1-Identification of Activated Sludge And

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    IDENTIFICATION OF ACTIVATED SLUDGE AND

    WASTEWATER CHARACTERISTICS USING

    RESPIROMETRIC BATCH-EXPERIMENTS

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

    1Department 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

    (First received June 1996; accepted in revised form August 1997)

    AbstractThis paper presents a procedure to obtain activated sludge kinetics and wastewater character-istics from respirometric batch-experiments. For identication of state variables and model parametersa modied version of the ASM no. 1 that describes the oxygen uptake rate of the nitrication processand organic matter elimination was used. It is demonstrated that the maximum nitrication rate of acti-vated sludge and the concentration nitriable nitrogen, and the rapid hydrolysis rate together with theconcentration slowly biodegradable organic compounds can be estimated accurately. Suggestions toimprove identiability problems are given. It is concluded that the proposed method oers possibilitiesto follow changes in sludge capacities, for both heterotrophic and autotrophic micro-organisms, andwastewater composition.# 1998 Elsevier Science Ltd. All rights reserved

    Key wordsactivated sludge, identication, respirometry, batch-experiments, characterization, bio-kinetic parameters, wastewater composition

    NOMENCLATURE

    iXB mass N per mass COD in biomass (gN gCOD1)

    kH rate of hydrolysis (h1)

    K half-saturation coecient: for heterotrophicbiomass (mgCOD l1); for autotrophic biomass(mgN l

    1)r respiration rate (mgO2 l1 h1)rend initial endogenous respiration rate (mgO2 l

    1 h1)S soluble substrate concentration (mgCOD l1)X particulate substrate concentration (mgCOD l1)Y yield coecient (mgCOD mg

    1 COD)mm maximum specic growth rate (h

    1)

    IndicesS1 and S2 index relative to readily biodegradable organic

    compound 1 and 2S index relative to slowly biodegradable organic

    compoundsi index relative to inert matterNH and NO index relative to ammonia or nitriteA1 and A2 index relative to autotrophic biomass

    Nitrosomonas or NitrobacterH inde x rel at ive t o h eter ot ro phic bio ma ssma x inde x rel at ive t o max imum r at espec inde x rel at ive t o s pec ic ra te

    INTRODUCTION

    For modelling as well as control purposes of waste-

    water treatment plants, information about the

    wastewater composition and activated sludge

    characteristics is essential.

    The traditional way of analyzing wastewater

    composition is based on relatively simple physical-

    chemical methods. Filters are used to distinguish

    the soluble, colloidal and suspended fractions. The

    physical-chemical method is, however, not process-

    related and therefore not able to fractionate the

    readily and slowly biodegradable part. This makes

    wastewater characterization by the physical-chemi-

    cal method less suitable for model simulation or

    control purposes.

    Recent studies were done to gain knowledge

    about activated sludge and wastewater character-

    istics 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 com-

    pound which can be biologically oxidized, is added

    to a batch-vessel which contains a volume of en-

    dogenous respiring activated sludge. After addition

    the respiration rate is measured over a period of

    time. The collected data compose a dynamic respir-

    ation rate prole which provides good means to

    determine wastewater characteristics and activated

    sludge kinetics.

    This paper presents the evaluation of a series ofrespirograms gained from the municipal wastewater

    treatment plant Nijmegen (The Netherlands). The

    Wat. Res. Vol. 32, No. 4, pp. 12401254, 1998# 1998 Elsevier Science Ltd. All rights reserved

    Printed in Great Britain0043-1354/98 $19.00 + 0.00PII: S0043-1354(97)00334-5

    *Author to whom all correspondence should be addressed.

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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 fractionswere compared with the measured analytical data:

    Nkj-N, NH4-N, COD and BOD5.

    MODEL PARAMETER IDENTIFICATION

    Structural and practical identiability

    In the calibration of model parameters identia-

    bility 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 vari-

    ables, 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 identiabil-

    ity; 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 identi-

    able it is not ensured that this parameter is alsopractically identiable. Vanrolleghem et al. (1995)

    showed that when a limited set of data is used for

    parameter estimation, the problem of highly corre-

    lated parameters was disturbing the uniqueness of

    the parameter estimates. In that case, a change in

    one parameter can be compensated by a pro-

    portional shift in another parameter, still producing

    a satisfying t between the experimental data and

    model predictions. Due to correlation's the esti-

    mated parameters may vary over a broad range and

    little physical meaning can be given to the par-

    ameters 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 identi-

    able. In their modied model no nitrication nor

    denitrication were considered and the death-

    regeneration concept was abandoned. The ques-

    tion arises: ``can the parameters, with the avail-

    able experimental data, be given unique values''.

    A useful tool to analyze the precision of par-

    ameter 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 thepractical identiability of model parameters. The

    uncertainty in least-squares parameter estimates yN

    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,

    Cov yN s2e

    XTX

    11

    where s2e is the residual error variance to be esti-

    mated from 1aN pN

    k1etkjy2 and X is the

    Jacobian matrix de(tkvy)/dyj with k = 1,...,N andj= 1,...,p.

    In this particular case: e(tkvy) = OUR(tk) OU R (tk,y), with OU R (tk,vy)

    2 as the pre-

    dicted OUR response at time instant tk as a func-

    tion ofy.

    Eigenvalue decomposition of the covariance

    matrix is dened by:

    VT Cov yNV L 2

    Where V is an orthogonal matrix of eigenvectors

    and L is a diagonal matrix with eigenvalues. The el-

    ements of L indicate whether a parameter combi-

    nation, 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 cor-

    responding 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 s2e 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 bio-kinetic parameters and biodegradable wastewater

    components a modied version of the ASM no. 1

    (Henze et al., 1987) was used. The following modi-

    cations 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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    . Due to the short term of this specic batch-exper-

    iment 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 respir-

    ation 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 di-cult 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 com-

    pound 1 (SS1) present in wastewater

    . oxidation of readily biodegradable organic com-

    pound 2 (SS2) present in wastewater and formedby hydrolysis of slowly biodegradable organic

    compounds (XS)

    . oxidation of ammonia (SNH, present in waste-

    water) to nitrite

    . oxidation of nitrite (SNO) to nitrate

    . endogenous respiration

    Parameter reduction

    The model consisted of a large amount of par-

    ameters and process variables. Some of the par-

    ameters, like mm and XB (for both autotrophs and

    heterotrophs) were structurally unidentiable fromrespiration data (Dochain et al., 1995). The amount

    of parameters was therefore reduced by combining

    non-identiable parameters to structurally identi-

    able 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:

    rNHmax

    iXB

    1

    YA1

    mm,A1XB,A1 3

    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 DOconcentration in the liquid phase to calculate the respir-ation rate of the activated sludge (Spanjers et al., 1996).

    Measuring principle. The peristaltic pump of the respi-rometer is continuously taking a sample of activatedsludge (24 l/h) from the batch vessel. After passing the res-piration vessel (0.75 l), where the dissolved oxygen at theinlet and outlet are measured, the sample is returning tothe batch vessel. Hereby the activated sludge is continu-ously recirculating. Due to the use of a single DO-elec-trode the measuring frequency is limited by the responserate of the DO-electrode (Spanjers and Klapwijk, 1990)and is xed at once a minute.

    An important feature before the addition of substratecan take place is the state of respiration of the activatedsludge. Because one of the goals is to assess the biologicalcharacteristics of the wastewater, it is important that theactivated sludge is respiring in the absence of the exogen-ous substrate; also called the endogenous respiration(Spanjers and Klapwijk, 1990). The time period to aeratethe sludge before it reaches the endogenous state dependson the loading regime of the plant and the spot where thesludge was sampled. Roughly the sludge should be aeratedfor 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 returnsludge.

    2. Aerate the sludge for the time period until endogenousrespiration rate is reached. To detect this state, one canfollow 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 batchvessel containing the activated sludge. The sample ofwastewater has to be aerated rst to prevent a oxygen

    Table 1. Model used for simulation wastewater respirogram

    component -> i 1 2 3 4 5 6j process SS1 SS2 XS SO SNH SNO Process rate

    1 growth heterotrophs on SS1 1

    YH 1YH

    YHiXB mm,H1

    SS1KS1SS1

    XBH

    2 growth heterotrophs on SS2 1

    YH 1YH

    YHiXB mm,H2

    SS2KS2SS2

    XBH

    3 growth N.somonas on SNH 3X43YA1

    YA1iXB

    1YA1

    mm,A1SNH

    KNHSNHXB,A1

    4 growth N.bacter on SNO 1X14YA2

    YA2iXB

    1YA2

    mm,A2SNO

    KNOSNOXB,A2

    5 endogenous respirationautotrophs and heterotrophs -1 rend

    6 Hydrolysis XS 1 -1 kHXS

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    drop in the batch-vessel which will aect the measuredrespiration rate.

    4. After the addition of wastewater the respiration ratewill increase due to the oxidation of organic and nitro-gen compounds.

    5. When the respiration rate has returned to the initialrate, i.e. the rate before adding wastewater (taking di-lution with wastewater into account), the completerespirogram is acquired.

    At the municipal wastewater treatment plant ofNijmegen, a series of respirometric batch-experiments wereperformed on 6 dierent days. The Nijmegen plant has aplug-ow conguration and is mainly treating domesticwastewater. The batch-experiments were commenced bytransferring 0.9 l of pre-settled wastewater to 1.5 l ofreturn sludge in a batch-vessel of 3 l. The applied S0/X0-ratio equals the ratio as it enters the rst compartment ofthe full-scale installation. The experimental conditions arepresented in Table 2.

    RESULTS AND DISCUSSION

    Figure 1 shows the six respiration rate curves

    gained after the addition of wastewater to thebatch-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 esti-

    mate 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 co-

    variance matrix of the estimated parameters are

    given in Appendix A. From the matrix of eigenvec-

    tors (Appendix A) we see that the vectors with thesmallest 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 (3.43-

    YA1)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 sen-

    sitivity plot (d/dy*y) of the parameters concerned.

    From Fig. 3(ad) the derivatives of the residualsto 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 res-

    piration rate, for instance rSs1 (Fig. 1) and more-

    over, 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 sepe-

    rately in this particular experimental setup. A simi-

    lar eect can also be seen from Fig. 3(b) for rNHmaxand (3.43-YA1) KNH.

    Results of the identiability analysis are summar-

    ized in Table 4.

    The parameter combination (1-YH)XS and kHcan 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 conse-quently 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 de-

    sign. Their results indicate that the parameter var-

    iances could be decreased by a factor of 2 when an

    amount of substrate is injected at an optimally cho-

    sen time instant during the experiment.

    Reduction of unknown model parameters also

    can be achieved by the performance of isolated sub-

    strate respirograms. With a sequential addition of

    synthetic substrates of nitrite and ammonia the bio-

    kinetic parameters of autotrophic bacteria can bededuced seperately. In this approach the calibrated

    biokinetic parameters for autotrophic bacteria can

    Table 2. Experimental conditions

    Date MLSS pH Temp COD BOD5 S0/X0*

    (June 1993) (g/l) () (8C) (mgCOD/ l) ( mgCO D/ l) (g COD/g COD)

    16 1.6 6.58 20.5 311 160 0.08818 1.95 7.62 21 247 160 0.05721 1.69 7.69 21 363 170 0.09723 1.59 7.23 20.5 364 185 0.10324 1.7 6.9 19.5 344 180 0.09125 1.76 7.39 20 387 210 0.099

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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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    be used as default settings. The only model par-

    ameters left to estimate are kH, rSmax and (1-YH)KS(in the case of one readily biodegradable organic

    compound) and the wastewater components: (1-

    YH)XS, (1-YH)SS and (3.43-YA1)SNH. This signi-

    cantly reduces the number of unknown parameters

    for parameter calibration of a wastewater respiro-

    gram.

    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/X0ratio determines whether catabolism or anabolism

    prevails. When anabolism prevails, organisms have

    sucient substrate for their growth and cell multi-

    plication dominates above storage and accumu-

    lation phenomena. In order to nd representative

    kinetic parameters it is important to work at low

    S0/X0 ratios. The threshold between low and highratios of S0/X0 is not strictly dened but may be

    considered between an interval of 2 and 4 as a cor-

    rect 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 aregiven 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, half-

    saturation 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/X0ratio which resulted in a considerable population

    shift among the fast-growing/low-anity organisms(Grady et al., 1996).

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

    Table 3. Model parameters, parameter combinations and state variables

    parameterparameter

    combination unit state variableparameter

    combination unit

    rSs1max1

    YH1mmYH1XBH (mgCOD/l.h) SS1* (1-YH) SS1 (mgCOD/l)

    rSs2max1

    YH2mmYH2XBH (mgCOD/l.h) SS2* (1-YH) SS2 (mgCOD/l)

    rNHmax iXB 1

    YA1mmYA1XBYA1 (mgNH4-N/l.h) XS* (1-YH) XS (mgCOD/l)

    rNOmax iXB 1

    YA2mmYA2XBYA2 (mgNO2-N/l.h) SNH* (3.43-YA1) SNH (mgNH4-N/l)

    KS1* (1-YH) KS1 (mgCOD/l)

    KS2* (1-YH) KS2 (mgCOD/l)KNH* (3.43-YA1) KNH (mgNH4-N/l)

    KNO* (1.14-YA2) KNO (mgNO2-N/l)kH - (1/h)

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

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    Figure 6 and Fig. 7 graphically show the time

    variation in the specic maximum substrate elimin-

    ation 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 infor-mation regarding the conversion of nitrite can be

    obtained.

    The maximum conversion rate shows a high vari-

    ation for both nitrifying organisms. Spanjers and

    Vanrolleghem (1995) observed, at the applied S0/X0ratio of 0.05, the wastewater appeared to be inhibi-

    tory 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 inhibitionof nitrication due to a decreasing pH, the maxi-

    mum nitrication rate for both organisms are

    Fig 3(a)(b) caption overleaf.

    Table 4. Identiability classication of a combination of biokinetic model parameters and initial state variables for this specic exper-imental design (Fig. 1)

    IdentiabilityGood Bad

    (1-YH)XS and kH (1-YH)Ks1 and rSs1maxrNHmax; (3.43-YA1)SNH and (1-YH)XS; (1.14-YA2)KNO(1-YH)XS; rNHmax and rSs2max (1-YH)Ss1 and (3.43-YA1)KNHrSs2max and (1-YH)Ss2

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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% errorbounds).

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    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 oxi-

    dation 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 con-centration but mainly relies on temperature.

    Hence, in many activated sludge models hydroly-

    sis 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 exper-

    iment it is suggested to characterize the hydroly-

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

    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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    Table 5 lists the values of hydrolysis rates which

    are reported by several authors and their exper-

    imental designs used.

    Wastewater composition

    A basic problem of the experimental set-up used

    is the fact that addition of wastewater in the batchvessel led to a delayed increase of the respiration

    rate in the attached respirometer. The assumption

    that the initial substrate concentration could be cal-

    culated from the injection at time zero was incor-

    rect. 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 waste-water composition are given in Fig. 9. For the esti-

    mation of dierent wastewater fractions the

    heterotrophic yield (YH) determines the absolute

    concentration of COD and, indirectly, via N-incor-

    poration into biomass, the concentration nitriable

    nitrogen. With the assumption of YH=0.67, and

    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).

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

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    taking into account that 20% of the inuent COD

    exist of biomass (Henze, 1992), the estimated cumu-

    lated organic fractions SS1, SS2, XS, Xi+Si (inert

    COD) and XBH are somewhat higher than the ana-

    lytical measured total COD (Fig. 10). From Fig. 10

    it can be seen that an applied YH of 0.5 corre-

    sponds 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 agree-

    ment 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 waste-

    water 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 im-portant to keep the pH constant at a non-inhibiting

    level.

    CONCLUSIONS

    From identiability analysis it is found that from

    a wastewater respirogram the maximum nitrication

    rate of activated sludge and the concentration nitri-

    able nitrogen, and the hydrolysis rate in combi-

    nation with the concentration slowly biodegradable

    organic compounds can be estimated accurately for

    the given system and experiment.

    The reliability of estimation of model parametersand state variables depends on the respiration pro-

    le and chosen model structure. It is recommended

    that the results of an eigenvalue decomposition of

    the covariance matrix related to given respirograms

    be evaluated.

    To improve the identiability of wastewater com-

    position 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 syn-

    thetic substrates. The assessed biokinetic parameters

    can then be used as default values which favour the

    estimation of the remaining unknown model par-

    ameters.

    Finally, it is demonstrated that respirometric

    batch-experiments are a useful tool in obtaining

    some activated sludge and wastewater character-

    istics. 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.

    AcknowledgementsThe authors wish to thank AnnekeRinia and Ron Blokzijl for their assistance in the researchcarried out. Jacques Segers and Dennis Piron from``Zuiveringsschap Rivierenland'' are thanked for their co-operation during the research.

    REFERENCES

    Chudoba P., Capdeville B. and Chudoba J. (1992)Explanation of biological meaning of the S0/X0 ratio inbatch cultivation. Wat. Sci. Techn. 26, 743751.

    Dochain D., Vanrolleghem P. and Daele van D. (1995)Structural identiability of biokinetic models of acti-vated sludge respiration. Wat. Res. 29, 25712578.

    Grady C. P. Jr., Smets B. F. and Barbeau D. S. (1996)

    Variability in kinetic parameter estimates: a review ofpossible causes and a proposed terminology. Wat. Res.30(3), 742748.

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

    H. Brouwer et al.1252

  • 7/28/2019 1-Identification of Activated Sludge And

    14/15

    Henze M., Grady C.P.L., Gujer W., Marais G.v.R. andMatsuo T. (1987). Activated sludge Model No.1.IAWPRC Scientic and Technical Report No.1,IAWPRC, Londen.

    Henze M. (1992) Characterization of wastewater for mod-elling 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 ModelNo. 2. IAWQ Scientic and Technical Reports. Preprintfor IAWQ Specialised Seminar on Modelling and Controlof Activated Sludge Processes, Copenhagen.

    Kappeler J. and Gujer W. (1992) Estimation of kineticparameters of heterotrophic parameters under aerobicconditions and characterization of wastewater foractivated 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 oxygendynamics in activated sludge processes. Proc. 13th IFAC

    World Congress, July 1996.Novak N., Larrea L. and Wanner J. (1994) Estimatiom ofmaximum specic growth rate of heterotrophic andautotrophic biomass: a combined technique of math-ematical 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 activatedsludge. Wat. Res. 30, 939953.

    San Pedro D. C., Mino T. and Matsuo T. (1994)Evaluation of the rate of hydrolysis of slowly biode-gradable COD (SBCOD) using starch as substrateunder anaerobic, anoxic and aerobic conditions. Wat.Sci. Tech. 30, 191199.

    Sollfrank U. and Gujer W. (1991) Characterization ofdomestic wastewater for mathematical modelling of theactivated sludge process. Wat. Sci. Tech. 23, 10571066.

    Spanjers H. and Klapwijk A. (1990). On-line meter for

    respiration rate and short-term biochemical oxygendemand in the control of the activated sludge process.In Advances in Water Pollution Control, Proc. 5thIAWPRC Workshop, 26 July3 August, Yokohama andKyoto, Japan.

    Spanjers H. and Vanrolleghem P. A. (1994). 50th PurdueIndustrial Waste Conference, Lewis, pp. 611118, 1995.

    Spanjers H. and Keesman K. J. (1994). Identication ofwastewater biodegradation kinetics. Proceedings 3thIEEE. Conference on Control Applications, 2426August, Glasgow, Scotland, pp. 10111016.

    Spanjers H. and Vanrolleghem P. A. (1995) Respirometryas a tool for rapid characterization of wastewater andactivated sludge. Wat. Sci. Tech. 31(2), 105114.

    Spanjers H., Vanrolleghem P. A., Gustaf O. and DoldP. (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 hetero-trophic and nitrifying populations of activated sludgewith an on-line respirographic biosensor. Wat. Sci.Tech. 28, 377387.

    Vanrolleghem P. A. and Van Daele M. (1994) Optimalexperimental design for structure characterization ofbiodegradation models: on-line implementation in arespirographic biosensor. Wat. Sci. Tech. 30, 243253.

    Vanrolleghem P. A., Van Daele M. and Dochain D.(1995) Practical identiability of a biokinetic modelof activated sludge respiration. Wat. Res. 29, 25612570.

    Appendix overleaf.

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    APPENDIX

    A

    EigenvalueDecompositio

    noftheCovarianceMatrix

    (1-YH)S

    s1

    0.00

    0.01

    0.02

    0.05

    0.07

    0.00

    0.39

    0.29

    0.13

    0.64

    0.57

    0.06

    0.04

    (1-YH)S

    s2

    0.18

    0.14

    0.30

    0.21

    0.84

    0.21

    0.18

    0.00

    0.06

    0.13

    0.06

    0.01

    0.01

    (1-YH)X

    s

    0.34

    0.35

    0.70

    0.30

    0.07

    0.08

    0.11

    0.24

    0.25

    0.12

    0.13

    0.01

    0.00

    kH

    0.91

    0.08

    0.21

    0.30

    0.16

    0.09

    0.03

    0.05

    0.03

    0.00

    0.00

    0.00

    0.00

    rNHmax

    0.12

    0.66

    0.43

    0.26

    0.13

    0.08

    0.07

    0.23

    0.24

    0.26

    0.29

    0.02

    0.00

    rNOmax

    0.02

    0.02

    0.05

    0.09

    0.21

    0.91

    0.01

    0.06

    0.14

    0.06

    0.10

    0.29

    0.01

    (3.43-YA

    1)SNH

    0.02

    0.61

    0.22

    0.19

    0.01

    0.16

    0.14

    0.42

    0.45

    0.23

    0.25

    0.04

    0.00

    rSs2max

    0.13

    0.17

    0.36

    0.75

    0.30

    0.02

    0.27

    0.02

    0.23

    0.02

    0.22

    0.05

    0.00

    (3.43-YA

    1)KNH

    0.01

    0.11

    0.08

    0.07

    0.04

    0.02

    0.02

    0.27

    0.51

    0.55

    0.59

    0.03

    0.01

    (1.14-YA

    2)KNO

    0.01

    0.01

    0.01

    0.04

    0.06

    0.28

    0.03

    0.02

    0.04

    0.06

    0.03

    0.95

    0.04

    (1-YH)Ks1

    0.01

    0.01

    0.02

    0.02

    0.08

    0.04

    0.14

    0.47

    0.34

    0.25

    0.17

    0.03

    0.74

    (1-YH)Ks2

    0.01

    0.03

    0.05

    0.30

    0.28

    0.01

    0.81

    0.22

    0.26

    0.08

    0.23

    0.05

    0.00

    rSs1max

    0.01

    0.01

    0.03

    0.03

    0.08

    0.04

    0.18

    0.53

    0.37

    0.24

    0.15

    0.02

    0.67

    Eigenvalues

    8.20E+

    05

    9.80E+

    04

    4.53E

    +

    04

    3.10E+

    04

    1.46E+

    04

    7.22E+

    03

    2.98E+

    03

    1.60E+

    03

    1.35E+

    03

    1.74E+

    02

    1.48E+

    02

    3.07E+

    01

    2.59E+

    00

    H. Brouwer et al.1254