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Journal of Environmental Science and Health, Part A

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A Review and Assessment of Emerging Technologies for the Minimization of Excess Sludge Production in Wastewater Treatment Plants
Gianni Andreottolaa; Paola Foladoria a Department of Civil and Environmental Engineering, University of Trento, Trento, Italy First published on: 01 September 2006

To cite this Article Andreottola, Gianni and Foladori, Paola(2006) 'A Review and Assessment of Emerging Technologies

for the Minimization of Excess Sludge Production in Wastewater Treatment Plants', Journal of Environmental Science and Health, Part A, 41: 9, 1853 1872, First published on: 01 September 2006 (iFirst) To link to this Article: DOI: 10.1080/10934520600779026 URL: http://dx.doi.org/10.1080/10934520600779026

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Journal of Environmental Science and Health Part A, 41:18531872, 2006 Copyright C Taylor & Francis Group, LLC ISSN: 1093-4529 (Print); 1532-4117 (Online) DOI: 10.1080/10934520600779026

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A Review and Assessment of Emerging Technologies for the Minimization of Excess Sludge Production in Wastewater Treatment Plants
Gianni Andreottola and Paola Foladori
Department of Civil and Environmental Engineering, University of Trento, Trento, Italy This paper focuses on the most promising technologies, available for full-scale applications, aimed to the on-site reduction of the excess sludge produced in municipal wastewater treatment plants. New techniques are added to the conventional stages of wastewater treatment, both integrated in the activated sludge bioreactors or applied as pretreatment for the enhancement of anaerobic digestion. A concise review about the alternatives based on physical, chemical or biological mechanisms is described. The present work highlights the efciency of two such techniques, sonolysis and alkaline thermolysis integrated on the return ow from the secondary settler into the activated sludge bioreactors. The investigation on the effect of sonolysis and alkaline thermolysis on activated sludge samples was carried out by evaluating the COD concentration released in soluble and colloidal form and biodegradability measured by respirometry. The physicochemical treatments of sludge have several advantages (easy management, stability in performances and exibility), but are associated with high operational costs that often limit the wide-scale applications. The application of hybrid methods, that couple almost two techniques for the enhancement of efciency with respect to a single one, could optimise the sludge reduction, giving a signicant saving in energy consumption for large-scale operations, but further research is needed. Key Words: Excess sludge production; Wastewater treatment; Sonolysis; Alkaline thermolysis.

Address correspondence to Gianni Andreottola, Department of Civil and Environmental Engineering, University of Trento, via Mesiano 77, 38050 Trento, Italy; E-mail: lisa@ing.unitn.it

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INTRODUCTION
In the municipal or industrial wastewater treatment plants (WWTP) the removal of biodegradable compounds by conventional activated sludge systems and the separation of organic/inorganic particulate by means of physicochemical processes (settlement or ltration) produce a large amount of primary and secondary sludge that have to be disposed. The fate of WWTP excess sludge is becoming an emerging problem due to the continuous increase in sludge production. The global quantity of sludge will rise in the next years as a consequence of the more stringent criteria for WWTP efuents (like in Europe) and due to the new building of WWTPs in developing countries.[1] In the last decades the most widely applied solutions in Europe for the disposal of dewatered sludge have been the agricultural landspreading (direct or after an appropriate biostabilization), the disposal in landll, the incineration or coincineration with waste, while the disposal in the sea is in practice forbidden. Recent new processes may be wet oxidation of liquid sludge or pyrolysis of dried sludge. With regards to the use of sludge on land, its property of soil amendment makes sludge suitable to be used with conventional fertilizers for supporting the progressive loss of organic matter and nutrients in soils due to intensive cultivation. Alternatives like incineration cause loss of sludge nutrients, not allowing, for example, recovery of phosphorus. Considering that phosphorus is an essential constituent of living organisms and reserves of phosphorus are limited, the sludge could have an important role in nutrients supply. On the other hand the possible contamination of sludge by micro-pollutants such as heavy metals, PAH, PCB or dioxins, due to diffused discharges from industrial sites, contributes to worsen the quality of sludge, limiting the application in the environment or precluding the agricultural use. Pollution of agricultural soils by heavy metals or organic micro-compounds can impact negatively both on soil fertility and on food chain, in terms of crop quality and human health. Referring to these aspects the regulation concerning sludge spreading on land is becoming more restrictive.[2,3] For example, the use of sewage sludge for agricultural purpose was limited in Sweden since 1999 and banned in Switzerland in 2005.[4,5] On the other hand, the alternative of sludge disposal in landll has been eliminated by law in many European countries, where the regulation restricts the disposal of waste with high organic matter content, preferring the disposal of ultimate residue. This is the consequence of the EU Directive 99/31 that introduced targets for the disposal of organic waste in landll from 2006. Moreover in many countries available spaces for landll sites are lacking, leading to a general increase of landlling costs. In some European countries taxes were introduced on landlling of organic waste, causing a further increase of the cost for sludge disposal in landll.[4]

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The perspective of a further increase of sludge amount produced by WWTPs in the next years, accomplished by the limits for its disposal, will cause a signicant increase of costs. In many WWTPs at international level, the cost for the disposal of dewatered sludge reaches an half of the whole plant management cost including energy, personnel and ordinary maintenance. For the mentioned reasons, the sludge reduction directly at the WWTP and with acceptable costs is becoming of primary importance. Furthermore at European level, the reduction of biodegradable waste and of sewage sludge production is promoted.[6,7] In this context the emerging technologies aimed to the minimization of excess sludge production, even if they require additional investment and management costs, can allow a global reduction of the whole cost for sludge disposal. Among the technologies for sludge minimization, those that can be applied directly at the WWTP rather than in off-site posttreatments have been pursued in this paper. The rst alternative allows to reduce costs for dewatering, transport, or drying and to enhance biodegradation of sludge directly in aerobic/anoxic/anaerobic bioreactors as a part of the carbon-oxygen cycle.[8,9]

HOW TO ACHIEVE THE SLUDGE MINIMIZATION?

The so called zero discharge of excess sludge is the quintessential objective of the sludge reduction. In the case of municipal wastewater, due to the presence of a signicant amount of inorganic or non biodegradable solids, that are difcult to be completely destroyed even with additional specic treatments, the zero discharge might be onerous to be reach. Therefore it is more feasible to refer to sludge minimization for indicating the objective of sludge reduction processes. Another aspect has to be considered: an excessive disruption of sludge and microorganisms in particular, can reduce the active biomass in the activated sludge plant (nitriers for example) causing a reduction in the removal efciency.[5] In this paper the meaning of the term minimization is adopted according to the one proposed by degaard in his recent overview.[1] In particular minimization is refereed to the reduction of dry mass of sludge, for example by means of sludge digestion or physicochemical lysis followed by biodegradation of the lysate. The reduction of mass of wet sludge obtained by means of dewatering, thickening or drying, as a consequence of water content decrease, was not considered in this context. The treatment of sludge for inducing its reduction can be achieved by introducing an additional stage that can be integrated with: (i) the activated sludge stage as shown in the ow sheet of Figure 1a or (ii) the anaerobic digestion, after thickening and before dewatering (see Fig. 1b).

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Figure 1: Flow sheet for inducing sludge reduction with an additional sludge treatment integrated with: (a) activated sludge stage (b) anaerobic digestion.

In both cases the additional sludge treatment contributes to two effects that take place simultaneously: (a) the dispersion of biological aggregates and activated sludge ocs with the consequent release of soluble and colloidal substrates, part of which are biodegradable, (b) the breakage and death of microorganisms due to the disruption of cellular membrane with the release of intercellular compounds. The result is the enhancement of sludge biodegradability due to the microbial cell lysis and the solubilisation of particulate COD. In the case of Figure 1a, a fraction of the return sludge is treated. The treatment promotes the solubilisation of sludge, that is recirculated into the bioreactors, typically the activated sludge tank, where the released biodegradable fraction is oxidised or, eventually, advantageously utilised as additional carbon source to enhance the nitrogen removal in pre-denitrication. A solubilisation up to 4060% of the total COD may be obtained. The biodegradation of the lysate originates a further growth of biomass in the activated sludge reactor, but globally the observed growth yield decreases. The biomass growth on lysate is called cryptic growth. Most part of the methods for sludge reduction, both physical, chemical or mechanical are aimed to the

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enhancement of the cryptic growth. A reduction around 30% (sometimes more) of the whole sludge production may be obtained.[1] The lysate produced by the sludge solubilisation is rich in soluble COD, but also nitrogen or phosphorous. The additional loads of ammonia can give an overload in the activated sludge reactor both for nitrication and denitrication. Some observations about this aspect were indicated by B hler and Siegrist.[5] o In the case of Figure 1b, the additional stage treats the excess sludge (primary or secondary or both) before the anaerobic digestion. In general a portion of the thickened sludge is injected into the additional sludge treatment. Usually the main factor limiting the anaerobic digestion is the low rate of hydrolysis of particulate matter. Therefore the pre-treatment of sludge aimed to its solubilisation allows to obtain the following advantages: (i) the enhancement of hydrolysis rate and the entire process rate; (ii) the reduction of hydraulic retention time in the digesters, and therefore a small volume could be sufcient or a large amount of sludge could be treated in the same volume; (iii) the increase of biogas production; and (iv) the enhancement of dewatering properties. The major benets were obtained in the pre-treatment of secondary sludge rather than primary sludge due to the low presence of readily biodegradable compounds in the secondary stream and its difculties in dewatering.[10]

OVERVIEW ON EMERGING TECHNOLOGIES

A variety of chemical, physical or biological approaches can be used for sludge reduction. Their development and applications on lab and pilot scale are not new to the researchers. In this paper it seems helpful to do a synthetic overview on the work done in this eld on the most promising methods applied for sludge minimization. Among the biological methods for sludge reduction, the treatment of sludge with a thermophilic aerobic digestion stage has been proposed with the aim to solubilise excess sludge by the action of thermophilic bacteria growing under aerobic or microaerobic conditions.[11] This thermophilic digestion was applied to solubilise sludge that was then recirculated in the activated sludge bioreactor, or as a pretreatment for anaerobic digestion.[12,13] Other methods based on biological mechanisms, like processes that refers to energy uncoupling conditions or to the control of the sludge retention time are reviewed by Liu and Tay.[8] In the last decade, strategies to enhance the grazing capacity of the bioreactors were also proposed.[14] The main limits of methods based on a biological approach is the difculty to model the phenomena and to predict exactly the expected efciency of the process. These limits can be overcome using physicochemical methods, in which the energy intensity or the chemical dosage were decided precisely on the basis of the wanted efciency in sludge

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reduction. Furthermore physicochemical methods can be easier to manage, stable in performances, and exible during operation.[9] For these reasons here in this research, methods based on a physicochemical action have been considered primarly. The physicochemical methods for the reduction of sludge dry mass include: (1) chemical oxidation with strong oxidants such as ozone[5,15,16] ; (2) thermal hydrolysis at temperature above 150 C[17] ; (3) acid or alkaline thermolysis at relatively low temperature (under 100 C) and normal pressures; (4) mechanical disintegration by shear forces or hydrodynamic cavitation[1820] ; and (5) ultrasonic cavitation[2123] Some of these mentioned methods, thermal treatment, ozonation and alkaline hydrolysis, were proposed initially in 90 years, especially as pretreatment to enhance the mesophilic anaerobic digestion. The widespread application of solubilisation methods for improving anaerobic digestion has been limited as a consequence of the high energy requirement and investment capital costs. Nowadays, some of the above-mentioned techniques are assuming an increasing interest, due to the increment in sludge disposal costs and the possibility to recover further energy by biogas. Methods based on thermochemical action, such as acid or alkaline thermolysis suffer from additional costs due to the consumption of reagents and energy required for heating. Ozonation of sludge is one of the most expensive treatments in terms of energy consumption but compensated by the high efciency in sludge reduction.[5] A synthesis of some applications of ozonation for sludge reduction was referred to by Liu.[9] Possible drawbacks are the release of biorefractory soluble compounds in the efuent that could impact on the receiving bodies.[9] Among mechanical disintegration methods, Muller et al. and Lehne et al. referred to stirred ball mills, operating with 0.11.5 mm beads (the better efciency in the case of the smaller beads diameters), and to high-pressure homogenizers in which the disintegration of sludge is due to the hydrodynamic cavitation.[20,24] The state of the art about the application of mechanical disintegration of sludge indicates that the high-pressure homogenizers appear the most efcient alternative in terms of energy saving, but full-scale applications and long-term experiences are quite poor. Ultrasounds application presents a good technical state of the art and a good operational stability. The acoustic cavitation produced by ultrasound waves at frequency above 20 kHz is not new for the degradation of refractory compounds in wastewater and some applications are well reviewed in Gogate.[25] Cavitation is the phenomenon of the formation, growth and subsequent collapse of microbubbles occurring in short times (milliseconds) and producing high levels of pressure and temperatures.[25] Generally the most useful frequencies are in the range 20200 kHz. The main mechanisms induced by ultrasonic irradiation can be synthesised as follows: (i) extreme

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temperature and pressure gradients within the bubbles during cavitational collapse; (ii) combustion or pyrolysis pathways occurring during bubble implosion; and (iii) production of high reactive free-radicals.[26] These factors contributes to the solubilisation of sludge, but in spite of the advantages of ultrasonic cavitation, this process requires the installation of high levels of power with a large energy consumption. Reviews on the acoustic cavitation and the related phenomena, underlining the potential applications, are available in the literature.[25] Despite the several investigations on lab or pilot scale, the references about successfully scaled-up applications are rare; some experiences in UK, Sweden, USA and Australia are recently referred to by Hogan et al.[22] The knowledge on the action of ultrasound cavitation on activated sludge is not exhaustive at the moment and a further optimisation of the operating parameters is required in order to avoid disadvantageous expenses.

Promising Hybrid Techniques

Hybrid techniques, that include the combination of one or more physical and chemical methods, appear at the moment an attractive alternative due to the increase in efcacy with respect to a single technology. Hybrid techniques regards, in general, the coupling of a mechanical action (for example acoustic cavitation) with a chemical action (like the dosage of ozone or alkaline chemicals). With this synergism the efciency of chemical dosage can be improved signicantly thanks to the disaggregation of the coarse and dense biological ocs induced by the physical-mechanical action. Combined methods, like alkaline treatment and sonication, was applied at lab scale by Chiu et al. to enhance anaerobic digestion.[27] Among oxidising agents, ozone is a powerful oxidising agent. The possibility to couple ozonation with an efcient physical treatment, such as ultrasonic cavitation, can give many simultaneous advantages. Besides the mechanisms indicated in the above paragraph, other synergetic actions can be underlined: 1. dispersion of activated sludge ocs by ultrasonic cavitation that increases the specic surface of aggregates and the susceptibility to the action of chemicals in the surrounding medium; enhancement of the ozone transfer in solution due to the action of ultrasonic waves; improvement of the reaction of ozone due to the thermolytical ozone decomposition occurring in the cavitation bubbles, with the consequent release of nascent oxygen, and the increase of the free radicals activity.[28]

2. 3.

In water treatment, Jyoti and Pandit demonstrated the advantages to apply ozonation coupled with ultrasonic cavitation or hydrodynamic cavitation

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(in which pressure variations are caused by velocity variations due to changes in geometry of the system, such as constricted orices, venture etc.).[28] In particular, in the eld of water disinfection, the hydrodynamic cavitation is associated with a minor requirement of energy with respect to ultrasonic cavitation. Not many contributes were found about the feasibility and the efcacy of hydrodynamic cavitation for the enhancement of the sludge reduction. Hydrodynamic cavitation is still rarely applied in the eld of wastewater or sludge treatment as compared to the ultrasonic cavitation. Recently, by taking experiences from pasteurisation, Latte-Trouqu and e Forster referred to a singular investigation on the improvement of anaerobic digestion (at both mesophilic and thermophilic temperature) by using a pretreatment with ultrasounds and -irradiation.[29]

EXPERIMENTAL ASSESSMENT OF PHYSICAL-CHEMICAL METHODS FOR SLUDGE MINIMIZATION

This research was aimed to evaluate the feasibility of some alternatives for the reduction (minimization) of the excess sludge produced by activated sludge plants. Two technologies were optimised and compared: (i) disintegration using ultrasounds at frequency of 20 kHz and (ii) thermo-alkaline hydrolysis at pH 812 and temperature up to 80 C. The feasibility of sonolysis for enhancing anaerobic digestion process and biogas production has been extensively referred to by several Authors, overall in lab and pilot scale applications. Some references with the relative operational conditions are referred to in Table 1 compared with the conditions investigated in this research. Aimed to the fact that many activated sludge plants have small or medium size, and the anaerobic digester is not always present, in this experimentation the efciency of sludge reduction by adopting the conguration of the case in Figure 1a was investigated (reduction of sludge integrated on the sludge recirculation into the bioreactors). The chemical lysis of activated sludge is usually performed using alkaline [(NaOH, Ca(OH)2 ], rather than acid chemicals (HCl or H2 SO4 ) since these latter seem to be less efcient to induce cell lysis when coupled with a thermal treatment.[32] Although several studies mention the inactivation of microorganisms in activated sludge when temperature increases over 4045 C[32,33] a combination of relatively high temperature with alkaline agents is required for obtaining a signicant solubilisation of sludge. Furthermore, the most efcient methods involved in chemical thermolysis couple high temperature and high pressure. The aim of this study was to evaluate the efciency of some low-cost alternatives to induce sludge solubilisation by alkaline thermolysis. Therefore a maximum threshold of temperature equal to 80 C was chosen. The alkaline

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Table 1: Synthesis of references and operational conditions for the application of sonolysis as anaerobic digestion pre-treatment

Frequency (kHz) kJ L1 Scale

Pilot scale Lab scale Lab scale Pre-treatment of anaerobic digestion

Specic power (W/mL) kJ kgTSS1 Application Results

Time (minutes)

Concentration of sludge

Reference
Tiehm et al.[ 21 ]

31

3.6 kW

1040

3.34.0%

increase of methane production of 2.2 times 64% increase of methane production

20 5000100000 17002100 Lab scale 500110000

0.33

20

9.4 gTS/L

1200 4800 400

30000 145500 42,200

200 1.85.4%

7.345.3 gTS/L

20

0.5

1060

Pilot scale Lab scale

23

0.47

1.5

2025 gTS/L

300 1800 42

increase of gas production (23%) increase of hourly biogas production Improved gas production (4050%) and dewaterability

Wang et al. [ 30 ] Chu et al. [ 31 ] Lehne et al. [ 20 ] Onyeche et al. [ 23 ] Latte & Forster[ 29 ] Hogan et al. [ 22 ] This study

Full scale Pilot scale

Pre-treatment of anaerobic digestion Pre-treatment of anaerobic digestion Pre-treatment of anaerobic digestion Pre-treatment of anaerobic digestion Pre-treatment of anaerobic digestion (plus -irradiation) Pre-treatment of anaerobic digestion In activated sludge stage

20

Varied

Varied

Varied

0320

080000

The

whole ranges investigated by authors are indicated.

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treatment was integrated on the return ow in the activated sludge reactor, according to the conguration shown in the case of Figure 1a.

MATERIALS AND METHODS Activated Sludge Samples

Activated sludge were taken from the MWWTP of Trento Nord (Italy), made up of primary settler, oxidation tank and secondary settler, without denitrication (avg. organic load = 0.11 kgBOD5 kgTSS1 d1 ; avg. sludge age = 12 days). Samples of activated sludge were taken from the oxidation stage, with Total Suspended Solid (TSS) concentration in the range 3.04.5 kgTSS m3 . Samples were collected and processed within 12 hours.

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Ultrasonic and Thermo-Alkaline Treatments

For the ultrasonic treatment a device Branson 250 Digital Ultrasonier, operating at 20 kHz, was applied. The horn tip (diameter 12.7 mm) was placed in the centre of a 200 mL cylindrical glass vessels containing 100 mL of sample (V). Sonication was applied at electrical power (P) in the range 20200 W and for duration of treatment (t) up to 4 minutes. The specic energy (Es ) varied up to 300 kJ L1 ; referring to the TSS concentration (x) the range of Es was 080000 kJ kgTSS1 . Specic energy was calculated as the ratio (P t)/(x V). In the case of the thermo-alkaline treatment, NaOH was chosen as alkaline agent for lab tests. The treatment conditions were optimised: temperature in the range 2080 C, pH in the range 812 and time of treatment in the range 1030 minutes.

Analytical Methods
Concentrations of total COD and TSS were measured according to Standard Methods.[34] Filtered COD was measured after ltration of the sample on 0.45 m membrane. Soluble COD was evaluated on the basis of the method proposed by Mamais et al.[35] Particulate COD is dened as the difference between total COD and 0.45 m ltered COD. Colloidal COD was considered as the difference between the 0.45 m ltered COD and the soluble COD. The measurement of biodegradable COD in treated samples was performed by respirometry. In particular the fraction of biodegradable COD in the lysate was evaluated by means of 24-hour respirometric tests, carried out according to the approach proposed by Vanrolleghem et al. for COD characterisation in raw inuent wastewater.[36] The respirometers used in this research were described previously in Ziglio et al.[37] The comparison between the respirograms obtained for the activated sludge samples before and

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after sonolysis or thermolysis, allows to calculate the amount of biodegradable COD released during the sludge disruption. This value gives the basis for the estimation of the sludge reduction capacity when the treated sludge is recycled into the oxidation tank and the biodegradable compounds can be completely oxidised under aerobic conditions.

RESULTS AND DISCUSSION

The optimization of each technology was assessed by considering the main parameters affecting the process: power, time and specic energy in the case of sonolysis, and pH, temperature and time of application, in the case of alkaline thermolysis. In both cases the efciency of sludge solubilization was evaluated on the basis of the dynamic of total COD, soluble and 0.45 m ltered COD in the lysates and the enhancement of biodegradability.

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Sonolysis
To take into account simultaneously power, time of treatment, volume and concentration of the treated sludge, the specic energy, Es , expressed in kJ kgTSS1 was used as reference parameter to discriminate increasing levels of ultrasonic treatment. During the treatment of sonication the concentration of total COD remained, in general, quite constant for increasing levels of Es (data not shown); in fact the process causes a release of soluble and colloidal COD with a correspondent decrease of particulate matter, but the total COD can be considered as a constant. Total COD concentration in untreated samples was equal to 3997 mg L1 on average. The increase of soluble and colloidal COD was measured as percentage of the total COD in the untreated samples and their dynamics as a function of Es are shown in Figure 2a and Figure 2b, respectively. The 0.45 m ltered COD (that is the sum of colloidal and soluble COD), present in very low concentrations in the untreated samples (at concentration around 4% of the total COD), increased appreciably with increasing levels of Es , showing a quite linear dependence. With respect to the soluble COD concentration in the untreated samples, around 50 mgCOD/L (equivalent to 3.1% of the total COD), a signicant increase of soluble COD was observed for Es over 30000 kJ kgTSS1 , reaching concentrations up to 874 mgCOD/L (20% of total COD). In synthesis, for Es up to 60000 kJ kgTSS1 , the released fraction of colloidal COD reaches an average percentage of 24% of total COD, while the soluble COD reaches the 20% of total COD. The progressive disaggregation of sludge ocs, that causes the reduction of particulate COD and the increase of ltered COD, was also demonstrated by observations under microscope.

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Figure 2: Fractions of soluble COD (a) and soluble COD (b) in the activated sludge samples after sonolysis for different values of Es .

In the evaluation of the capacity of excess sludge reduction the estimation of the biodegradability of lysate represents a key parameter. The biodegradable fraction of the lysate was evaluated by respirometry for different levels of Es , by comparing two respirograms: (i) the rst one for the untreated activated sludge in endogenous conditions and (ii) the second one after the addition of a known amount of sludge after sonolysis. The biodegradable COD in treated

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sludge was assessed on the basis of the difference of the integrals of OUR (Oxygen Uptake Rate) calculated for the two respirograms. For the whole range of Es tested, the biodegradable COD was the 44% of the soluble COD on average, while it was only the 18% of ltered COD (soluble+colloidal). These percentages were found to be quite independent by the applied level of Es . An example of the COD fractionation in the lysate (calculated taking into account soluble, colloidal, particulate and biodegradable fractions) produced after sonolysis at Es equal to 54000 kJ kgTSS1 is shown in the diagram of Figure 3b, compared with the COD fractionation of untreated sludge (Fig. 3a). With regards to the unbiodegradable fraction of COD, it could still include biodegradable compounds characterized by a very slow hydrolysis, requiring time longer than the duration of the respirometric tests equal to 24 hours. In synthesis, the following observations can be made about sonolysis and the solubilisation mechanisms of activated sludge: 1. 2. for any level of Es the reduction in size of biological ocs was observed; COD was converted from particulate form to colloidal and soluble form;

Figure 3: COD fractionation in (a) untreated sludge and (b) sludge after sonolysis applied with Es equal to 54000 kJ kgTSS1 .

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for low level of Es the colloidal form is predominant; the soluble COD was released overall for high levels of Es , over 30000 kJ kgTSS1 ; the rapidly biodegradable COD is on average the 44% of soluble COD; higher is the release of soluble COD, higher is the biodegradability of lysate.

In the case of the full-scale application of sonolysis the sustainable levels of energy should be lower than the maximum values of Es investigated in this experimentation, that seems to be much expensive. A more feasible application, with lower applied energy, allows to obtain a dispersion of oc aggregates with an increase in the fraction of COD under 0.45 m. In this case the enhancement of process rate, in oxidation tanks or during anaerobic digestion, is related mainly to the dispersion of particles bioocculated by activated sludge ocs, instead to the death of cells. By increasing of the specic surface, the accessibility between bacteria, enzymes and substrates and therefore the removal rate during the process are enhanced. For the treatment of sludge with power savings, the low concentration of activated sludge is not a good alternative in general and therefore the application on thickened sludge is a better choice.[20] Optimization is necessary in order to evaluate the best combination of energy consumption and sludge concentration, on the basis of the involved mechanisms of ultrasonic cavitation. Most part of experiences referred to in the literature apply sonotrodes at frequency between 20 and 200 kHz. In fact this range of frequency is the most feasible for instruments applicable at large scale. Gogate suggests the use of reactors operating at multiple frequencies (in particular two or three low frequencies) in order to produce more intense cavitation.[25] Further efforts have to be made to effectively scale up these technologies for the simultaneous enhancement of efciency in sludge reduction and the saving in energetic costs.

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Alkaline Thermolysis
The increase of 0.45 m ltered COD was measured as percentage of the total COD in the untreated samples and their dynamics are shown in Figure 4. The results are expressed as a function of pH values and temperature simultaneously. Two different times of treatment, equal to 10 and 30 minutes, were considered in Figure 4a and Figure 4b, respectively. The maximum release of 0.45 m ltered COD and soluble COD was observed for 30 minutes of alkaline treatment at pH 12 and temperature between 60 C and 80 C. Under these operational conditions (60 C, pH 12 for 30 minutes) the alkaline hydrolysis gives an increase of 0.45 m ltered COD from 32 mgCOD/L in the untreated samples to 1800 mgCOD/L after the

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Figure 4: Fractions of 0.45 m ltered COD as a function of pH and temperature for different treatment times: (a) 10 minutes, (b) 30 minutes.

treatment (corresponding to 38% of total COD). The soluble COD released in the same treatment reached 30% of the total COD. For a pH of 12 maintained for 30 minutes and temperature of 60 C the release of ltered COD, was similar to that observed during sonolysis under energy levels of 60,000 kJ kgTSS1 . The biodegradability of sludge lysates reaches 33% of 0.45 m ltered COD and 35% of soluble COD, calculated as average of all the measured

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Figure 5: COD fractionation in (a) untreated sludge and (b) sludge after alkaline thermolysis applied at pH 12 and 60 C for 30 minutes.

values. A synthesis of the results about the COD fractionation in the lysate is shown in the diagram of Figure 5b, compared with the fractionation in the untreated samples (Fig. 5a). Analogously to the COD fractionation in the case of sonolysis, the unbiodegradable fraction of COD could still include compounds requiring time for hydrolysis longer than the duration of the respirometric tests equal to 24 hours. Operational costs for alkaline thermolysis regard the expenses for: (i) energy for heating the sludge until the chosen temperature, (ii) dosage of alkaline agent, (iii) pumping or mixing in the reactor, and (iv) eventual dosage of acid chemicals for neutralization of treated sludge before the discharge in oxidation tank. In the optimization of the conditions for the full-scale application of alkaline treatment, cost and efciency of solubilisation have to be considered simultaneously. By operating at relatively low alkaline levels, near pH 10 for example,[38] the release of soluble COD is not maximised, with respect to the values obtainable at pH 12 (as shown in Fig. 4), but it could be not necessary a further neutralization of pH before the inlet in the aerobic activated sludge reactor. This aspect could reduce signicantly the costs for the treatment

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due to the saving for alkaline chemicals and the successive neutralization. Furthermore it is probably more advantageous to operate at relatively low pH, but adopting higher temperatures (for example around 60 C). From a preliminary cost evaluation, it seems that alkaline thermolysis ensures less operational costs than sonolysis, but further investigations on the efciency of alkaline treatment for excess sludge reduction, coupled with economical evaluations, could be helpful.

CONCLUSIONS
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The aim of present research was to investigate the effect of sonolysis and alkaline thermolysis on activated sludge samples, by taking into account the main operational parameters affecting the processes. The efciency of sludge solubilization was evaluated on the basis of the COD concentration released in soluble and colloidal form during the treatment and the increase in biodegradability. To sum up, sonolysis is efcient in the disruption of activated sludge aggregates, both in terms of increase of soluble and colloidal COD, but high energy consumption is required. A more suitable choice in terms of costs sustainability is the application of moderate energy levels that allow the dispersion of oc aggregates in order to promote the whole biodegradation process thanks to the reduction of oc size. By increasing of the specic surface, the accessibility between bacteria, enzymes and substrates and therefore the removal rate during the process are enhanced. In the case of anaerobic digestion of wastewater excess sludge, the benets in terms of increase in methane production are appreciable as demonstrated more times in literature. With regards to alkaline thermolysis, the maximum release of soluble COD was observed for 30 minutes of alkaline treatment at pH 12 and temperature of 6080 C. Under these operational conditions the level of solubilisation is similar to that observed during sonolysis under energy levels of 60,000 kJ kgTSS1 . The physicochemical treatments of sludge have several advantages (easy management, stability in performances and exibility), but are associated with high operational costs that often limit the wide-scale applications. The optimal technology for sludge reduction has to be selected on the basis of the comparison between the costs for the specic additional treatment and the costs for sludge disposal, including transport, dewatering, handling, storage, drying or incineration. The application of hybrid methods appears as a possible alternative to improve the efciency in sludge reduction, but the additional costs have to be considered. Further development and researches are needed, in order to

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optimise the operating conditions for sludge reduction and cost minimisation, evaluating possible synergisms between different methods. In summary, physicochemical treatment could be an attractive alternative for sludge reduction, but the relationship between efciency of solubilisation, biodegradability and additional costs represents a further objective for the future.

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