainless steel mesh) reactors were fed synthetic wastewater with a COD of 200 mg/L including 2 mg/L linear alkyl benzene sulfonate (LAS) to evaluate the influence of specific operating conditions (i.e, hydraulic retention time, HRT, and solids retention time, SRT) on the measured rate of LAS biodegradation. The reactors were operated in parallel under a constant SRT of 10 d, and HRTs of 2, 4, 6, and 12 h. Subsequently, the reactors were operated under a constant HRT of 6 h, and SRTs of 3, 6, 10, and 15 d. The biodegradation responses of LAS were measured using a respirometric method, and the extant kinetic parameters were evaluated using the Monod model. The extant kinetic parameters obtained from these experiments suggest that the HRT had little impact on the measured kinetic parameters (µ ˆ = 0.14 ± 0.06 h-1, KS = 0.4 ± 0.3 mg COD/L, and Y = 0.67 ± 0.02 mg biomass COD formed/mg LAS COD utilized) at a constant SRT of 10 d. The SRT had a more noticeable effect on the measured biodegradation kinetics (e.g., Y increased from 0.50 ± 0.08 to 0.66 ± 0.05 mg/mg when the SRT increased from 3 to 10 d at a constant HRT of 6 h). Extant kinetics for LAS biodegradation were measured in the field at two activated sludge wastewater treatment plants operated at different conditions. The field results were similar to the results from laboratory systems operated to simulate the field conditions (µ ˆ values ranged from 0.02 - 0.05 h-1, KS values ranged from 0.11 0.39 mg COD/L, and yield values ranged from 0.46 - 0.50 mg biomass COD formed/mg LAS COD utilized). The week to week variability in measured LAS kinetic parameters was greater with the field samples than with the laboratory samples, possibly due to the non-steady state nature of the treatment plants. The long term variability in the field kinetic parameters was comparable to the laboratory variability. These results confirm the efficacy of the extant respirometric technique to measure biodegradation rates of surfactants in laboratory and field systems operated at a range of HRT and SRT conditions. Keywords: Linear alkyl benzene sulfonate (LAS), biodegradation, extant kinetics, respirometer, activated sludge

Surface active agents (surfactants) are components of widely used household laundry detergents, household cleaners, shampoos, cosmetics, antistatic agents, textile aids, and textile softeners. Linear alkyl benzene sulfonate (LAS) was introduced in 1965 as a biodegradable

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alternative to non-biodegradable branch-chained alkyl benzene sulfonates (ABS) and since has become the common anionic surfactant in commercial detergent formulations. For example, in 1994, 950,000 metric tons of LAS were used in Europe, North America, and Japan alone (Nielsen et al., 1997). Trehy et al. (1995) reported environmental LAS concentrations in the influent (3.0 – 7.7 mg/L) and effluent (0.003 – 0.086mg/L) of the activated sludge process from 10 U.S. domestic wastewater treatment plants. Kaiser et al. (1997) reported LAS concentrations in the influent to domestic wastewater treatment plants typically ranges from 1 mg/L to 5 mg/L. LAS consists of a mixture of phenol-substituted alkyl chains (with an average chain length of 11.8) with all homolog chains having a negatively charged, bound sulfonate group. LAS alkyl chain lengths typically range from C10 to C14 in the United States and from C10 to C13 in Europe (They et al., 1996). C12 LAS is a representative homolog that can be used to study LAS biodegradation characteristics. Representative structures for LAS and C12 LAS are shown in Figure 1 “Chemical structure of linear alkylbenzene sulfonate (LAS) and C12 LAS.” Because of its widespread household use, LAS is commonly present in the influent to municipal activated sludge POTWs and is discharged to natural water bodies at low concentrations. As a result, the fate of LAS in wastewater treatment plants has been the subject recent studies. For instance, Krueger et al. (1998) observed that LAS was readily biodegraded in activated sludge systems and the LAS had a half-life of 1-2 days. Others have reported on the complexity in the measurement of LAS biodegradation intermediates which cause difficulties in biodegradation analysis (Holt et al, 1995; Trehy et al., 1996; Crescenzi et al., 1996; Federle et al, 1997; Mampel et al, 1998; Krueger et al, 1998). A study by Nielsen et al. (1997), confirmed that LAS was completely degraded in wastewater treatment plants. Trehy et al. (1996) reported that the removal from four activated sludge systems averaged 99.5% for LAS and 99.1% for LAS intermediates. Surfactants are complex organic chemicals where hydrophobic and hydrophilic groups are joined together in the same molecule. A study of the fate of LAS in wastewater treatment plants should consider the microbial degradation of surfactants under different microbial growth conditions, since LAS is biodegraded by a consortia of microorganisms (van Ginkel, 1996). Consequently, the growth conditions of the degrading consortia will determine to a large extent the removal characteristics of LAS and its intermediate degradation products in activated sludge wastewater treatment systems. Operating conditions, such as the SRT, will contribute to the resulting growth kinetics of the degrading microorganisms. Chudoba et al., (1989) suggested that both the maximum volumetric removal rate (qv,max ) and maximum specific removal rate (qmax) of xenobiotic compounds were dependent on the SRT of the mixed culture. van Ginkel (1996) demonstrated the importance of SRT for maintaining sufficient surfactant-degrading microorganisms in wastewater treatment plants. In addition, HRT was found to have an effect, although less dramatic than the effect of the SRT. In a previous study using porous pots to simulate activated sludge, effluent concentrations of LAS were found to be a function of influent concentrations when the HRT was less than 10 h (Kaiser et al., 1997). In an effort to determine the fate of LAS in wastewater treatment systems, research has focused on the development of a technique to measure LAS biodegradation kinetics. Federle et al. (1997) determined that primary and complete biodegradation of LAS were best described by a

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80 to 7. activated sludge samples from local wastewater treatment plants were evaluated using the same extant respirometric procedure.0 during the respirometer tests (Ellis and Anselm. For all kinetic measurements. but the methods to determine the kinetic constants were labor-intensive and time consuming.” Sludge wastage was performed automatically three times per day using a timer or once per day manually to maintain the desired SRT. The composition of the phosphate buffer used in this study consisted of 6.8% C12 LAS. The fraction of the biomass involved in the biodegradation of LAS was assumed to be equal to the fraction of energy (COD) supplied to the culture by LAS (Blackburn et al. dodecyl benzene sulfonate-sodium salt. 6.1987 and Magbanua et al.. 1999). and the results were compared with those from the laboratory study. Surfactant LAS used in this study was a mixture of LAS homologs with 96. The porous pot reactors consisted of a stainless steel mesh with a pore size of 65. Phosphate buffer was added to the biomass sample to maintain the pH at approximately 6.5% active fraction.67g/L Na2 HPO4 (HO2 and 3. 12 h and SRTs of 3.. Materials. A similar competent biomass fraction (2. 1999). a competent biomass fraction of 2. The extant kinetic parameters of LAS were measured over a range of operating conditions at several activated sludge wastewater treatment plants. 1998). Consequently. Zhang et al. The goal was to be able to use the resulting kinetics to describe. an injection concentration of 2 mg/L as COD was used. MATERIALS AND METHODS Porous pot reactors.. in liquid form with 51.e. To evaluate the influence of HRT and SRT. The main objective of the present study was to determine the efficacy of the extant respirometric technique to measure the biodegradation kinetic parameters of surfactants in laboratory and field activated sludge. They were operated in parallel as continuous stirred tank reactors (CSTRs) for a period of one year.9%) was determined for the field experiments. All Rights Reserved. and eventually to predict.7% was used for the laboratory experiments.. and in porous pot reactors simulating activated sludge in the laboratory. Copyright (c) 2000 Water Environment Federation..WEFTEC 2000 first-order approach with the first-order rate constants of 0. 15 d.7 mg/L as COD by the standard COD test. . In addition.50-0. the extant kinetic parameters were measured at HRTs of 2. 6. 10. 1 mg/L LAS was found to be equivalent to 2. The kinetics and removal of LAS in municipal activated sludge treatment systems have been previously studied using laboratory continuous-flow activated sludge systems and radiolabelled LAS (Kaiser et al. and approximately 10 mL buffer solution was added per L sample. First-order rate constants of LAS removal were determined during this study. (1999) found that the biodegradation rate of anionic surfactants over a range of concentrations (i.39g/L KH2 PO4. 4.53h-1. suband supra-critical micelle concentrations) followed the Monod kinetics. The laboratory apparatus consisted of two porous pot reactors with a working volume of 1-L. the fate of LAS in activated sludge systems. which provided effective separation of suspended solids eliminating the need for a separate clarifier as shown in Figure 2 “Laboratory porous pot system.

Belvedere. The tests were conducted with biomass from the Boone Water Pollution Control Plant (WPCP). 5 ml of mixed liquor from a local municipal wastewater treatment plant was added to the reactors every other day. The reactors were operated at room temperature 22 ± 2 -C. a low concentration (2 mg/L as COD) injection of LAS was made to the respirometric vessel. The raw wastewater was collected from the Boone WPCP and diluted to 200 mg/L as COD.. The composition of the synthetic wastewater is shown in Table 1 “Characteristics of synthetic wastewater. Respirometric tests were used as a surrogate measurement of LAS disappearance in batch kinetic tests as described previously (Ellis et al. Preliminary experiments to ascertain the reliability and reproducibility of the extant technique for measuring surfactant kinetics included experiments to determine the effect of the initial substrate concentration.1 -C. The biodegradation response was modeled in an Excel™ spreadsheet. and the effect of reinjecting LAS to the same biomass sample. All Rights Reserved. To evaluate the validity of using synthetic wastewater for the laboratory studies. The DO response data was collected continuously at a sampling frequency of 10 Hz through a data acquisition board installed in a personal computer. and the kinetic parameters were estimated by nonlinear regression using a fourth-order Runge-Kutta approximation of the Monod equation .” Both wastewaters were fed at a concentration of 200 mg COD/L. The temperature was controlled by a water bath at 25 ± 0. The dissolved oxygen (DO) concentration was measured by a DO meter (Model 3550. CO). Iowa. and the DO probes were fitted with high sensitive membranes. In the test. The initial dissolved oxygen concentration was elevated to approximately 16-18 mg/L using pure oxygen to prevent oxygen from becoming limiting during the entire respirometric response. two porous pot reactors were fed synthetic wastewater to evaluate the influence of HRT and SRT on the biodegradation responses. It was assumed that the actual wastewater contained a similar amount of LAS (which was confirmed by subsequent analysis).WEFTEC 2000 Extant Respirometric Tests. To maintain a diverse microbial consortium. SC). Yellow Springs. the effect of the initial DO concentration. 1996). The reactors were operated in parallel under a Copyright (c) 2000 Water Environment Federation. resulting in a low initial substrate to biomass concentration ratio (S0: X0) ensuring that the test was a measure of the extant kinetics of the biomass (Grady et. After it was determined that synthetic wastewater was an acceptable substitute for real wastewater. This addition represented less than 2% of the feed COD to the reactors and less than 2% of the porous pot mixed liquor concentration at all operating conditions. When a linear decrease in DO was observed. and 2 mg/L LAS (5. . Grab samples of the influent to Boone plant were collected and measured by liquid chromatography/mass spectroscopy (LC/MS) to determine the LAS influent concentration. al. 1996a).. The biomass was continuously stirred using a magnetic stir bar.4 mg/L as COD) was added to the synthetic wastewater.. Extant tests were run to determine whether the kinetic parameters in the two reactors were comparable. The resulting data file was averaged to provide a DO measurement every 2 to 4 seconds and normalized to subtract the background endogenous oxygen uptake rate. a sideby-side comparison of porous pot reactors fed synthetic and raw wastewater was performed. phosphate buffer was added to the biomass sample from the laboratory porous pot reactor or field activated sludge aeration basin. Boone. The sample was then placed in a 250 mL sealed respirometric vessel with a constant temperature water jacket (Tudor Glass Co.

5 mg/L as shown in Table 2 “Concentration of LAS in the influent to the Boone Water Pollution Control Plant. an extended aeration activated sludge plant with an HRT of approximately 18 h and SRT in the range of 24 . Therefore. since LAS contributed 2. a conventional activated sludge plant with an HRT of approximately 4 . To estimate of the competent fraction of LAS degrading biomass. For instance. Additional field tests were conducted at the Iowa City Wastewater Treatment Plant (WWTP). and HRTs of 2. To evaluate the effect of different initial conditions on the extant respirometric technique.86 mg/L (7.. since the biomass obtained 2..72 mg COD/L) and influent COD concentration of 265 mg/L were used to calculate a COD fraction of 2. 16 mg/L was found to be the lower limit to allow the complete biodegradation of LAS in the laboratory experiment prior to oxygen becoming limiting (at approximately 1 mg/L). All Rights Reserved.WEFTEC 2000 constant SRT of 10 d. et al. 6. An additional porous pot operating condition was run at 18 h HRT and 30 d SRT to simulate the operating conditions at the Boone WPCP. and SRTs of 3. and the results indicated a range of LAS concentrations from 1. the competent fraction of degrading biomass in the porous pot reactors was estimated as 2. The C12 homolog was used as the representative test compound for this study. . From this table it can be seen that C12 LAS accounted for about 20% of the total LAS concentration. The upper DO concentration limit of the DO meter was approximately 20 mg/L. Similarly.9% of the biomass had the capacity to degrade LAS (Magbanua. it was assumed that 2. a series of experiments was performed. an average LAS concentration of 2. The biomass for these experiments was obtained from a porous pot reactor with an HRT of 6 h and a SRT of 15 d.” These results suggest that the initial DO concentration in this range did not have an impact on the resulting measured kinetic parameters. A typical respirometric response of a biomass sample to an injection of LAS in the respirometric procedure is given in Figure 3 “Normalized respirometric response and model fit for an Iowa City WWTP biomass sample to an injection of LAS.” These findings are similar to the results reported by Kaiser et al. 4. After many repetitions of LAS biodegradation. The majority of the field tests were conducted at the Boone WPCP. 1998).9% of its energy from LAS. and 12 h. and a range of DO concentrations from 16 to 20 mg/L was used to evaluate the influence of the initial DO on the measured kinetic parameters.” The biomass for this Copyright (c) 2000 Water Environment Federation.9%.30 d. different initial DO concentrations were used when measuring the oxygen consumption to evaluate if this had any effect. 10. 6. Subsequently. Similar results were obtained when comparing the kinetics for LAS by biomass that had received one injection and biomass that had received several repeated injections. and 15 d.6 h and SRT of approximately 6 d.7%.7% of the feed COD. RESULTS AND DISCUSSION LAS concentrations were measured in the influent to the Boone WPCP. the reactors were operated under a constant of HRT of 6 h. and the results are shown in Table 3 “Influence of the initial DO Concentration on the extant kinetics of LAS. 1997.9% was used for the field studies. A competent fraction of 2.

. Experiments to test the influence of a range of HRTs (2 h. In these experiments. 6 h and 12 h) with a constant SRT of 10 d on the biodegradation kinetics of LAS were performed. the experiments to test the influence of a range of SRTs (3 d.” Copyright (c) 2000 Water Environment Federation. Sykes (1999) has suggested that the KS value for a multicomponent wastewater is a cumulative function of the individual KS values for the individual substrates.” In addition. Consequently. Subsequently. During the comparison of raw and synthetic wastewater in the porous pot reactors operated at a HRT of 12 h and SRT of 8 d. Robinson and Tiedje.1983). In a separate experiment. As expected for the total wastewater.WEFTEC 2000 experiment was obtained from the Iowa City WWTP and had a mixed liquor volatile solids concentration of 1990 mg/L.. and this would explain a KS value greater than 2 mg/L as COD for these experiments. not just one component of the wastewater such as LAS) was injected into the extant respirometer. 10 d. 2 mg COD/L of the total wastewater (i. This is likely due to incomplete biodegradation of the entire organic fraction of the wastewater injection during the approximately 30 minute time period of the extant test. 4 h. k (where k = q ˆ/KS). Effect of HRT and SRT on LAS biodegradation. One exception to this was the standard deviations for KS which were somewhat higher. 15 d) with a constant HRT of 6 h were conducted. All Rights Reserved. the extant kinetics of the composite synthetic and raw wastewater was measured using the corresponding biomass from the Boone plant.e. the reproducibility of the kinetic parameter estimates was demonstrated by the standard deviations within an experiment. The similarity in the biodegradation kinetic parameters obtained with the biomass from the two porous pot reactors and by the Boone biomass sample suggests that the synthetic wastewater was a valid alternative to raw wastewater for the subsequent porous pot reactor studies to examine the influence of HRT and SRT on LAS kinetics. The goodness of fit of the Monod model is illustrated by this figure. These results (Table 5 Extant kinetic parameters of synthetic and raw wastewater by Boone biomass”) also indicated very similar responses between the two systems with respect to the pseudo-first order rate coefficient. It is likely that the particulate COD fraction of the synthetic and raw wastewater samples took longer to degrade during the test. The results are shown in Table 4 “Extant kinetic parameters from porous pot reactors fed synthetic and actual wastewater. the trends in the kinetic responses are shown in Figure 4 “Extant biodegradation kinetics of LAS as a function of HRT” and Figure 5 “Extant biodegradation kinetics of LAS as a function of SRT. It can also be seen from this data that the composite wastewater samples had significantly higher yield values than LAS alone. 1996a) due to the correlation between the parameters at these experimental conditions (Robinson. The results of the extant biodegradation tests are shown in the Table 6 “Influence of HRT and SRT on the biodegradation kinetics of LAS.” Comparison with the Student t-test indicates that there was no significant difference between the parameters obtained from the two systems at an α=0. the interesting results from this experiment was the similarity in response by the Boone biomass sample to the synthetic and raw wastewater samples. Typically the standard deviations were within 20% of the mean values for most of the measured parameters.. separate estimates of q ˆ and KS are not possible (Ellis et al. and in these instances. the KS values were higher than the injection concentration (2 mg/L as COD).05. 6 d. biodegradation kinetics were measured periodically. In any event. In addition. the k value (L/mg(h) was reported. 1985.

The biodegradation rate for LAS will slightly decrease when the SRT is long enough.09-0. q ˆ. These results suggest that the laboratory simulation of the field conditions provided an accurate assessment of the actual kinetic capabilities. . In pure culture studies.09 h-1. But when the HRT is long enough. and Y between the three biomass samples tested at an α = 0.69 mg/mg for yield. The effect of SRT on the biodegradation of LAS is shown in Figure 5. There appeared to be a slight decrease in µ ˆ. 0. KS.16 mg COD/L and a Y of 0. a KS of 0. All Rights Reserved. At lower HRTs more variability in the extant kinetic parameters was observed. 0..66 mg/mg.WEFTEC 2000 It can be seen from Table 6 and Figure 4 that the kinetic parameters were fairly constant with a µ ˆ of 0.65~0. was not strong.13~0.(1997) where effluent concentration of LAS remained constant and relatively independent of influent concentrations at higher HRTs. suggesting a low velocity.9% was used for all the field data analysis.e. To further evaluate the capability of the respirometer technique to obtain comparable kinetics of LAS from the lab and the field.14 h-1. and KS at long SRT conditions. a q ˆ of 0. Similar results were observed by Kaiser et al.0. The evidence for this. The similar ranges of the kinetic values and the similar trends with respect to changes in HRT and SRT give more evidence to support the conclusions obtained in the laboratory study. but stayed constant at longer SRTs. one porous pot reactor was run to simulate the operating conditions of the Boone WPCP under a HRT of 18 h and a SRT of 30 d. The yield increased slightly with increased SRT at low SRT conditions. Sokol (1987.50-0. Compared with HRT. The interesting finding from this data is that the variability of the field data was comparable to the variability seen in laboratory activated sludge systems operated Copyright (c) 2000 Water Environment Federation. During this study. field biomass samples were collected periodically and the extant kinetics of LAS were measured. This could be explained by the fact that at lower HRTs the reactors behaved less like ideal CSTR systems (i. 92) observed a much more pronounced decrease in µ ˆ values for cultures grown at increasing long SRTs. at HRTs longer than 6 h.08 . 88a. Table 7 “Extant kinetics of LAS at the Boone and Iowa City plants and laboratory porous pots simulating field conditions” and provides a comparison of the extant kinetics of LAS measured using laboratory biomass simulating field conditions and biomass from the Boone and Iowa City plants. 88b.33 h-1 for q ˆ and 0. These results also suggest that SRT did not have a dramatic effect on the measured biodegradation kinetics of LAS. A competent biomass fraction of 2. KS. the effect of HRT can be ignored.78 mg COD /L for KS.20 h-1 for µ ˆ values. and Y values for the Boone WPCP.05. Table 7 and Figure 6 show the variability in the measured µ ˆ. This would be important for operating laboratory systems to predict full-scale performance with regard to the impact of operational changes on the biodegradation kinetics of specific organic compounds. The results in Table 7 are also shown in Figure 4 and Figure 5 to compare with the results of the laboratory study concerining the impact of HRT and SRT. The results of these experiments indicate that operating conditions have some impact on the complete biodegradation of LAS.09-0. SRT has more impact on the biodegradation of LAS. high affinity enzyme system at these conditions. Student-t tests suggest that there were no significant differences in the values of µ ˆ . q ˆ. but varied at lower HRTs. The extant kinetics ranges of LAS obtained from the biomass fed by synthetic wastewater are 0.05-0. there was more opportunity for short circuiting and variations in flow at shorter HRTs). however.

whether due to the short term changes in operating conditions or gradual changes in the microbial community structure.14 ± 0.67 ± 0.66 ± 0. In fact. This work was funded by the Water Environment Research Foundation (98CTS-3). were not significantly different at the 95% confidence level. and no official endorsement should be inferred.g. 1996b). The SRT had more noticeable effect on the measured biodegradation kinetics (e.08 to 0. the extant kinetics (µ ˆ . and fluctuating operating conditions would be considerably greater than laboratory systems intentionally operated at steady-state. varying flow rates. LAS biodegradation kinetics in laboratory porous pot reactors were independent of whether the reactor was fed synthetic or real wastewater.WEFTEC 2000 at steady-state over a prolonged period of time (Bielefeldt and Stensel.. Y increased from 0. the Boone WPCP and Iowa City WWTP. and Ellis et al. KS. similar extant kinetic parameters resulted. Copyright (c) 2000 Water Environment Federation..50 ± 0. This variability. ACKNOWLEDGMENTS The authors thank Bill Begley and David Lee at Procter and Gamble for their expertise and assistance in determining LAS concentrations and Dave Mozena at the Boone WPCP and Steven Julius at the Iowa City Wastewater Treatment Plant for their help in collecting mixed liquor samples. These findings suggest that there is not a wide variation in the kinetic response for LAS among different treatment plants. .e. The usefulness of the extant respirometric technique to rapidly and reproducibly track changes in LAS biodegradation kinetics in activated sludge cultures in the laboratory and the field was demonstrated. One might expect that the variability of full-scale systems which have varying influent concentrations. the resulting changes in biodegradation rates can be accounted for during the design and operation of activated sludge systems. and Y) from both field sites.3 mg COD/L. The week to week variability in LAS biodegradation kinetics at the Boone plant was significant.06 h-1. When the laboratory porous pot reactors were operated to simulate field conditions. 1999. CONCLUSION The efficacy of the extant respirometric technique to measure the extant kinetics of LAS biodegradation by field and laboratory biomass was demonstrated in this study. and Y = 0. was not substantially different from what has been seen in laboratory activated sludge systems intentionally operated at steady-state.05 mg/mg when the SRT increased from 3 to 10 d at a constant HRT of 6 h). These findings raise important questions as to what causes the variability in biodegradation kinetics.02 mg biomass COD/mg substrate COD) with the possible exception that the biokinetic parameters were more variable at the low HRT conditions (i.4 ± 0. KS = 0.. Once the kinetic variability is characterized. The influence of HRT on the measured biodegradation kinetics was minimal (µ ˆ = 0. when HRT < 6 h). All Rights Reserved. This manuscript has not been subjected to the Foundation’s peer and administrative review and therefore does not necessarily reflect the views of the Foundation.

New York. R. 1178-1184. Marchiori.. D. 5/6. and Marcomini. (1989) Determination of kinetic constants of activated sludge microorganisms responsible for degradation of xenobiotics. Barber L. R. T.. S. (1987) Molecular microbial ecology of naphthalene-degrading genotype in activated sludge.. T. F. Water Environment Research. Wat.. D.WEFTEC 2000 REFERENCES Bielefeldt. P. G... M. 34. K. and Grady. 30. S. C. and Lim.. Smets.P. Environ. (1996a) Respirometric technique for determination of extant kinetic parameters describing biodegradation. 21. (1996) Simultaneous determination of alkylbenzenesulfonates and dialkyltetralinsulfonates in water by liquid chromatography. Jr.. W. 68. Corcia. 31. R. B. C. Magbanua B. A. Krueger. J. E. and Itrich. (1999) Effect of batch discharges on extant biodegradation kinetics in activated sludge systems. Wat. E. K. J. B. Kaiser. Wat. 742-748. Sci..L. Guckert. Ellis T.. C..F. G. Blackburn. G. Ellis.. and Barbeau.. 71. Sawyer. J. L. Res. N. and Anselm.. Environ.. C. All Rights Reserved. Jr. and Cech. Smets. 35-42.. and Grady C. C. Inc.. Barbeau. 733-740.. 30. S. 917-926. Radakovich. T. J. T. Daigger. Smith. Marcel Dekker.. J.. H. P. (1996b) Changes in measured biodegradation kinetics during the long term operation of completely mixed activated sludge (CMAS) reactors. Jr. (1997) Comprehensive approach for assessing the kinetics of primary and ultimate biodegradation of chemicals in activated sludge: Application to linear alkylbenzene sulfonate... Technol.G. 290-298. Samperi. (1996) Variability in kinetic parameter estimates: possible causes and a proposed terminology. Sci. A. July. and Gledhill.. (1999) Evaluation of biodegradation kinetic testing methods and long term variability in biokinetics for BTEX metabolism. The 2nd International IAWQ Conference on Microorganisms in Activated Sludge and Biofilm Processes. NY. L. Smets B. A. T. Ellis. J. (1999) Biological Wastewater Treatment. and Stensel H. Jr. Water Science and Technology. S. C. Res. W. Albokova. California. 2nd Edition. 33. Jain. 884. G.. K. and Sayler... Res. F. J. and Field. L... 21-23. V. 722-730. W.. Federle. B. R. P. B. Grady.(1997) Comparison of activated sludge microbial communities using biolog™ microplates. Chudoba. Water Environment Research. A. Res. Crescenzi. Grady.. Wat. L.. Technol..S. S. D. .. C. 23. R. D. Jr. (1998) Biodegradation of the surfactant linear Alkylbenzenesulfonate in sewage- Copyright (c) 2000 Water Environment Federation. Berkeley.. D. 14311438..

). J. O. G. T. 1960-1963. Jr. C. Nielsen. 61-113. Tech. Marshall (Ed. Gledhill. E. A. 15. and Russell. J. 20.. and Eckhoff. J.. (1985) Determining microbial kinetic parameters using nonlinear regression analysis. (1983) Nonlinear estimation of Monod growth kinetic parameters from a single substrate depletion curve. K.. Journal of Environmental Engineering. Britton. L. M. R. Ritter. Sokol. and Cook. All Rights Reserved. Sokol. M. Nielsen. A. Tech. 32. 45. (1992) Metabolic responses of microorganism growing on inhibitory substrates in nonsteady state culture. Copyright (c) 2000 Water Environment Federation. Mieure. Technol. E. Beall. W.. Environ... and Grady C. Environmental Toxicology and Chemistry.. Mampel.C. A. H.WEFTEC 2000 Contaminated groundwater: A comparison of column experiments and field tracer tests. L. P. W. Sokol.. (1987) Oxidation of an inhibitory substrate by washed cells. 31. Sykes. A. (1995).. Sci. W. 55-62.. Chem. 223-229. Sci. Biotechnology and Bioengineering. 54. 3954-3961. 17.. (1988b) Uptake rate of phenol by Pseudomonas putida grown in unsteady state. W. Jr. 30. N.. Sokol. C. Biotechnology and Bioengineering. Vol.. Trehy. S. P.. In: Advances in Microbial Ecology. Sci.. (1998) Estimation of the competent biomass concentration for the degradation of synthetic organic compounds in an activated sludge culture receiving a multicomponent feed. M. M. 123-140. 233-240. Robinson. T. J.. (1999) Value of Monod’s affinity constant in activated sludge. Environmental Toxicology and Chemistry.. J.. Hitzler. S. (1998) Desulfonation of biotransformation products from commercial linear alkylbenzene sulfonates. 780-781.. 30. P. 921-927. C. Magbanua. L. L. Wat. and Tiedje. 32. J. E. L. and Migiro. A. Environ. Technol. 3397-3404. . 38. Perkins. Ecotox. McCormick. 921-927. Applied and Environmental Microbiology. Plenum Press. Biotechnology and Bioengineering. Biotechnol. Envion. A. W. (1990) Chronic toxicities of surfactants and detergent builders to algae. Poole. W. 8. (1988a) Dynamics of continuous stirred-tank biochemical reactor utilizing inhibitory substrate. Saf. J. M. New York. 125. L. Adamove J. (1997) Biodegradation of coproducts of commercial linear alkylbenzene sulfonate. Lewis M. Robinson. Environmental monitoring for Linear Alkylbenzene Sulfonates. A. 1097-1103.. Dialkyltetralin Sulfonates and their biodegradation intermediates. M.1453-1458. B. A review and risk assessment.

Biodegradation. 115-124. Valsaraj.. Zhang. G. W. C. and Roy. Constant. 151-164. Res. 33. (1996) Complete degradation of xenobiotic surfactants by consortia of aerobic microorganisms.and surpra-critical micelle concentrations (CMCs). Wat. C. (1999) Aerobic biodegradation kinetics of four anionic and nonionic surfactants at sub. D. Copyright (c) 2000 Water Environment Federation.WEFTEC 2000 van Ginkel. . All Rights Reserved.... 7. D. K. T.

Characteristics of synthetic wastewater fed to the porous pot reactors.6 60.0 60. mg/L 37. .0 3. .0 10.0 1.5 2.0 0.0 7.0 20. All Rights Reserved.0 6.g/L 100 62 159 18 22 74 5 Copyright (c) 2000 Water Environment Federation.0 Concentration.WEFTEC 2000 Table 1.0 10. Macronutrients Urea Nutrient broth Lauric acid Potato starch Non-fat dried milk Dietary fiber Sodium acetate Na(HCO3) K3PO4 • H2O FeSO4 • 7H2O LAS AS Micronutrients NiSO4 • 6H2O ZnCl2 CuCl2 • 2H2O CoCl2 • 6H2O MnSO4 • H2O EDTA K2MoO4 Concentration.

03 C14 LAS mg/L <0.86 1.1 1. Date Collected 9/23/99 9/23/99 10/7/99 10/7/99 10/8/99 10/8/99 avg ± s.05 <0.76 C11 LAS mg/L 0. C10 LAS mg/L 0. .05 Total LAS C10-14 mg/L 1.92 2.56 0.18 0.68 1.86 ± 1. All Rights Reserved.05 <0.05 <0.41 C13 LAS mg/L <0. Concentration of LAS in the influent to the Boone Water Pollution Control Plant.36 0.12 2.46 1.36 2.08 1.54 0.72 4.58 4.05 <0.05 0.1 0.74 0.22 <0.66 1.20 ± 0.WEFTEC 2000 Table 2.18 0.16 0.05 <0.05 <0.82 0.05 <0.2 ± 0.05 <0.9 1.55 ± 0.88 C12 LAS mg/L 0.50 1.05 <0.03 ± 0.61 Copyright (c) 2000 Water Environment Federation.61 1.44 0.94 1.d.

681 0. S. . No.770 19.014 0.159 0. All Rights Reserved.082 0. mg/L 16.060 0. KS.215 0. h -1 0.089 0. q ˆ.067 0.645 17.006 q ˆ. The MLVSS concentration of the biomass was 1550 mg/L and the LAS injection concentration was of 2 mg COD/L.215 The µ ˆ.011 KS. Influence of the initial DO concentration on the extant kinetics of LAS. All parameters are in terms of COD units.085 0.057 0. and biomass yield coefficient.051 0.661 18.d.732 0.079 Y.084 0.WEFTEC 2000 Table 3. mg/mg 0. in the Monod equation.703 0.077 0.749 19. Y values refer to the maximum specific growth rate. refers to the standard deviation of the mean.567 1.897 18.055 0. half-saturation coefficient. mg COD/L 0.d. maximum specific substrate removal rate.668 0.071 0. µ ˆ .059 0.098 0. respectively.061 0. Copyright (c) 2000 Water Environment Federation.733 0.032 0. h -1 0.725 0.056 0. 1 2 3 4 5 6 Average s.067 0.098 0.677 0.677 18.030 Initial DO.

727 0.014 0.089 0. mg/L n Reactor fed synthetic wastewater 1 10 20 30 40 47 0.100 0.100 0.386 ± 0. 8 d SRT).400 0.029 0.042 0. h-1 q ˆ.080 0.033 0.337 0.314 0.094 0.065 0.036 0.425 0.459 ± 0.011 The parameters are as defined in Table 3.035 ± 0.06 0.093 0.321 0. .047 2650 1380 808 633 604 604 1 1 1 1 1 3 7 avg ± s.347 ± 0.54 0.330 0.03 0.312 0.196 0. 0.16 0.d.WEFTEC 2000 Table 4.307 0.035 0.049 0.428 0. KS.089 0. Extant Kinetic parameters from porous pot reactors fed synthetic and actual wastewater (12 h HRT.033 ± 0.16 0.425 0.439 0.011 Reactor fed raw wastewater 1 10 20 30 40 47 0.027 0.03 0.021 0.089 0.099 ± 0. 0.905 0.135 0. h-1 COD Y.318 0.102 ± 0 031 0.136 2650 1080 772 614 592 632 1 1 1 1 2 7 12 avg ± s.298 0. mg/L as Day µ ˆ .369 0. All Rights Reserved.130 0.d. mg/mg MLVSS.348 ± 0.112 0.400 0.593 0.100 0.053 0.030 0.54 0. Copyright (c) 2000 Water Environment Federation.06 0.

mg/L * Reactor 1 was the porous pot reactor fed synthetic wastewater and the injected substrate was synthetic wastewater resulting in a concentration of 2 mg/L as COD.871 0. All Rights Reserved.081 0.0157 2 0.716 ± 0.00935 0.WEFTEC 2000 Table 5. mgCOD/mgCOD 0. L/mg(h 0.0143 ± 0.0149 ± 0.825 ± 0.044 Y. Reactor 2 was fed actual wastewater from the Boone Water Pollution Control Plant and the injected substrate was actual wastewater resulting in a concentration of 2 mg/L as COD.0071 0.773 0.0119 avg: 0. Extant kinetic parameters of synthetic and raw wastewater by Boone WPCP biomass.0037 0.659 avg: 0.0199 1 0. .822 0.853 avg: 0.0188 0.0157 0.755 0. The k value is the pseudo-first order rate coefficient (where k = q ˆ/KS) measured in the extant technique when separate estimates of q ˆ and KS are not possible. System k .824 592 604 MLVSS. Copyright (c) 2000 Water Environment Federation.00987 avg: 0.

05± 0.70±0.33± 0.26±1.11± 0.08± 0.26±1.07 24.08 0. Copyright (c) 2000 Water Environment Federation. .20± 0.01 3.13±0.60 0.02 2.35± 0.81 0. The influence of HRT and SRT on the biodegradation kinetics of LAS. mg/mg 0.00±0. h-1 q ˆx.66 ± 0.15 0.69± 0.65±0.42±0..26±10.10±16. mg/L 3574±263 2244±26 1336±41 785±19 250 472± 13 1336± 41 1550 n 10 10 10 10 10 10 10 10 0.05 0.04 0.34 0.12 0.69±0.74 0.WEFTEC 2000 Table 6. h-1 µ ˆ X. All Rights Reserved.18 0.81±0.05 0.65± 0.13 28.15±0.18 0.13±0.80 0.68± 0.10± 0. The parameters are as defined in Table 3.26± 0.01 0.17 2.03 4.08±0.06±0. mgCOD/L 0.13 36.34±0.16± 0.74 0.03 4.35 0.10±4. day day 2 4 6 12 6 6 6 6 10 10 10 10 3 6 10 15 µ ˆ. HRT.24 1.06 0.86 0.50± 0.14±0.17 Y.15 0. mg(L× h)-1 KS.10 0.72 1.03 VSS.59±0.93±8.15 0.51±1.78± 0.02 0.02 The biomass used for these tests were obtained from the porous pot reactors at steady-state-conditions under different operating conditions.81±0.09± 0..07 0.01±0.02 0.42 6.04 0..16± 0.20 0.83±0.52±0.05 17. SRT.09± 0.47± 0..16±0.11 0.18± 0.30 0.24 1.42 0.10 K(q ˆ/KS) L(mgCOD h)-1 0.73± 0.04 0.24 0.07 0.51±1.08± 0.99 0. mg(L× h)-1 q ˆ.08± 0.18± 0..88 5.88 4.09± 0.25±0.68± 0.66±0.11 0.09±0.02 1.56 0.02 6.

0.58 0.85 0. Date µ ˆ .02 0. n = 10 ave ± s.08 0.06±2. h-1 µ ˆ X.54 0. h-1 KS.14±0.53 0.16 0.55 0.49 7. 0.05±0.21 0.09 0.0 2.36 0.21 2650 2250 3100 3415 4380 7500 3756 Iowa City Wastewater Treatment Plant.30±2. mg/mg MLVSS.48±0.16 0. Extant kinetics of LAS at the Boone and Iowa City plants and laboratory porous pots simulating field conditions.05 0. mgCOD/L Y.01 0.0 2. All Rights Reserved.15 0.60 4.05±0.06 0.39±0. . 0.08 0.99 2.02 0.28 2.d.d.19±0. mg/L Boone WPCP 8/23/99 9/6/99 3/23/00 4/1/00 4/06/00 4/19/00 ave ± s.14 1990 Porous pot simulation of Boone WPCP.01 5.11±0. 0.07 0.50±0. 0.02±0.04 0.02 0.10±0. n = 5 ave ± s.13 2250 The parameters are as defined in Table 3.21 0.14±0.40 0.06 0.03±0.06 0.04 0.28 0.45 5.d.0 4.02 0. Copyright (c) 2000 Water Environment Federation.WEFTEC 2000 Table 7.10 0.46±0.56 0. 0. mg (L(h)1 q ˆ.

WEFTEC 2000 Figure 1. All Rights Reserved. Chemical structure of linear alkylbenzene sulfonate (LAS) and C12 LAS where x plus y equals 7 to 11 depending on the length of the alkyl chain (Trehy et al. 1996). CH3 (CH2 )X CH (CH2 )Y CH3 SO3 LAS CH3 (CH2 )9 CH CH3 SO3 Na + C12 LAS Copyright (c) 2000 Water Environment Federation. .

. All Rights Reserved.WEFTEC 2000 Figure 2. Laboratory porous pot system. Sludge wastage Influent (200 mg/L COD) Effluent Stainless steel pot (vol~1000mL) Air bubble Plexiglas Cylinder Copyright (c) 2000 Water Environment Federation.

.WEFTEC 2000 Copyright (c) 2000 Water Environment Federation. All Rights Reserved.

All Rights Reserved. .WEFTEC 2000 Copyright (c) 2000 Water Environment Federation.

WEFTEC 2000 Copyright (c) 2000 Water Environment Federation. . All Rights Reserved.

.WEFTEC 2000 Copyright (c) 2000 Water Environment Federation. All Rights Reserved.