PII: S0043-1354(97)00334-5

Wat. Res. Vol. 32, No. 4, pp. 12401254, 1998 # 1998 Elsevier Science Ltd. All rights reserved Printed in Great Britain 0043-1354/98 $19.00 + 0.00

IDENTIFICATION OF ACTIVATED SLUDGE AND WASTEWATER CHARACTERISTICS USING RESPIROMETRIC BATCH-EXPERIMENTS

M H. BROUWER1*, A. KLAPWIJK1* and K. J. KEESMAN2

Department of Environmental Technology, Wageningen Agricultural University, Bomenweg 2, NL-6703 HD Wageningen, The Netherlands and 2Department of Agricultural Engineering and Physics, Wageningen Agricultural University, Bomenweg 4, NL-6703 HD Wageningen, The Netherlands
1

(First received June 1996; accepted in revised form August 1997) AbstractThis paper presents a procedure to obtain activated sludge kinetics and wastewater characteristics from respirometric batch-experiments. For identication of state variables and model parameters a modied version of the ASM no. 1 that describes the oxygen uptake rate of the nitrication process and organic matter elimination was used. It is demonstrated that the maximum nitrication rate of activated sludge and the concentration nitriable nitrogen, and the rapid hydrolysis rate together with the concentration slowly biodegradable organic compounds can be estimated accurately. Suggestions to improve identiability problems are given. It is concluded that the proposed method oers possibilities to follow changes in sludge capacities, for both heterotrophic and autotrophic micro-organisms, and wastewater composition. # 1998 Elsevier Science Ltd. All rights reserved Key wordsactivated sludge, identication, respirometry, batch-experiments, characterization, biokinetic parameters, wastewater composition

NOMENCLATURE iXB kH K r rend S X Y mm Indices S1 and S2 S i NH and NO A1 and A2 H max spec mass N per mass COD in biomass (gN gCOD ) rate of hydrolysis (h1) half-saturation coecient: for heterotrophic biomass (mgCOD l1); for autotrophic biomass (mgN l1) respiration rate (mgO2 l1 h1) initial endogenous respiration rate (mgO2 l1 h1) soluble substrate concentration (mgCOD l1) particulate substrate concentration (mgCOD l1) yield coecient (mgCOD mg1 COD) maximum specic growth rate (h1) index relative to readily biodegradable organic compound 1 and 2 index relative to slowly biodegradable organic compounds index relative to inert matter index relative to ammonia or nitrite index relative to autotrophic biomass Nitrosomonas or Nitrobacter index relative to heterotrophic biomass index relative to maximum rate index relative to specic rate
1

INTRODUCTION

For modelling as well as control purposes of wastewater treatment plants, information about the wastewater composition and activated sludge characteristics is essential.
*Author to whom all correspondence should be addressed.

The traditional way of analyzing wastewater composition is based on relatively simple physicalchemical methods. Filters are used to distinguish the soluble, colloidal and suspended fractions. The physical-chemical method is, however, not processrelated and therefore not able to fractionate the readily and slowly biodegradable part. This makes wastewater characterization by the physical-chemical method less suitable for model simulation or control purposes. Recent studies were done to gain knowledge about activated sludge and wastewater characteristics from a so-called respirogram (Kappeler and Gujer, 1992; Spanjers and Keesman, 1994; Spanjers and Vanrolleghem, 1995; Vanrolleghem and Van Daele, 1994; Dochain et al., 1995; Vanrolleghem et al., 1995). A respirogram is obtained in a batch assay where a sample of wastewater, or a compound which can be biologically oxidized, is added to a batch-vessel which contains a volume of endogenous respiring activated sludge. After addition the respiration rate is measured over a period of time. The collected data compose a dynamic respiration rate prole which provides good means to determine wastewater characteristics and activated sludge kinetics. This paper presents the evaluation of a series of respirograms gained from the municipal wastewater treatment plant Nijmegen (The Netherlands). The

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primary goal was to investigate the identiability of biokinetic model parameters and initial state variables from a wastewater respirogram only. Additionally, the obtained wastewater fractions were compared with the measured analytical data: Nkj-N, NH4-N, COD and BOD5.

E RP, from given single output data y E RN and in this case the available OUR data, is given by the covariance matrix of the estimates, T 1 Cov yN s2 1 e X X where s2 to be estie is the residual error variance 2 and X is the mated from 1aN p N k1 etk jy Jacobian matrix de(tkvy)/dyj with k = 1,...,N and j = 1,...,p. In this particular case: e(tkvy) = OUR R (tk,y), with OU R (tk,vy)2 as the pre(tk) OU dicted OUR response at time instant tk as a function of y. Eigenvalue decomposition of the covariance matrix is dened by: NV L V T Cov y 2

MODEL PARAMETER IDENTIFICATION

Structural and practical identiability In the calibration of model parameters identiability analysis plays an important role. The key question of the identiability analysis was dened by Dochain et al. (1995) as follows: ``Can we expect, given a set of measured state variables, to give the model parameters a unique value, via parameter estimation?'' Herein a distinction was made in identiability on the basis of the model structure only (structural identiability; Dochain et al., 1995) or on the type and quality of available data (practical identiability; Vanrolleghem et al., 1995). Dochain et al. (1995) studied the structural identiability of kinetic models describing the activated sludge process from the assumption that only respiration data were available. They concluded, for four types of models, that only a smaller set of the combinations of the original parameters were structurally identiable. In the case of a parameter that is structurally identiable it is not ensured that this parameter is also practically identiable. Vanrolleghem et al. (1995) showed that when a limited set of data is used for parameter estimation, the problem of highly correlated parameters was disturbing the uniqueness of the parameter estimates. In that case, a change in one parameter can be compensated by a proportional shift in another parameter, still producing a satisfying t between the experimental data and model predictions. Due to correlation's the estimated parameters may vary over a broad range and little physical meaning can be given to the parameters obtained. Parameter uncertainty evaluation Dochain et al. (1995) showed that from a modied ASM no. 1 seven combinations of the ve original parameters were structurally identiable. In their modied model no nitrication nor denitrication were considered and the deathregeneration concept was abandoned. The question arises: ``can the parameters, with the available experimental data, be given unique values''. A useful tool to analyze the precision of parameter estimates is the eigenvalue decomposition of the covariance matrix (Vanrolleghem et al., 1995; Lukasse et al., 1996). Let us recall very briey the theory to study the practical identiability of model parameters. The N uncertainty in least-squares parameter estimates y

Where V is an orthogonal matrix of eigenvectors and L is a diagonal matrix with eigenvalues. The elements of L indicate whether a parameter combination, given the weights of the associated eigenvector, aects the sum of squares. A small eigenvalue (li) corresponds with a relatively large uncertainty in the direction of the associated (Vi) vector. If, for instance, an element Vi,j is large as compared to other elements in this column, the corresponding parameter value is dicult to estimate accurately. In other words: for this parameter the respirogram is non-informative and consequently a wide range of parameter values can be used to describe the experimental data. Notice that in equation 1 the term s2 e stems from the output data and since it is a scalar it can be interpreted as a scaling factor. Consequently, the analysis could also have been performed with the Fisher Information Matrix. XTX directly, as in Vanrolleghem et al. (1995).

ACTIVATED SLUDGE MODEL

Modied IAWQ-model In order to investigate the identiability of biokinetic parameters and biodegradable wastewater components a modied version of the ASM no. 1 (Henze et al., 1987) was used. The following modications and assumptions were introduced: . Nitrication was modelled as a two-step process; ammonia was converted to nitrite by Nitrosomonas and nitrite was converted to nitrate by Nitrobacter. . Readily biodegradable organic substrate was split up into two fractions (SS1 and SS2) (Spanjers and Vanrolleghem, 1994). . Slowly biodegradable organic substrate (XS) was, due to hydrolysis, converted to SS2. . Hydrolysis was modelled as rst-order kinetics (Sollfrank and Gujer, 1991).

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Table 1. Model used for simulation wastewater respirogram

j 1 2 3 4 5 6

process

component -> i

1 SS1 Y1H

2 SS2

3 XS

4 SO
YH 1 YH YA1 3X43 YA1 YA2 1X14 YA2 YH 1 YH

5 SNH iXB iXB iXB Y1 A1

6 SNO

Process rate
SS1 mm,H1 KS1 SS1 XBH SNH mm,A1 KNH SNH XB,A1 SNO mm,A2 KNO SNO XB,A2 SS2 mm,H2 KS2 SS2 XBH

growth heterotrophs on SS1 growth heterotrophs on SS2 growth N.somonas on SNH growth N.bacter on SNO endogenous respiration autotrophs and heterotrophs Hydrolysis XS

Y1H

iXB Y1 A2

-1 1 -1

rend kHXS

. Due to the short term of this specic batch-experiment the endogenous respiration was assumed to be constant. . iXB was assumed to be 0.086 gN gCOD1 (Henze et al., 1987). The modications were introduced because the ASM no. 1, as such, was not able to produce a satisfying t between modelled and measured respiration data. Not incorporated in the model were: . Growth and decay processes of autotrophic and heterotrophic biomass. These parameters were left out of consideration because the experiments performed didn't allow their estimation. Due to the short term of the experiment and the low S0/ X0-ratio used (S0 and X0 were the initial substrate and biomass concentration; expressed in COD), decay respectively growth of biomass were dicult to obtain. . Hydrolysis of slowly hydrolysable organic matter according to ASM no. 1. . Denitrication, because dissolved oxygen was non-limiting in the performed experiments. . Ammonication, because this process was assumed to be instantaneous (Henze et al., 1994). From Table 1 it can be seen that the oxygen uptake rate is composed of: . oxidation of readily biodegradable organic compound 1 (SS1) present in wastewater . oxidation of readily biodegradable organic compound 2 (SS2) present in wastewater and formed by hydrolysis of slowly biodegradable organic compounds (XS) . oxidation of ammonia (SNH, present in wastewater) to nitrite . oxidation of nitrite (SNO) to nitrate . endogenous respiration Parameter reduction The model consisted of a large amount of parameters and process variables. Some of the parameters, like mm and XB (for both autotrophs and heterotrophs) were structurally unidentiable from respiration data (Dochain et al., 1995). The amount of parameters was therefore reduced by combining

non-identiable parameters to structurally identiable parameter combinations (Vanrolleghem and Verstraete, 1993; Spanjers and Vanrolleghem, 1994; Dochain et al., 1995). For instance, the maximum nitrication rate (specic for Nitrosomonas) could be measured with an excess of exogenous substrate described by the following equation:   1 rNHmax iXB m XB,A1 3 YA1 m,A1 In this equation iXB, YA1, mm,A1 and XB,A1 were combined to one measurable parameter rNHmax.
EXPERIMENTAL PROCEDURE

The experimental set-up consisted of a batch-vessel (3 l) which was directly attached to a continuous respirometer (RA-1000; Manotherm). The respirometer is classied as a continuous ow-through measurement which uses the DO concentration in the liquid phase to calculate the respiration rate of the activated sludge (Spanjers et al., 1996). Measuring principle. The peristaltic pump of the respirometer is continuously taking a sample of activated sludge (24 l/h) from the batch vessel. After passing the respiration vessel (0.75 l), where the dissolved oxygen at the inlet and outlet are measured, the sample is returning to the batch vessel. Hereby the activated sludge is continuously recirculating. Due to the use of a single DO-electrode the measuring frequency is limited by the response rate of the DO-electrode (Spanjers and Klapwijk, 1990) and is xed at once a minute. An important feature before the addition of substrate can take place is the state of respiration of the activated sludge. Because one of the goals is to assess the biological characteristics of the wastewater, it is important that the activated sludge is respiring in the absence of the exogenous substrate; also called the endogenous respiration (Spanjers and Klapwijk, 1990). The time period to aerate the sludge before it reaches the endogenous state depends on the loading regime of the plant and the spot where the sludge was sampled. Roughly the sludge should be aerated for a period of 2 h without feed (Spanjers and Klapwijk, 1990). The experimental procedure was as follows: 1. Add a known volume of sludge to the batch-vessel. This may be sludge from the aeration tank or return sludge. 2. Aerate the sludge for the time period until endogenous respiration rate is reached. To detect this state, one can follow the course of the measured respiration rate. 3. After the endogenous rate is reached a known volume of pre-aerated wastewater can be added to the batch vessel containing the activated sludge. The sample of wastewater has to be aerated rst to prevent a oxygen

Use of respirometry to characterise sludge

Table 2. Experimental conditions Date (June 1993) 16 18 21 23 24 25 MLSS (g/l) 1.6 1.95 1.69 1.59 1.7 1.76 pH () 6.58 7.62 7.69 7.23 6.9 7.39 Temp (8C) 20.5 21 21 20.5 19.5 20 COD (mgCOD/l) 311 247 363 364 344 387 BOD5 (mgCOD/l) 160 160 170 185 180 210 S0/X* 0 (gCOD/gCOD) 0.088 0.057 0.097 0.103 0.091 0.099

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drop in the batch-vessel which will aect the measured respiration rate. 4. After the addition of wastewater the respiration rate will increase due to the oxidation of organic and nitrogen compounds. 5. When the respiration rate has returned to the initial rate, i.e. the rate before adding wastewater (taking dilution with wastewater into account), the complete respirogram is acquired. At the municipal wastewater treatment plant of Nijmegen, a series of respirometric batch-experiments were performed on 6 dierent days. The Nijmegen plant has a plug-ow conguration and is mainly treating domestic wastewater. The batch-experiments were commenced by transferring 0.9 l of pre-settled wastewater to 1.5 l of return sludge in a batch-vessel of 3 l. The applied S0/X0ratio equals the ratio as it enters the rst compartment of the full-scale installation. The experimental conditions are presented in Table 2.

RESULTS AND DISCUSSION

Figure 1 shows the six respiration rate curves gained after the addition of wastewater to the batch-vessel containing endogenously respiring sludge. Directly after the addition of wastewater to the activated sludge the respiration rate increases and within two minutes the maximum respiration rate is reached. The gures contains rough data. Observe that Fig. 1(af) shows a respirogram with a double nitrogen tailing. A double tailing is created when the conversion rate of nitrite into nitrate (Nitrobacter) is lower than ammonia into nitrite (Nitrosomonas) and consequently nitrite is accumulated. A double nitrogen tailing is previously recognized by Ossenbruggen et al. (1996). For all six respirograms the model is used to estimate the model parameters and state variables. In Fig. 2 the measured and modelled total respiration rate (16 June 1996) and the estimated respiration rates for the ve wastewater components are shown. The modelled respiration rate matches the measured respiration rate. Identiability analysis The model contains 9 biokinetic parameters and 4 initial state variables, listed in Table 3. Results of an eigenvalue decomposition of the covariance matrix of the estimated parameters are given in Appendix A. From the matrix of eigenvectors (Appendix A) we see that the vectors with the smallest eigenvalues (column 10, 11, 12 and 13) contains the following dominant weights on the

parameters and initial state variables: (1-YH)Ss1, rSs1max and the saturation coecients (3.43YA1)KNH and (1.14-YA2)KNO (roughly, elements >0.3). Consequently, these parameters/states are dicult to obtain with the given experimental data set. The poor identiability is conrmed by the sensitivity plot (d/dy*y) of the parameters concerned. From Fig. 3(ad) the derivatives of the residuals to the parameters and state variables become visible and it is shown that for some parameters only a small part of the curve is sensitive for a change of the residual of the estimate. When only a very few data points are related to the substrate induced respiration rate, for instance rSs1 (Fig. 1) and moreover, as no saturation behaviour can be observed, no information is retained to dierentiate between rSs1max and (1-YH)KS1. In this case only the rst order constant rSs1max/(1-YH)KS1 can be estimated. Notice, furthermore, from Fig. 3(d) that the high sensitive peaks of (1-YH)XS and kH coincides and thus these parameters cannot be identied seperately in this particular experimental setup. A similar eect can also be seen from Fig. 3(b) for rNHmax and (3.43-YA1) KNH. Results of the identiability analysis are summarized in Table 4. The parameter combination (1-YH)XS and kH can be estimated very precisely in combination. However, this will not guarantee both parameters can be separately estimated with the same accuracy. To improve the reliability of estimation Lukasse et al. (1996) suggested to reduce the amount of model parameters by giving them xed values. Those parameters which were not sensitive to the model output were given a xed value and consequently the remaining model parameters could be obtained with higher accuracy. Another approach was suggested by Vanrolleghem et al. (1995). They suggested the use of an optimal experimental design. Their results indicate that the parameter variances could be decreased by a factor of 2 when an amount of substrate is injected at an optimally chosen time instant during the experiment. Reduction of unknown model parameters also can be achieved by the performance of isolated substrate respirograms. With a sequential addition of synthetic substrates of nitrite and ammonia the biokinetic parameters of autotrophic bacteria can be deduced seperately. In this approach the calibrated biokinetic parameters for autotrophic bacteria can

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Fig 1. (a)(c).

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Fig. 1. Wastewater respirograms obtained at 6 dierent days.

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Fig. 2. Wastewater respirogram (16 September 1993) with measured and modelled respiration rates.

be used as default settings. The only model parameters left to estimate are kH, rSmax and (1-YH)KS (in the case of one readily biodegradable organic compound) and the wastewater components: (1YH)XS, (1-YH)SS and (3.43-YA1)SNH. This signicantly reduces the number of unknown parameters for parameter calibration of a wastewater respirogram. Biokinetic parameters With the objective to obtain biokinetic constants from batch cultivated biodegradation experiments it is demonstrated that the applied S0/X0 is extremely important (Chudoba et al., 1992; Novak et al., 1994; Spanjers and Vanrolleghem, 1994). The S0/X0 ratio determines whether catabolism or anabolism prevails. When anabolism prevails, organisms have sucient substrate for their growth and cell multiplication dominates above storage and accumulation phenomena. In order to nd representative kinetic parameters it is important to work at low S0/X0 ratios. The threshold between low and high ratios of S0/X0 is not strictly dened but may be

considered between an interval of 2 and 4 as a correct estimation (Chudoba et al., 1992). The wastewater treatment plants generally work at very low actual S0/X0 ratios. The applied actual S0/X0 ratio varied between 0.057 and 0.103 (Table 2). Therefore it is expected that the observed biokinetic parameters will represent true values. The estimated biokinetic heterotrophic parameters are given in Fig. 4 and Fig. 5. The parameter values found are readily in agreement with values reported in literature using similar calibration techniques (Spanjers and Vanrolleghem, 1994). However, halfsaturation coecients found by other research groups show signicantly higher values: 2.5 to 4 mgCOD/l (Kappeler and Gujer, 1992), 5 mgCOD/ l (Sollfrank and Gujer, 1991) and 20 mgCOD/l (Henze et al., 1987). Dierences found can be explained by the applied experimental conditions. Kappeler and Gujer worked at a very high S0/X0 ratio which resulted in a considerable population shift among the fast-growing/low-anity organisms (Grady et al., 1996).

Table 3. Model parameters, parameter combinations and state variables parameter rSs1max rSs2max rNHmax rNOmax KS1* KS2* KNH* KNO* kH parameter combination
1 YH 1 1 YH 2

unit (mgCOD/l.h) (mgCOD/l.h) (mgNH4-N/l.h) (mgNO2-N/l.h) (mgCOD/l) (mgCOD/l) (mgNH4-N/l) (mgNO2-N/l) (1/h)

state variable SS1* SS2* X S* SNH*

parameter combination (1-YH) SS1 (1-YH) SS2 (1-YH) XS (3.43-YA1) SNH

unit (mgCOD/l) (mgCOD/l) (mgCOD/l) (mgNH4-N/l)

mmYH1 XBH mmYH2 XBH

iXB Y1 mmYA2 XBYA2 A2 (1-YH) KS1 (1-YH) KS2 (3.43-YA1) KNH (1.14-YA2) KNO -

iXB Y1 mmYA1 XBYA1 A1

* Under the assumption of known biomass yield (YH, YA1 and YA2).

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Table 4. Identiability classication of a combination of biokinetic model parameters and initial state variables for this specic experimental design (Fig. 1) Good (1-YH)XS and kH rNHmax; (3.43-YA1)SNH and (1-YH)XS; (1-YH)XS; rNHmax and rSs2max rSs2max and (1-YH)Ss2 Identiability Bad (1-YH)Ks1 and rSs1max (1.14-YA2)KNO (1-YH)Ss1 and (3.43-YA1)KNH

Figure 6 and Fig. 7 graphically show the time variation in the specic maximum substrate elimination rate for Nitrosomonas and Nitrobacter. Taking into account the poor identiability of rNOmax (Appendix A), special care should be paid to these values. On June 23 and 24 the observed respirogram shows only one tailing. From this type of respirogram it is obvious that no information regarding the conversion of nitrite can be obtained.

The maximum conversion rate shows a high variation for both nitrifying organisms. Spanjers and Vanrolleghem (1995) observed, at the applied S0/X0 ratio of 0.05, the wastewater appeared to be inhibitory to nitrication. Inhibition of nitrication was not veried. However, due to a low pH on June 16 and 24 (Table 2) inhibition of the nitrication rate could have been occurred. In the case of inhibition of nitrication due to a decreasing pH, the maximum nitrication rate for both organisms are

Fig 3(a)(b) caption overleaf.

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Fig. 3. Sensitivity plot of the model parameters and state variables.

Fig. 4. Estimated specic maximum substrate elimination rates for heterotrophic organisms (95% error bounds).

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Fig. 5. Estimated half-saturation coecients readily biodegradable compounds SS1 and SS2 (assumed YH=0.67); (95% error bounds).

underestimated. Consequently, the area of the curve which is attributed to oxidation of XS is estimated larger and a smaller area is attributed to the oxidation of SNH which results in an overestimation of XS and underestimation of SNH. According to the ASM no. 1 the hydrolysis constant kH slightly depends on the biomass concentration but mainly relies on temperature. Hence, in many activated sludge models hydrolysis of slowly biodegradable organic substrate is simplied to a rst order conversion. Because it is not possible to deduce the hydrolysis rate of

slowly biodegradable COD from a 2-h experiment it is suggested to characterize the hydrolysis process as fast hydrolysis (Sollfrank and Gujer, 1991; Spanjers and Vanrolleghem, 1995). The hydrolysis rate of slowly biodegradable organic substrate is given in Fig. 8. The hydrolysis shows a rather constant rate, except on June 24. The estimated values are in the range of previous works. Dierences can be explained by the medium or temperature which is used to obtain the hydrolysis rate. In some cases a dierent time scale is used.

Fig. 6. Estimated specic maximum substrate elimination rate for Nitrosomonas and Nitrobacter (assumed YA1=0.18 and YA2=0.06); (95% error bounds).

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Fig. 7. Estimated half-saturation ammonia and nitrite coecients (assumed YA1=0.18 and YA2=0.06); (95% error bounds).

Fig. 8. Estimated hydrolysis rate of slowly biodegradable organic substrate (95% error bounds).

Table 5. Reported rst order hydrolysis rates Authors This study San Pedro et al. (1994) Kappeler and Gujer (1992) Sollfrank and Gujer (1991) Sollfrank and Gujer (1991) Spanjers and Vanrolleghem (1995) kH (h ) 0.732.17 0.05 to 0.14 0.17 to 0.21 0.75 1.04 2.4
1

temp. (8C) 19.521 20 14 10 20 20

time scale OUR ``short-term''

medium wastewater starch wastewater wastewater wastewater wastewater

OUR ``short-term''

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Fig. 9. Estimated organic wastewater fractions: XS, Ss1, Ss2; assumed XBH and measured total COD, euent COD (Xi + Si) and BOD5 (assumed YH=0.67).

Table 5 lists the values of hydrolysis rates which are reported by several authors and their experimental designs used. Wastewater composition A basic problem of the experimental set-up used is the fact that addition of wastewater in the batch vessel led to a delayed increase of the respiration rate in the attached respirometer. The assumption that the initial substrate concentration could be calculated from the injection at time zero was incorrect. This phenomenon could be corrected by injecting the sample of wastewater in both batch

and respiration vessel in appropriate amounts (equal dilutions), or by applying mass balances for both vessels as done by Spanjers and Vanrolleghem (1994). Because the maximum respiration rate was reached within 2 min after the addition we think the possible error made was almost negleglible. The estimated and analytical measured wastewater composition are given in Fig. 9. For the estimation of dierent wastewater fractions the heterotrophic yield (YH) determines the absolute concentration of COD and, indirectly, via N-incorporation into biomass, the concentration nitriable nitrogen. With the assumption of YH=0.67, and

Fig. 10. Cumulated total COD calculatedfor YH=0.5 and 0.67, compared to measured total COD.

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Fig. 11. Estimated and analyzed nitrogen wastewater fractions: SNH (nitriable nitrogen) and NH4-N and Nkj-N (assumed YA1=0.18 and YA2=0.06).

taking into account that 20% of the inuent COD exist of biomass (Henze, 1992), the estimated cumulated organic fractions SS1, SS2, XS, Xi+Si (inert COD) and XBH are somewhat higher than the analytical measured total COD (Fig. 10). From Fig. 10 it can be seen that an applied YH of 0.5 corresponds more reasonable to the measured values. The estimated nitriable nitrogen concentration shows some inconsistency with the nitrogen found from chemical analysis (Fig. 11). Spanjers and Vanrolleghem (1995) found values in good agreement with the ammonia concentration found by analysis. They rst calculated YA1 from a dosage of known amount of ammonia and used this value to obtain the ammonia concentration from the wastewater experiment. YA1 values of 0.36 and 0.56 were found. Dierences could be explained by a poorly controlled pH during the experiment (Table 2), which is aecting the estimated maximum oxidation rates and consequently the inuent composition. Therefore we would like to stress that it is very important to keep the pH constant at a non-inhibiting level.
CONCLUSIONS

that the results of an eigenvalue decomposition of the covariance matrix related to given respirograms be evaluated. To improve the identiability of wastewater composition the number of unknown model parameters should be reduced. In this paper it is suggested that the biokinetic parameters be obtained separately, with the addition of a sequence or mixture of synthetic substrates. The assessed biokinetic parameters can then be used as default values which favour the estimation of the remaining unknown model parameters. Finally, it is demonstrated that respirometric batch-experiments are a useful tool in obtaining some activated sludge and wastewater characteristics. Automation of the procedure could make it possible to follow changes of activated sludge as well as wastewater characteristics in time and is therefore recommended.
Acknowledgements The authors wish to thank Anneke Rinia and Ron Blokzijl for their assistance in the research carried out. Jacques Segers and Dennis Piron from ``Zuiveringsschap Rivierenland'' are thanked for their cooperation during the research.

From identiability analysis it is found that from a wastewater respirogram the maximum nitrication rate of activated sludge and the concentration nitriable nitrogen, and the hydrolysis rate in combination with the concentration slowly biodegradable organic compounds can be estimated accurately for the given system and experiment. The reliability of estimation of model parameters and state variables depends on the respiration prole and chosen model structure. It is recommended

REFERENCES

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Use of respirometry to characterise sludge Henze M., Grady C.P.L., Gujer W., Marais G.v.R. and Matsuo T. (1987). Activated sludge Model No.1. IAWPRC Scientic and Technical Report No.1, IAWPRC, Londen. Henze M. (1992) Characterization of wastewater for modelling of activated sludge processes. Wat. Sci. Tech. 25, 115. Henze M., Gujer W., Mino T., Matsuo T., Wentzel M. C. and Marais G. v. R. (1994). Activated Sludge Model No. 2. IAWQ Scientic and Technical Reports. Preprint for IAWQ Specialised Seminar on Modelling and Control of Activated Sludge Processes, Copenhagen. Kappeler J. and Gujer W. (1992) Estimation of kinetic parameters of heterotrophic parameters under aerobic conditions and characterization of wastewater for activated sludge modelling. Wat. Sci. Tech. 25, 1992, 125139. Lukasse L. J. S., Keesman K. J. and Straten van G. (1996) Grey-box identication of dissolved oxygen dynamics in activated sludge processes. Proc. 13th IFAC World Congress, July 1996. Novak N., Larrea L. and Wanner J. (1994) Estimatiom of maximum specic growth rate of heterotrophic and autotrophic biomass: a combined technique of mathematical modeling and batch cultivations. Wat. Sci. Tech. 30, 171180. Ossenbruggen P. J., Spanjers H. and Klapwijk A. (1996) Assesment of a two-step nitrication model for activated sludge. Wat. Res. 30, 939953. San Pedro D. C., Mino T. and Matsuo T. (1994) Evaluation of the rate of hydrolysis of slowly biodegradable COD (SBCOD) using starch as substrate under anaerobic, anoxic and aerobic conditions. Wat. Sci. Tech. 30, 191199.

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Sollfrank U. and Gujer W. (1991) Characterization of domestic wastewater for mathematical modelling of the activated sludge process. Wat. Sci. Tech. 23, 10571066. Spanjers H. and Klapwijk A. (1990). On-line meter for respiration rate and short-term biochemical oxygen demand in the control of the activated sludge process. In Advances in Water Pollution Control, Proc. 5th IAWPRC Workshop, 26 July3 August, Yokohama and Kyoto, Japan. Spanjers H. and Vanrolleghem P. A. (1994). 50th Purdue Industrial Waste Conference, Lewis, pp. 611118, 1995. Spanjers H. and Keesman K. J. (1994). Identication of wastewater biodegradation kinetics. Proceedings 3th IEEE. Conference on Control Applications, 2426 August, Glasgow, Scotland, pp. 10111016. Spanjers H. and Vanrolleghem P. A. (1995) Respirometry as a tool for rapid characterization of wastewater and activated sludge. Wat. Sci. Tech. 31(2), 105114. Spanjers H., Vanrolleghem P. A., Gustaf O. and Dold P. (1996) Respirometry in control of the activated sludge process. Wat. Sci. Tech. 34(2), 117126. Vanrolleghem P. A. and Verstraete W. (1993) Simultaneous biokinetic characterization of heterotrophic and nitrifying populations of activated sludge with an on-line respirographic biosensor. Wat. Sci. Tech. 28, 377387. Vanrolleghem P. A. and Van Daele M. (1994) Optimal experimental design for structure characterization of biodegradation models: on-line implementation in a respirographic biosensor. Wat. Sci. Tech. 30, 243253. Vanrolleghem P. A., Van Daele M. and Dochain D. (1995) Practical identiability of a biokinetic model of activated sludge respiration. Wat. Res. 29, 2561 2570.

Appendix overleaf.

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APPENDIX A

Eigenvalue Decomposition of the Covariance Matrix

H. Brouwer et al.

(1-YH)Ss1 (1-YH)Ss2 (1-YH)Xs kH rNHmax rNOmax (3.43-YA1)SNH rSs2max (3.43-YA1)KNH (1.14-YA2)KNO (1-YH)Ks1 (1-YH)Ks2 rSs1max Eigenvalues

0.00 0.18 0.34 0.91 0.12 0.02 0.02 0.13 0.01 0.01 0.01 0.01 0.01 8.20E + 05

0.01 0.14 0.35 0.08 0.66 0.02 0.61 0.17 0.11 0.01 0.01 0.03 0.01 9.80E + 04

0.02 0.30 0.70 0.21 0.43 0.05 0.22 0.36 0.08 0.01 0.02 0.05 0.03 4.53E + 04

0.05 0.21 0.30 0.30 0.26 0.09 0.19 0.75 0.07 0.04 0.02 0.30 0.03 3.10E + 04

0.07 0.84 0.07 0.16 0.13 0.21 0.01 0.30 0.04 0.06 0.08 0.28 0.08 1.46E + 04

0.00 0.21 0.08 0.09 0.08 0.91 0.16 0.02 0.02 0.28 0.04 0.01 0.04 7.22E + 03

0.39 0.18 0.11 0.03 0.07 0.01 0.14 0.27 0.02 0.03 0.14 0.81 0.18 2.98E + 03

0.29 0.00 0.24 0.05 0.23 0.06 0.42 0.02 0.27 0.02 0.47 0.22 0.53 1.60E + 03

0.13 0.06 0.25 0.03 0.24 0.14 0.45 0.23 0.51 0.04 0.34 0.26 0.37 1.35E + 03

0.64 0.13 0.12 0.00 0.26 0.06 0.23 0.02 0.55 0.06 0.25 0.08 0.24 1.74E + 02

0.57 0.06 0.13 0.00 0.29 0.10 0.25 0.22 0.59 0.03 0.17 0.23 0.15 1.48E + 02

0.06 0.01 0.01 0.00 0.02 0.29 0.04 0.05 0.03 0.95 0.03 0.05 0.02 3.07E + 01

0.04 0.01 0.00 0.00 0.00 0.01 0.00 0.00 0.01 0.04 0.74 0.00 0.67 2.59E + 00