PII: S0043-1354(00)00105-6 Wat. Res. Vol. 34, No. 14, pp. 3580±3590, 2000 7 2000 Elsevier Science Ltd. All rights reserved Printed in Great Britain 0043-1354/00/$ - see front matter www.elsevier.com/locate/watres CALIBRATION AND VALIDATION OF ACTIVATED SLUDGE MODEL NO. 3 FOR SWISS MUNICIPAL WASTEWATER G. KOCHM, M. KUÈHNI, W. GUJERM and H. SIEGRIST*M Swiss Federal Institute for Environmental Science and Technology (EAWAG) and Swiss Federal Institute of Technology (ETH), CH-8600, DuÈbendorf, Switzerland (First received 13 September 1999; accepted in revised form 14 December 1999) AbstractÐASM3 was tested against experimental data from aerobic and anoxic batches as well as fullscale experiments from various WWTPs treating Swiss municipal wastewater. A set of kinetic and stoichiometric parameters emerged from these tests. The calibrated ASM3 allows the sludge production and the denitri®cation capacity to be successfully modeled with a standardized set of parameters. The readily degradable inlet substrate SS,o was estimated from respiration measurements by curve ®tting. This contradicts the suggestion of the IAWQ task group that SS,o in ASM3 may be approximated by the total soluble COD as determined by 0.45 mm membrane ®ltration. Aerobic and anoxic respiration of storage products is insigni®cant compared to growth on these products. 7 2000 Elsevier Science Ltd. All rights reserved Key wordsÐActivated Sludge Model No. 3, ASM3, kinetics, stoichiometrics, full-scale experiments, batch experiments NOMENCLATURE A C H I o ir ini NH NO O, O2 r S STO X autotrophic organisms component with soluble and particulate fractions heterotrophic organisms inert organic material input internal recirculation initial condition ammonium nitrogen nitrate+nitrate nitrogen, anoxic oxygen, aerobic return sludge organic substrate, soluble component cell internal storage product particulate component INTRODUCTION Thanks to today's better scienti®c insights into the biological processes of wastewater treatment, the IAWQ Task Group on Mathematical Modeling for Design and Operation of Biological Wastewater Treatment Processes was able to introduce Activated Sludge Model No. 3 (ASM3) (Gujer et al., *Author to whom all correspondence should be addressed. Tel.: +41-1-823-5054; fax: +41-1-823-5389; e-mail: [email protected] 1999). ASM3 corrects some de®ciencies of ASM1 (Henze et al., 1987). It includes the storage of organic substrates as a new process and lysis is replaced by an endogenous respiration process. As a result, the hydrolysis becomes less dominant for the rates of oxygen consumption and denitri®cation compared to the ASM1 and is now independent of the electron donor. Furthermore, all processes (except for hydrolysis) run at a reduced rate under anoxic as compared to aerobic conditions. The ASM3 also takes smaller anoxic yield coecients into account. A set of kinetic and stoichiometric parameters for the reliable prediction of the nitri®cation and denitri®cation rates in wastewater treatment plants (WWTPs) treating Swiss municipal diluted waste water is proposed in this paper. The most important parameters of ASM3 are ®rst estimated on the basis of batch experiments with activated sludge from dierent WWTPs. For the parameter estimation and the sensitivity analysis, ASM3 was implemented in AQUASIM (Reichert, 1998). Sensitivity analysis are necessary to check, which model parameter can be determined with the aid of the available batch experiments. Based on the multitude of experiments with dierent carbon sources (single substrate and mixed substrate), dierent electron acceptors (nitrate and oxygen) and dierent time constants (long term and short term experiments), the most important model parameters could be esti- 3580 Calibration and validation of ASM No. 3 mated. The uncertainty of parameter estimation is reduced by simultaneously evaluating all the experiments. With multiple experiments at dierent temperatures or with activated sludge from dierent plants the uncertainty could be further reduced. Nevertheless, it is very likely that the same dynamic behavior can be used to explain several parameter combinations. It should be considered that in this paper only a possible way to calibrate ASM3 is suggested and that the experiments were initially designed to calibrate ASM1 and not ASM3. Further experiments will have to be performed in future, speci®cally for calibrating ASM3 more accurately (e.g. heterotrophic storage of organic substrate). ASM3 was then validated for the heterotrophic processes with a wide variety of experimental data from pilot- and full-scale experiments. The experiments were used to calibrate the nitri®cation rates and the sludge production. For these parameters a real validation was not possible. The initial sludge composition of all the batch experiments (the heterotrophic biomass XH,ini, the storage products XSTO,ini and the slowly degradable substrate XS,ini) was simultaneously estimated from the simulations of the full-scale experiments. CALIBRATION OF ASM3 WITH BATCH EXPERIMENTS Endogenous respiration under aerobic and anoxic conditions Batch experiments with sludge from the TuÈffenwies pilot plant (Fig. 6) showed a considerably reduced decay rate of the autotrophic and heterotrophic organisms under anoxic compared to aerobic conditions (Siegrist et al., 1999). This eect can be reproduced in ASM3 by taking into account an aerobic and a slower anoxic endogenous respiration rate for the biomass XH and XA. The decay rates bH,O2 and bH,NO for the heterotrophic biomass at 208C (Table 3) were estimated with AQUASIM from the decrease of the total COD at 14 and 208C, 3581 respectively (Fig. 1). The sensitivity analysis shows that both, the decay rate bH and the initial sludge composition XH,ini, are sensitive in these experiments and strongly correlated with each other. Therefore XH,ini was estimated simultaneously from pilot plant steady state simulation. The determined decay rates bH,O2 and bH,NO for the heterotrophic biomass at 208C were 0.30 and 0.10 dÿ1, respectively. From the decrease of the maximal autotrophic respiration rate also bA,O2 and bA,NO for the autotrophic biomass at 208C were estimated to 0.20 and 0.10 dÿ1, respectively (Siegrist et al., 1999). Sensitivity analysis with both batch and pilot-scale experiments showed, that the respiration rate bSTO for the internal storage products is insigni®cant compared to growth on these products and could not be estimated from the batch tests. Therefore, bSTO was set equal to the endogenous respiration rate analogous to the original ASM3. Aerobic degradation of acetate A tailing-o of the oxygen-consumption curve is often observed in respiration tests (Fig. 2). This phenomenon can be modeled with the storage products XSTO introduced in ASM3. A set of stoichiometric and kinetic parameters for the aerobic storage and growth of the heterotrophic biomass XH could be estimated (Fig. 2) on the basis of aerobic batch experiments with activated sludge from the ZuÈrich±Glatt WWTP (Siegrist et al., 1995) and acetate as the substrate. The parameters YSTO,O2 and kSTO are most sensitive after acetate addition during substrate respiration and could be uniquely determined based on the oxygen consumption curve (Fig. 2). Before and after substrate respiration mainly YH,O2, KSTO and mH are sensitive. The saturation constant KS could be determined during the sudden decrease of the oxygen consumptive rate. The initial sludge composition results from the steady state WWTP simulation. For both experiments, the net (true) yield of heterotrophic biomass produced per unit of substrate removed results in Ynet; O2 YSTO; O2 YH; O2 Fig. 1. Decrease of activated sludge COD from the TuÈenwies pilot plant in anoxic and aerobic batch experiments. CCOD,ini=3500 gCOD mÿ3, XH,ini=1200 gCOD mÿ3. Best ®t with bH,O2=0.30 dÿ1, bH,NO=0.10 dÿ1, yT=0.078Cÿ1 (values at T = 208C). 3582 G. Koch et al. Fig. 2. Heterotrophic oxygen-consumption rate in batch experiments (T = 158C) from 27 November 1992 (left) and 8 December 1992 (right). Acetate addition at 0.053 and 0.081 d, XH,ini=1300 and 1100 gCOD mÿ3, respectively. Sludge from the ZuÈrich±Glatt WWTP, pre-aerated for several hours. Best ®t for both experiments with YH,O2=0.80 gXH gÿ1XSTO, YSTO,O2=0.72 gXSTO gÿ1SS, KS=4.0 gCOD mÿ3, mH=3.0 dÿ1, KSTO=0.1 gXH gÿ1XSTO and kSTO=5.0 dÿ1 (values at T = 208C). 0:72 0:80 0:58gXH g ÿ1 SS , which is about 8% higher than the value suggested by Gujer et al. (1999) (Table 3). Aerobic degradation of soluble COD from primary sludge acidi®cation The characteristic of the oxygen-consumptive curve depends strongly on the available substrate. An aerobic batch experiment with activated sludge from the Neugut±DuÈbendorf WWTP (Fig. 9) and soluble COD from primary sludge acidi®cation as the substrate (Moser-Engeler et al., 1999) was therefore performed (Fig. 3) and con®rmed twice by identical experiments. The net yield from the readily degradable fraction of the total soluble COD Ynet; O2 YSTO; O2 YH; O2 0:80 0:80 0:64gXH g ÿ1 SS is considerably higher than that observed from the acetate batch and suggested by Gujer et al. (1999) (Table 3). To obtain a good ®t Fig. 3. Heterotrophic oxygen-consumption rate in the batch experiment from 19 December 1996. Substrate addition at 0.042 d, XH,ini=880 gCOD mÿ3. T = 108C. Sludge from the aerobic compartment of the Neugut± DuÈbendorf WWTP. Best ®t with YH,O2=0.80 gXH gÿ1XSTO, YSTO,O2=0.80 gXSTO gÿ1SS, KS=10 gCOD mÿ3, mH=3.0 dÿ1, KSTO=0.1 gXH gÿ1XSTO and kSTO=11 dÿ1 (values at T = 208C). Some 80% of the soluble COD were volatile fatty acids. of measured data, the aerobic storage rate constant kSTO has to be increased by about 100%. The maximum oxygen-consumption rate based on dissolved fermentation products is obviously much higher than that based on single-substrate acetate. This observation is in agreement with the measurements of maximum denitri®cation rates on dierent single substrates and mixed fermentation products (Moser-Engeler et al., 1998). Because of the wide variety of substrates in the fermentation products and their individual uptake rates, the saturation constant for substrate SS is greater than that for the single-substrate acetate. It is assumed that fermentation products tend to induce oxygen-consumption curves which are more similar to wastewater than to acetate as a single substrate. Aerobic degradation of COD from wastewater The aerobic yield coecients for storage and growth as well as the high aerobic storage-rate constant kSTO calculated from the batch with fermentation products was con®rmed by 14 analyzed respiration curves with sludge and wastewater from the TuÈenwies pilot plant (eight batch experiments, two of them shown in Fig. 4) and the Neugut± DuÈbendorf WWTP (six batch experiments). In contrast to the original ASM3 (Gujer et al., 1999) where the readily degradable inlet substrate SS,o may be approximated by the total soluble inlet COD SCOD,o as determined by 0.45-mm membrane ®ltration, the SS,o was estimated from respiration measurements by curve ®tting (all estimated SS,o and measured SCOD,o are summarized in Table 1). Otherwise, completely dierent aerobic yields for the municipal wastewater components (mainly colloidal rather than soluble degradable COD) and dierent fermentation products (mainly fatty acids) as the substrate are required. The level of the basic respiration (respiration after consumption of readily degradable substrate) could only be modeled by a Calibration and validation of ASM No. 3 3583 Fig. 4. Typical heterotrophic oxygen-consumption rates for diluted (SS,o=30 gCOD mÿ3, left) and concentrated (SS,o=75 gCOD mÿ3, right) un®ltered wastewater. Measurements from 20 November 1996. The ratio of sludge to wastewater volume in the batch reactor was 1:3 (left) and 1:4 (right), respectively. T = 158C. Activated sludge from the TuÈenwies pilot plant. Best ®t for eight experiments in total with YH,O2=0.80 gXH gÿ1XSTO, YSTO,O2=0.80 gXSTO gÿ1SS, KS=10 gCOD mÿ3, mH=3.0 dÿ1, KSTO=0.1 gXH gÿ1XSTO, kSTO=13 dÿ1 and kH=9.0 dÿ1 (values at T = 208C). substantial increase of the hydrolysis rate constant kH . Anoxic degradation of soluble COD from primary sludge acidi®cation To quantify the reduction of the anoxic yield and the reduction factor for storage and growth, an anoxic batch experiment with activated sludge from the Neugut-DuÈbendorf WWTP and soluble COD from primary sludge acidi®cation as the substrate was analyzed (Fig. 5). From parameter identi®cation with AQUASIM, an anoxic net yield of Ynet; NO YSTO; NO YH; NO 0:70 0:65 0:46 gXH g ÿ1 SS was estimated, which is about 30% lower than the net aerobic yield. On the basis of thermodynamic calculations, a 15% lower net yield can be predicted (Maurer and Gujer, 1998; Orhon et al., 1996). Copp and Dold (1998) determined an average reduction in net yield of about 38% from batch experiments with dierent organic substrates and biomasses. McClintock et al. (1988) and Purtschert and Gujer (1999) observed a reduction of 45 and 25%, respectively, which clearly also con®rms the signi®cant reduction of the anoxic compared with the aerobic yield. The calibrated reduction factor for storage and growth ZNO 0:50 is slightly lower than that suggested by Gujer et al. (1999). The saturation constant KS for the fermentation products as the substrate was found to be identical under aerobic and anoxic conditions (compare the calibrated parameters in Fig. 3 and Fig. 5). VALIDATION OF ASM3 WITH PILOT AND FULL-SCALE EXPERIMENTS ASM3 is validated with a number of pilot- and full-scale experiments on the basis of the kinetic and stoichiometric parameters determined from batch experiments (Table 3). The sludge production in the various WWTPs is calibrated with the fraction of inert particulate COD XI,o from the waste- Table 1. Wastewater characterization based on 14 respiration experiments with sludge and wastewater from the TuÈenwies pilot plant and the Neugut±DuÈbendorf WWTPa WWTP TuÈenwies pilot plant TuÈenwies pilot plant TuÈenwies pilot plant TuÈenwies pilot plant TuÈenwies pilot plant TuÈenwies pilot plant TuÈenwies pilot plant TuÈenwies pilot plant Neugut±DuÈbendorf Neugut±DuÈbendorf Neugut±DuÈbendorf Neugut±DuÈbendorf Neugut±DuÈbendorf Neugut±DuÈbendorf a Experiment T (8C) CCOD,o (gCSB mÿ3) SCOD,o (gCSB mÿ3) SI,o+SS,o (gCSB mÿ3) SI,o+SS,o/SCOD,o 29 October 1996, 10:00 29 October 1996, 13:30 30 October 1996, 10:00 30 October 1996, 13:30 19 November 1996, 10:00 19 November 1996, 14:30 20 November 1996, 10:00 20 November 1996, 13:30 28 February 1996, 16:00 3 August 1995, 11:00 4 August 1995, 03:00 4 August 1995, 10:00 18 July 1995, 11:00 21 July 1995, 09:00 16 16 16.5 16.5 14.5 15 15 15 13 20.5 20.5 20.5 19 19 390 400 390 565 330 435 345 545 480 315 140 520 280 350 170 190 170 190 140 210 135 195 250 185 65 205 ± 120 25+15=40 25+35=60 25+40=65 35+55=90 20+30=50 25+70=95 20+30=50 35+75=110 30+160=190 20+85=105 10+35=45 30+35=65 15+70=85 20+60=80 0.24 0.32 0.38 0.47 0.36 0.45 0.37 0.56 0.76 0.57 0.69 0.32 ± 0.67 CCOD,o=total COD inlet concentration (primary euent), SCOD,o=total soluble COD inlet concentration determined by 0.45-mm membrane ®ltration, SS,o=readily degradable inlet substrate determined by curve ®tting, SI,o=inert soluble COD inlet concentration (about 0.06CCOD,o, Table 4). 3584 G. Koch et al. taken from dierent zones of the pilot plant (Fig. 8). The simulation with the calibrated ASM3 corresponds well to the measurements. WWTP Neugut±DuÈbendorf Fig. 5. Denitri®cation rate in the batch experiment from 12 December 1995. Substrate addition at 0.021 d, XH,ini=700 gCOD mÿ3. T = 208C. Sludge from the aerobic compartment of the Neugut±DuÈbendorf WWTP. Best ®t with YH,NO=0.65 gXH gÿ1XSTO, YSTO,NO= 0.70 gXSTO gÿ1SS, KS=10 gCOD mÿ3, mH=3.0 dÿ1, KSTO=0.1 gXH gÿ1XSTO, kSTO=11 dÿ1, ZNO=0.50 (values at T = 208C). water (Table 4), the observed nitri®cation rate with the maximum autotrophic growth rate mA and the saturation constant for ammonium KA,NH (Table 2). TuÈenwies pilot plant Tracer experiments showed that the ¯ow characteristic of the TuÈenwies pilot plant (total volume of activated sludge tank 1.2 m3) can be simulated as a cascade of eight CSTRs, corresponding to the six anoxic and two aerobic compartments. The sludge blanket was characterized with reactors R1 and R10 (Fig. 6). Ammonium and nitrate were added to the in¯uent to avoid nitrate limitation in the anoxic compartments. A maximum growth rate mA 1:8 d ÿ1 T 20 ^ C and a saturation constant for ammonium KA, NH 1:0 gN m ÿ3 best ®ts the measured ammonium concentrations (Fig. 7) and oxygen-consumption rates (results not shown) of the nitri®ers. The high mA is probably due to the relatively high air ¯ow in the pilot plant, leading to improved CO2 stripping and increased pH. A good prediction of the nitrogen elimination can be observed (Fig. 7). Pro®les of the heterotrophic oxygen-consumption could be determined with activated sludge samples The experimental lane at the Neugut±DuÈbendorf WWTP treats the wastewater for about 15,000 population equivalents (p.e.) and consists of six reactor compartments (R2±R4 anoxic, R5±R7 aerobic, Fig. 9). The ¯ow regime of the activated sludge tank behaves almost like a cascade of six CSTRs. This could be concluded from tracer experiments. Besides the composite samples from the in¯uent and euent, the variation of the denitri®cation capacity within the tanks was also observed with on-line nitrate, nitrite and ammonium equipment. To avoid nitrate limitation in the anoxic compartments and to simulate the eect of the nitrogen-rich supernatant from the sludge digestion that will be built on Neugut in future, nitrogen fertilizer with 25% NH4-N, 25% NO3-N and 50% urea, respectively, was added to the in¯uent. A substantial nitrite accumulation occurred in compartment R6 due to the high temperatures prevailing during the investigated period (T = 20± 228C). On the basis of a nitrogen balance over the anoxic zone (R1±R4), the fraction of the denitri®ed nitrite bNO2 in the total denitri®cation capacity (equation (1)) was about 20%. Due to the signi®cantly smaller COD equivalent of nitrite SNO2 compared to nitrate SNO3 iCOD, NO2 ÿ3:43 and iCOD; NO3 ÿ4:57 gCOD gN ÿ1 , respectively), the denitri®cation potential increases. In ASM3, this can be considered in conjunction with a reduced COD equivalent iCOD, NO for nitrate plus nitrite (SNO) within the composition matrix (equation (2)), leading to increased stoichiometric coecients nj,SNO and therefore to about 8% higher anoxic storage and growth rates. bNO2 Qo SNO2, o Qir SNO2, R6 Qr SNO2, R7 Qo SNO, o Qir SNO, R6 Qr SNO, R7 0:20 1 Table 2. Maximum autotrophic growth rate (T = 208) and saturation constant for ammonium from pilot and full-scale experimentsa WWTP TuÈenwies pilot plant Neugut±DuÈbendorf WWTP Neugut±DuÈbendorf WWTP ZuÈrich±WerdhoÈlzli WWTP ZuÈrich±WerdhoÈlzli WWTP ZuÈrich±WerdhoÈlzli WWTP ZuÈrich±Glatt WWTP a Experiment mA [dÿ1] KA,NH [gN mÿ3] Remarks 11±12 March 1997 26±27 August 1997 3±4 February 1998b 8 March 1998c 2 December 1993c 4±5 December 1996 9±10 November 1992 1.8 0.9 1.4 1.0 1.0 1.0 2.0 1.0 1.0 1.0 2.0 1.5 1.0 2.0 No chemical precipitation No chemical precipitation No chemical precipitation Fe(II) addition in aerobic zone Fe(II) addition in aerobic zone Fe(II) addition in aerobic zone Fe(II) addition in anoxic zone bA,O2=0.20 dÿ1. Experiments not shown. c Experiments discussed in Siegrist et al. (2000). b Calibration and validation of ASM No. 3 3585 Fig. 6. Flow scheme and operating conditions of the TuÈenwies pilot plant. The total sludge retention time yX,tot (incl. R1 and R10) was 17 d. The oxygen concentration in the reactors R8 and R9 was controlled. iCOD, NO bNO2 iCOD, iCOD, NO3 NO2 1 ÿ bNO2 ÿ4:34gCOD gN ÿ1 2 With a maximum growth rate mA 0:9 d ÿ1 (T = 208C) and a saturation constant for ammonium KA, NH 1:0 gN m ÿ3 , the modeled ammonium pro®le (Fig. 10) and autotrophic oxygen-consumption rates (results not shown) ®t the measurements best. With the kinetic and stoichiometric parameters calculated from the batch experiments, the heterotrophic oxygen-consumption rates (results not shown) as well as the total denitri®cation rate (Fig. 10) are slightly underestimated. WWTP ZuÈrich±WerdhoÈlzli The ZuÈrich±WerdhoÈlzli WWTP (600,000 p.e.) is split up into two lanes, north and south. Both lanes have six parallel activated-sludge tanks (6 5000 m3) and six rectangular clari®ers with transverse ¯ow. The activated sludge tanks have a 28% anoxic volume (Fig. 11). The Kjeldahl-nitrogen load of the digester supernatant is about 20% of the load in the primary euent. Here, ASM3 was tested with three experiments (8 March 1988, before installation of anoxic zones; 2 December 1993; 4±5 December 1996) performed at the ZuÈrich±WerdhoÈlzli WWTP with respect to process optimization in the water lane. The ¯ow scheme and the simulation results with the calibrated ASM3 of the ®rst two experiments are discussed in Siegrist et al. (2000). Figure 12 shows the simulation of the third experiment with the calibrated ASM3 (best reproduction of the nitri®cation capacity with mA=1.0 dÿ1 and KA, NH 1:0 gN m ÿ3 at T = 208C). The measured and modeled denitri®cation rates correlate well without any adjustments of the calibrated ASM3. The same experiment could also successfully be modeled with a slightly modi®ed ASM1 (Koch et al., 1999). WWTP ZuÈrich±Glatt The activated sludge system of the WWTP ZuÈrich±Glatt (110,000 p.e.) consists of four parallel lanes (4 1810 m3) and four circular secondary Fig. 7. Modeled (lines) and measured (dots) ammonium (left) and nitrate+nitrite (right) concentrations in R7 and in the euent of the secondary clari®er on 11±12 March 1997. The average total COD and ammonium inlet concentrations during the previous three weeks were 290 gCOD mÿ3 and 38 gN mÿ3 (ammonium dosage). 3586 G. Koch et al. Fig. 8. Modeled and measured pro®les of the actual heterotrophic oxygen-consumption rate. The time axis corresponds to the hydraulic retention time of a sludge package in the TuÈenwies pilot plant (space time). clari®ers with central inlets. The experimental lane had a 33% anoxic volume (Fig. 13, see also Siegrist et al., 1995). The Kjeldahl-nitrogen load of the reject water from digester supernatant is about 15% of the load in the primary euent. With the set of parameters obtained from the batch experiments, the modeled nitrate pro®les reproduce the measurements well (Fig. 14). The maximum growth rate of the nitri®es mA has to be increased to 2.0 dÿ1 for a best ®t, which is substantially higher than generally assumed. The relatively high estimated saturation constant for ammonium KA, NH 2:0 gN m ÿ3 partly compensates the high maximum growth rate. Adjustment of ASM3 after the pilot and full-scale experiments The calibrated ASM3, validated with pilot and Fig. 9. Flow scheme and operating conditions of the Neugut DuÈbendorf WWTP (experimental lane). The total sludge retention time yX,tot (including the sludge blanket R1) was 20 d. The oxygen concentration in the reactors R6 and R7 was controlled. Fig. 10. Modeled and measured ammonium (left) and nitrate+nitrite (right) concentration in dierent reactors on 26±27 August 1997. The average total COD and ammonium inlet concentrations in the previous three weeks were 320 gCOD mÿ3 and 15.7 gN mÿ3 (without N-dosage) respectively. The strong variation in nitrogen dosage in the previous week was considered in the simulation. T = 218C. See Table 4 for the COD inlet fractions and Table 3 for the model parameters. Calibration and validation of ASM No. 3 3587 Table 3. Calibrated kinetic and stoichiometric parameters at T = 208 with exponential temperature dependence yT in parentheses Symbol Kinetic parameters Hydrolysis rate constant Hydrolysis saturation constant Heterotrophic organisms XH Aerobic storage rate constant Anoxic reduction factor for growth/storage Saturation/inhibition constant for oxygen SO Saturation/inhibition constant for SNO Saturation constant for substrate SS Saturation constant for storage Heterotrophic maximum aerobic growth rate Saturation constant for ammonium SNH Saturation constant for bicarbonate SHCO Aerobic endogenous respiration rate of XH Anoxic endogenous respiration rate of XH (from batch and full-scale experiments respectively) Aerobic respiration rate for XSTO Anoxic respiration rate for XSTO Autotrophic organisms (nitri®ers) XA Autotrophic maximum growth rate Ammonium substrate saturation constant for nitri®ers Oxygen substrate saturation constant for nitri®ers Bicarbonate saturation constant for nitri®ers Aerobic endogenous respiration of nitri®ers Anoxic endogenous respiration of nitri®ers Stoichiometric parameters Production of XI in endogenous biomass respiration Aerobic yield of stored products per SS Anoxic yield of stored products per SS Aerobic yield of heterotrophic biomass growth on XSTO Anoxic yield of heterotrophic biomass growth on XSTO Yield of autotrophic biomass per g NO3-N Nitrogen content of SI Nitrogen content of SS Nitrogen content of XI Nitrogen content of XS Nitrogen content of XH and XA Unit ASM3 (Gujer et al., 1999) Calculated values kH KX dÿ1 gXSgÿ1XH 3.0 (0.04) 1.0 kSTO ZNO KO KNO KS KSTO mH KNH KHCO bH,O2 bH,NO gSS gÿ1XH dÿ1 ± gO2 mÿ3 gN mÿ3 gCOD mÿ3 gXSTO gÿ1XH dÿ1 gN mÿ3 mol mÿ3 dÿ1 dÿ1 5.0 (0.07) 0.6 0.2 0.5 2.0 1.0 2.0 (0.07) 0.01 0.1 0.2 (0.07) 0.10 (0.07) bSTO,O2 bSTO,NO dÿ1 dÿ1 0.2 0.1 0.3a 0.15a mA KA,NH KA,O KA,HCO bA,O2 bA,NO dÿ1 gN mÿ3 gO2 mÿ3 mol mÿ3 dÿ1 ± 1.0 (0.105) 1.0 0.5 0.5 0.15 (0.105) 0.05 (0.105) 1.320.4 (0.105) 1.420.5 0.5 0.5 0.20 (0.105) 0.10 (0.105) fXI YSTO,O2 YSTO,NO YH,O2 YH,NO YA iNSI iNSS iNXI iNXS iNBM gXI gÿ1XH gXSTO gÿ1SS gXSTO gÿ1SS gXH gÿ1XSTO gXH gÿ1XSTO gCOD gNÿ1 gN gCODÿ1 gN gCODÿ1 gN gCODÿ1 gN gCODÿ1 gN gCODÿ1 0.20 0.85 0.80 0.63 0.54 0.24 0.01 0.03 0.02 0.04 0.07 0.20 0.80 0.70 0.80 0.65 0.24 0.01 0.03 0.04 0.03 0.07 9.0 (0.04) 1.0 12 (0.07) 0.5 0.2 0.5 10 0.10 3.0 (0.07) 0.01 0.1 0.3 (0.07) 0.10 and 0.15 (0.07) a bSTO could not be calibrated with the experiments and is not sensitive to the change in respiration rates. Analogous to the original ASM3 (Gujer et al., 1999). bSTO was set equal to the endogenous respiration rate bH. full-scale experiments, reproduces the observed nitrate+nitrite pro®les quite well. Nevertheless, the denitri®cation capacity is systematically underestimated in all the experiments. From a sensitivity analysis with AQUASIM (Reichert, 1998) performed with the TuÈenwies experiment from 11±12 March 1997 after model calibration, the most sensitive parameters with respect to the concentrations SNH and SNO in the dierent tanks could be estimated. The parameters most sensitive to the change in denitri®cation capacity are the anoxic yields (YSTO,NO, YH,NO), the inlet substrates XS,o and SS,o and the endogenous respiration rate bH. By changing only bH,NO as the most sensitive kinetic parameter for reproducing the SNO pro®les of the plant, the modeled concentrations of the batch experiments would change only slightly. Therefore bH,NO is suitable for model adjustment. With a 50% higher anoxic endogenous respiration rate (bH,NO=0.15 instead of 0.10 dÿ1 and the anoxic reduction factor 0.50 instead of 0.33, respectively) the denitri®cation rates and thus the modeled nitrate plus nitrite pro®les of all experiments produced a better ®t (modeled pro®les not shown). With this Table 4. Fractions of total COD inlet concentrations (primary euent) WWTP TuÈenwies pilot plant Neugut±DuÈbendorf WWTP Neugut±DuÈbendorf WWTP ZuÈrich±WerdhoÈlzli WWTP ZuÈrich±WerdhoÈlzli WWTP ZuÈrich±WerdhoÈlzli WWTP ZuÈrich±Glatt WWTP a Experiment SS,o SI,o XI,o XS,o XSTO,o XH,o XA,o 11±12 March 1997 26±27 August 1997 3±4 February 1998 8 March 1988a 2 December 1993a 4±5 December 1996 9±10 November 1992 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.20 0.20 0.15 0.20 0.20 0.20 0.25 0.55 0.55 0.60 0.55 0.55 0.55 0.50 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.09 0.09 0.09 0.09 0.09 0.09 0.09 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Experiments discussed in Siegrist et al. (2000). 3588 G. Koch et al. Fig. 11. Flow scheme and operating conditions of the ZuÈrich±WerdhoÈlzli WWTP (experimental lane). The total sludge retention time yX,tot (including the sludge blanket R1 and the inlet channel R7, Koch et al., 1999) was 16 d. The oxygen concentration in the reactors R4 to R6 was controlled. adjustment, bH,NO loses its physical meaning, including any uncertainties in the model parameters and the structure of ASM3. To ®t the total inlet nitrogen CTN,o (equation (3)) and that total nitrogen content of the activated sludge iN,CSB (equation (4)), iNXS and iNXI must be 0:03 gN gX Sÿ1 and 0:04 gN gX Iÿ1 , respectively (Table 3). CTN, o iNXI XI, XA, o o iNXS XS, iNBM XH, o SNH iNSI SI, iNSS SS, iNCSB o in SNO gN m ÿ3 in 3 iNXI XI iNXS XS iNBM XA XH iCSBTSS XTS gN gCSB ÿ1 most sensitive kinetic parameters mA, bA,O2 and KA,NH enable a good ®t of the measured and modeled ammonium pro®les to be obtained in all experiments. Nevertheless, the ®tted maximum growth rates of the nitri®ers vary strongly in the investigated WWTPs. It is not clear whether the inhibition eects to the nitri®es in the dierent plants due to Fe(II), digester supernatant, wastewater composition, etc. or the general uncertainties in parameter ÿ1 estimation (especially if yX; aer mA; net are responsible for the wide variation in mA. The ®tted mA and KA,NH correspond to a net growth rate of mA, net 0:25 d ÿ1 with a standard deviation of 20.1 dÿ1 at T = 108C for 4.0 mM alkalinity, 3.0 gO2 mÿ3 and 10 gNH4-N mÿ3, which is similar to the values given by Gujer (1986). 4 From ammonium pro®les and the autotrophic oxygen-consumption rate during peak ¯ow, the maximum growth rate mA and the saturation constant for ammonium KA,NH were estimated in all fullscale experiments (summarized in Table 2). The CONCLUSIONS ASM3 was tested against a wide variety of experimental data. A set of kinetic and stoichiometric parameters is proposed to describe the sludge production, the nitri®cation and denitri®cation ca- Fig. 12. Modeled and measured ammonium (left) and nitrate+nitrite (right) concentration in dierent reactors on 4±5 December 1996. The average total COD and ammonium inlet concentrations during the previous three weeks were 200 gCOD mÿ3 and 17 gN mÿ3, respectively. T = 148C. See Table 4 for the COD inlet fractions and Table 3 for the model parameters. Calibration and validation of ASM No. 3 3589 Fig. 13. Flow scheme and operating conditions of the ZuÈrich±Glatt WWTP (experimental lane). The total sludge retention time yX,tot (including the sludge blanket R1) was 15 d. The oxygen concentration in the reactors R4 and R5 was controlled. pacity. Aerobic and anoxic batch experiments as well as pilot- and full-scale experiments from dierent WWTPs were successfully modeled with the calibrated ASM3. To further improve the prediction of denitri®cation capacity in full-scale experiments, the anoxic endogenous respiration rate bH,NO should be increased by 50% compared to the value obtained from speci®c decay experiments in the batch reactors. This adjustment leads to bH,NO becoming less physically meaningful, including now uncertainties in the model parameters and structure. The respiration rate on internal storage products is signi®cant compared to growth on these products. This was concluded from sensitivity analyses with both batch and full-scale experiments. Therefore, this process was set equal to the endogenous respiration rate. Readily degradable inlet substrate SS,o was estimated from respiration measurements by curve ®tting. This contradicts the idea of the IAWQ Task Group, who assumed that SS,o may be approximated by the total soluble COD as determined by 0.45-mm membrane ®ltration. This de®nition would lead to dierent heterotrophic yields to be selected for the simulation of batch experiments with wastewater and single substrates, respectively. Because of the poor correlation between soluble inlet COD and readily degradable inlet COD, respiration tests are still recommended for WWTP simulation to decrease model uncertainty. The maximum autotrophic growth rate mA resulting from parameter estimation with full-scale data during peak ¯ow varies greatly from one plant to another. It is not clear whether the nitri®ers in some plants are partly inhibited by the Fe(II), digester supernatant or the wastewater composition. In principle, uncertainties in parameter estimation or model structure may also play an important role in the wide range of the ®tted mA. The parameters of the nitri®ers may be estimated more accurately on the basis of inhibition tests and additional batch experiments with activated sludge from dierent WWTPs. In any case, for unknown wastewater the kinetics of nitri®cation should be investigated under dierent operation conditions in order to obtain relief simulation results. Obviously, ASM3 as well as ASM1 is capable to describe the dynamic behavior in common WWTPs satisfactorily. In situations where for example the storage of readily degradable substrate is dominant (e.g. batch tests or WWTPs treating industrial waste water with a high amount of COD) or for Fig. 14. Modeled and measured ammonium (left) and nitrateÿnitrite (right) concentration in dierent reactors on 9±10 November 1992. The average total COD and ammonium inlet concentrations during the previous three weeks were 180 gCOD mÿ3 and 15 gN mÿ3, respectively. T = 158C. See Table 4 for COD inlet fractions and Table 3 for the model parameters. 3590 G. Koch et al. WWTPs with substantial non aerated zones, ASM3 generates better simulation results. REFERENCES Copp J. B. and Dold P. L. 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