Session 1 Sludge treatments and their effects on pathogens Treatment and disinfection of sludge using quicklime A.D. Andreadakis Department of Water Resources, Faculty of Civil Engineering, National Technical University of Athens, 5 Iroon Polytechniou St., Zorgafou, Athens 15773, Greece Introduction Lime is a readily available alkali, which is widely used in sewage treatment. Utilisation of lime has the following benefits: a) conditions all types of sludge, b) precipitates toxic metals and removes nutrients, c) destroys the pathogenic agents, d) reduces the biochemical and biological oxygen demand and suspended solids, e) eliminates offensive odours. Two forms of application of lime are usually distinguished: a) as unslaked (quick-) lime - CaO and b) as slaked lime - Ca(OH)2. Furthermore during treatment of sludge, lime can be added to the sludge before thickening, before dewatering, or after dewatering. No significant difference has been observed between the effect of hydrated lime and quicklime when treating sludge with high water content, as is the case of undewatered sludge (Tullander, 1993). In reaction with water CaO within a few minutes forms Ca(OH)2. For that reason if quicklime is used in sludge with a high water content the same effect will be attained in practice as with hydrated lime, but with a lower dose of chemicals (1:1.3). As the handling of quicklime is more complicated, hydrated lime is normally used in small treatment plants and quicklime in large plants. When quicklime is slaked to the hydrated form, energy is emitted 1160 kJ/kg CaO. Theoretically, 350-400 kg CaO/m3 water can bring the temperature near the boiling point. However, as the quantities of lime used in practice normally are related to the dry solids content of the sludge, the treatment of undewatered sludge will not result in any significant rise of temperature. The effects of liming undewatered sludge, usually at the dose of 10-20 kg/m3 can be summarised as follows: i) improvement of sludge dewatering properties (in some cases in combination with addition of ferrous sulphate or ferric chloride), ii) pH increase to about 11.5-12, which lasts for about two weeks, iii) no increase of temperature, iv) inactivation of bacterial and viral pathogens, but limited effect on parasites and v) regrowth of bacterial pathogens. In the case of dewatered sludge, addition of quicklime, results in a significant temperature rise and high dry solid content due to evaporation. This in turn leads to improved sludge handling characteristics and long lasting disinfection. 31 This paper deals with quicklime treatment of dewatered sludge and reviews important aspects of the process involved, such as temperature and dry solids content increase, pH rise and maintenance, sludge sanitation, sludge handling and physicochemical characteristics, nutrients availability to the plant and technological possibilities. Chemical reactions Calcium can be easily found in the form of CaCO3. However, addition of CaCO3 to sludge has very limited effect on pathogen destruction, due to the limited pH rise that can be obtained up to 8.5. For this reason calcium carbonate is thermally treated at a temperature of 1100-1200 °C, to produce CaO. CaCO3 + 42.5 kcal → CaO + CO2 (1) The quality of the final product (quicklime) depends on the quality of CaCO3 and the thermal process and this quality in term determines the rate of temperature increase of the subsequent reaction of CaO with water. CaO + H2O → Ca(OH)2 + 15 kcal (2) With addition of the appropriate quantity of CaO a pH increase to approximate 12.5 can be obtained. However, it should be noted that unless excess CaO is used, a consequent reduction of the pH can be observed due to the reaction of the produced Ca(OH)2 with the CO2 of the atmosphere or that produced due to biological activity. Ca(OH)2 + CO2 → CaCO3 + H2O (3) CaCO3 + CO2 → Ca2+ + 2HCO-3 (4) Temperature and solids content increase The expected temperature rise can be theoretically estimated assuming that 100% of the heat released (1160 kJ/kg CaO) is utilised and considering the specific heat values of water, initial solids (TS1) and lime. ∆T= 1160x%CaO 4.16(100%–%TS1) + 0.25x%TS1 + 0.3x%CaO (5) Equation (5) gives an almost linear increase of ∆T with CaO dose. For dewatered sludges with TS content in the range 20-30% respective increases of 3.4 to 3.9 °C for each percent CaO dose (1% CaO = 10 kg CaO per tonne of sludge) can be theoretically expected. In practice due to heat losses and quicklime quality (less than 100% active CaO), the observed temperature increases are limited to 60-82% of the theoretical values. The time needed to effect the temperature increase is approximately one to two hours after mixing, depending on lime quality. 32 The increase in the solids due to quicklime addition is almost linear. Theoretically the new solids content (TS2) can be calculated, by considering the chemical reaction (2) as follows: %TS2= %TS1 + [74/56x%CaO] x100% 100% + %CaO (6) A further slight increase of solids can occur due to formation of CaCO3 as a result of reactions with CO2. The solid content increase results in a more compact sludge, which can be stored and handled more easily. pH increase and maintenance It has been found (Carl Bro S/A, 1997), that in order to raise the pH in sludge from 7 to 12.5, 1.7 mmoles of (OH) are needed per gr TS, so that the buffering capacity of proteins of sludge is neutralised. Since 56 mg CaO produce 2 mmoles (OH), 50 mg CaO are needed per gr TS. For sludge with 20-30% TS, 1-1.5% CaO are needed to effect the increase to 12.5. At this dose there is no excess CaO to neutralise CO2 and organic acids production. Therefore, a higher dose typically above 2% CaO is normally needed. It is not unusual to use doses in the range 6-10% CaO in order to ensure maintenance of the high pH over sufficiently long periods (several months). One of the main reasons for CO2 production and subsequent pH reduction is biological activity within the sludge. Due to inefficient mixing and lack of buffering capacity, at a dose 2% CaO several regions of the sludge are unstable in the sense that the pH is lower than 12, thus allowing microbial activity and production of CO2. As a consequence, a very quick reduction of pH in the whole of the sludge can be observed leading to low pH values to the order of 8-9 within few weeks. The same happens with a dose of 4% CaO, although at a slower rate (a couple of months). For both doses odours can develop. Sufficiently long periods (over three months) of stable pH around 12.5 can be ensured with doses in the range 6-10%. Another factor that has to be taken into consideration is the reaction with external CO2 of the atmosphere and/or CO2 produced by fungi activity at the surface of the sludge. However, with proper storage (low surface area/volume ratios, low temperatures) this factor can be minimised. Sludge sanitation The effect of CaO on selected bacteriological parameters after mixing is shown in Table 1, which indicates that substantial reduction of pathogens can be achieved even for a dose of 2% CaO. However, Tables 2 and 3 show that a reduction of pathogens over prolonged periods (over 1 day) require a dose of over 4% CaO. The effects of the duration time under high pH and of the temperature seem to vary with the pathogen type. Prolonged exposure, over several days, of coliforms to a high pH environment enhances their removal while increased temperatures appear to be effective only in the 33 Table 1: Influence of CaO on bacteriological parameters 4 hours after mixing, 20 °C (Carl Bro S/A, 1997). CaO Dose Coliforms % 0 2 4 6 8 10 number/g 23x104 33x101 13x101 33x101 13x101 13x101 Temperature Streptococcus resistant Coliforms number/g number/g 49x103 11x104 – <100 – <100 – <100 – <100 – <100 Clostridium perfrigens Salmonella number/g 30x103 18x102 14x102 13x102 9x102 2x102 number/g Traced in 10 g – – – – – Table 2: Influence of the CaO dose and storage time on the microbial load [Carl Bro S/A, 1997]. Temperature Coliforms Temperature resistant Coliforms Clostridium perfringens Vegetative Days 1 1 14 1 14 1 14 Salmonella Spores 1 14 CaO Dose 1 14 Identification in 10 g of sludge % °C 0 2 4 6 6 8 8 10 10 15 15 20 20 20 20 26 20 28 20 33 20 39 number/g sludge 10x106 33x102 70x102 70 70 63 26 9 34 33 11 49x104 46 4.9 5.0 5.0 <2 <2 6 5 <2 <2 33x104 2.3 <2 <2 <2 <2 <2 <2 <2 <2 <2 49x104 <2 <2 <2 <2 <2 <2 <2 <2 <2 <2 90x103 30x102 13x102 12x102 60x101 20x102 11x102 18x102 70x101 11x101 <10 10x104 10x102 6x101 10x101 <10 100 <10 <10 <10 <10 <10 90x103 <10x102 <10 <10 <10 <10 <10 <10 <10 <10 <10 40x103 <10x101 100 <10 <10 <10 <10 <10 <10 <10 <10 + – – – – – – – – – – – – – – – – – – – – – case of vegetative clostridium perfrigens. Quicklime treatment of sludge is also effective with respect to removal of parasites. Comparative studies of Ascaris ova growth with (10% CaO, Table 5) and without CaO (Table 4) addition, reveal the presence of multicell ova and development of fully grown larva up to 71% in the reference sample, while practically only unicellular ova are observed with quicklime treatment. Furthermore, Table 6 indicates that the ova can loose the ability to grow, even under favourable conditions after prolonged exposure to a mixture of sludge CaO (i.e. exposure for five months). 34 Table 3: Reduction of the microbial load in terms of negative logarithms (Carl Bro S/A, 1997). CaO Dose °C after 1st day % 0 2 4 6 6 8 8 10 10 15 15 20 20 20 20 26 20 28 20 33 20 39 Coliforms 4 hr – 2,8 3,2 3,8 – 5,2 – 3,2 – – – 1 day – 3,5 3,2 5,2 5,2 3,2 5,6 6,0 5,5 5,5 6,0 Clostridium perfringens 14 day 1,3 5,3 6,3 6,3 6,3 >6,7 >6,7 6,2 6,3 >6,7 >6,7 Vegetative 1 day 14 day – 0,1 1,5 2,0 1,8 2,2 1,9 3,0 2,2 4,0 1,5 1,7 3,0 1,9 >4,0 1,2 1,7 >4,0 – 2,1 >4,0 – 2,9 >4,0 – >4,0 >4,0 4 hr – 1,2 1,3 1,4 Spores 1 day 14 day – 0,4 2,0 >4,0 >4,0 >4,0 >4,0 >4,0 >4,0 >4,0 >4,0 >4,0 >4,0 >4,0 >4,0 >4,0 >4,0 >4,0 >4,0 >4,0 >4,0 >4,0 Table 4: Ascaris ova growth (Reference Sample) (Carl Bro S/A, 1997). GROWTH STAGE Non fertilised ova Unicellular Bicellurar Four cells > 8 cell Premature larva Fully grown larva TOTAL 0 1 99 0 0 0 0 0 100 14 9,6 85 1 0 0,7 3,7 0 100 28 11,3 4 0 0 16,7 11,3 56,7 100 DAY 42 9,2 0 0 0 24,6 8,5 57,7 100 56 6,7 8 1 0 19,2 6,7 59,3 100 70 5,3 9,7 0,3 10,3 3,3 71 100 150 3,3 10 1 0,3 13,3 2,8 69,3 100 70 0 99.3 0 0 0 0.7 0 100 150 0 100 0 0 0 0 0 100 Table 5: Ascaris ova growth (CaO 10% treated sludge) (Carl Bro S/A, 1997). GROWTH STAGE Non fertilised ova Unicellular Bicellurar Four cells > 8 cell Premature larva Fully grown larva TOTAL 0 1 99 0 0 0 0 0 100 14 1.3 98 0.7 0 0 0 0 100 28 1.7 96 1 0.3 1 0 0 100 DAY 42 0 92.3 0 0 7.7 0 0 100 56 0 92.7 0.3 0 3 4 0 100 35 Table 6: Ascaris ova cultivation in formaldehyde solution 1% after being isolated out of sample treated with 10% CaO (Carl Bro S/A, 1997). GROWTH STAGE Ova retention time in sample before cultivation (weeks) 2 4 6 8 20 1.7 3.3 0 0 0.4 0.7 7.3 11.7 40.7 63.4 0 1.7 2.3 0 2.3 0 0.3 2.3 0.3 0.6 24 26.7 54.7 37.4 32.7 6.3 4.3 7.7 6.3 0.6 67.3 56.7 21 15.3 0 100 100 100 100 100 Non fertilised ova Unicellular Bicellurar Four cells > 8 cell Premature larva Fully grown larva TOTAL Other significant aspects The long term effect of CaO treatment on sludge characteristics is shown in Table 7. Upon quicklime addition, an increase in total solids content and pH is observed, while volatile solids content, phosphorus, nitrogen and ammonia contents are reduced. With storage over seven months total solids content tends to gradually increase while pH, is slightly reduced, remain however above 12. It is only after a storage period of two years that a drastic reduction of pH and alkalinity are observed. The total solids content increases significantly, wile the ratio of total solids volatile to total solids is reduced due to degradation of the organic material. This degradation also explains the higher phosphorus content observed. Sludge obtains a wood-like texture with slight but not unpleasant odour. With respect to phosphorous availability to plants, it has been observed (Akrivos et al., 1999), that upon lime addition and pH increase the available phosphorous is limited to Table 7: Long term effects of the CaO treatment (10%) on sludge characteristics (Carl Bro S/A, 1997). Parameter Units pH TS g/kg TS Volat. g/kg TSVol/TS % Tot-P g/kg TS Tot-N g/kg TS NH3-N g/kg Alcalinity mmol/kg Odours * Before CaO addition 36 0* 7.1 168 101 60 17 32 1.5 – 0 12.5 283 87 31 9.8 19 0.27 – – 14 12.5 292 86 29 9.6 17 0.21 2390 – Days 45 12.5 291 90 31 – 17 0.27 2700 – 120 12.3 332 93 28 9.3 17 0.31 3080 – 210 12.1 303 104 34 – 17 0.18 2700 – 720 8.4 531 103 19 17 13 – 1340 – approximately 68%. However, with neutralisation to normal pH (as it happens when sludge is introduced to the soil) the available phosphorous is increase to over 90%. Finally, practical experience has shown that both batch or continuous plug flow systems can be used for quickliming of sludge and that the most important technological aspect is related to the sludge-CaO mixing efficiency of the system. Conclusions Addition of quicklime to dewatered sludge and subsequent storage under a pH of over 12 for at least three months ensures a high degree of sludge sanitation. This sludge can be used as a soil conditioner and fertiliser without any restrictions as far as pathogens are concerned. Even after prolonged storage, there is a very limited reduction of nitrogen, while the availability of phosphorous for plant growth is high (over 90%) under conditions of neutralised pH, which is very quickly established upon mixing of the sludge with the soil. Finally, quicklime treatment improves the handling characteristics of the sludge and allows for long term storage without development of odour. Acknowledgements The results presented in this paper originate from studies conducted by Carl Bro A/S and the National Technical University of Athens within the framework of a joined EU project (Hygienic Sludge Management for Agricultural Utilisation), sponsored by the Directorate-General for Research (formely DG XII) of the European Commission. The contribution of the other partners of the project namely, NAMA Consulting Engineers and Planners SA, VKI and the Municipal Enterprises of Water and Sewerage of Lamia and Rethymnon, is also acknowledged. References Tullander V., (1983), “Quicklime treated sludge”, Environmental effects of organic and inorganic contaminants in sewage sludge, Davis, Hucker & L’Hermite (eds), D. Reidell Publishing Company. Carl Bro A/S, (1997), “Treatment of Sludge with Lime”, Research Report Akrivos J., Mamais D., Katsara K., Andreadakis A., (1999), “Agricultural Utilisation of Lime Treated Sewage Sludge”, Proceedings of the Specialised Conference on Disposal and Utilisation of Sewage Sludge, Athens, Greece, October 13-15, 1999. 37 Anaerobic digestion of sludge: focusing on degradation of the contained organic contaminants Angelidaki, I.1, and Ahring, B.K.1,2 Anaerobic Microbiology/Biotechnology group Department of Biotechnology, Building 227 The Technical University of Denmark, 2800 Lyngby, Denmark. Tel. +45 45256187; e-mail: ria@ibt.dtu.dk 1The 2School of Engineering and Applied Science Department of Civil and Environmental Engineering University of California Abstract Great interest has been devoted in the recent years for recycling of the waste created by modern society. A common way of recycling the organic fraction is amendment on farmland. However, these wastes can contain possible hazardous components in small amounts, which can prevent their use in farming. The objective in our study has been to develop biological methods by which selected organic xenobiotic compounds can be biotransformed by anaerobic or aerobic treatment. Screening tests assessed the capability of various inocula to degrade two phthalates (DBP, and DEHP), four polycyclic aromatic hydrocarbons (PAHs), four linear alkylbenzene sulfonates (LAS) and three nonylphenol ethoxylates (NPEO) under aerobic and anaerobic conditions. Under aerobic conditions, a large number of the selected xenobiotics could be degraded by choosing the appropriate inoculum. Aerobic degradation of DEHP was only possible with leachate from a landfill as inoculum. Anaerobic degradation of some of the compounds was also detected. Leachate showed capability of degrading phthalates, and anaerobic sludge showed potential for degrading PAH, LAS and NPEO. Furthermore, anaerobic digestion of sludge amended with either pyren and LAS or 4nonyl phenol and DEHP in continuously stirred tank reactors showed anaerobic transformation of the tested compounds. The results are very promising as they indicate that a great potential for biological degradation is present, though the inoculum containing the microorganisms capable of transforming the recalcitrant xenobiotics has to be carefully chosen. 38 Introduction Within the European Union the total amount of produced sludge is about 6.5 million tons per year (Smith 1996). There are several disposal routes for sludge, including ocean dumping, incineration, spreading on agricultural land, soil incineration, land spreading in forestry or landfilling. At present the disposal of sludge on landfills is with 40% the most important outlet in the EU while 37% of the sewage sludge produced within the EU was used for agricultural purposes in 1994 (Hall 1994). The amount of sewage sludge requiring disposal is expected to increase significantly in the future due to recent environmental developments. The Helsinki agreement called for the banning of ocean sludge dumping by 1987 and the Urban Waste Water Directive 91/271/EEC, required waste water treatment plants with secondary treatment and nutrient removal in sensitive areas (Kiely 1997). With increasing sludge protection in the EU larger larger amounts of sewage sludge will be recycled for agricultural purposes (Smith 1996). This approach seems to be reasonable since agricultural land can become nutrient deficient due to intensive cultivation. In addition to sewage sludge other wastes such as organic industrial wastes, manures, and organic household waste can with great advantage be recycled and used in farmland as fertilizers and as soil improving components. However, this type of waste can contain possible hazardous components in small amounts, which might show adverse effects on the ecosystem, e.g. the farmland amended with sewage sludge. Indeed, linear alkylbenzene sulfonate (LAS) compounds such as those used in household detergents, nonylphenols, nonylphenol ethoxylates, polycyclic aromatic hydrocarbons (PAH), and phthalates have recently been identified as major anthropogenic organic components in sewage sludge. There is a special public concern about organic components, which may have a potential for acute toxicity, mutagenesis, carcinogenesis or teratogenesis or posses estrogenic effects. The concentrations of LAS in raw wastewater have been reported to range from 3 mg/l to 21 mg/l (Brunner et al., 1988, De Henau et al., 1989, Holt et al. 1995, Ruiz Bevia et al., 1989). Although LAS and other common surfactants have been reported to be readily biodegradable by aerobic processes, much of the surfactant load into a sewage treatment facility (reportedly 20-50%) is associated with suspended solids (Greiner and Six 1997, and McAvoy et al. 1998) and thus escapes aerobic treatment processes. LAS is reported not to be biodegraded by anaerobic biological processes usually employed in sludge stabilization (McEvoy and Giger, 1985; Swisher, 1987), and it may be found in the gram per kilogram range in anaerobic sludge. According to Mackay et al. (1996) the emission of LAS to soil is predominant due to sludge application on agricultural soil and landfilling. The presence of surfactants in sludge may have undesirable environmental effects since the surfactant molecules may leach to groundwater contributing to groundwater contamination. Alkylphenol ethoxylates such as NPnEOs is a group of non-ionic surfactants with world-wide application and are evidently less biodegradable than LAS (e.g. Swisher, 1970; Steinle, 1964; Pitter, 1968) and a wider range of removals from 0-90% based on specific analyses such as UV and IR spectroscopy (Swisher, 1970). This suggests that 39 only partial degradation occurs, such as conversion from polyethoxylates to nonylphenol diethoxylate (NP2EO), nonylphenol monoethoxylate (NP1EO), and nonylphenol (NP). The latter is the most recalcitrant of the intermediates formed during alteration of the NPnEO molecules. Mass balances done on treatment plants in Switzerland (Brunner et al., 1988) support these findings. Due to the low water solubility and lipophilic properties of PAHs, these compounds are removed from sewage partly by biodegradation, partly by adsorption on to sludge. According to Bodzek et al. (1997) PAHs are found in significant amounts in sludge (up to 2000 mg/kg sludge dry mass). The PAHs are mostly originating from fossil fuel combustion and industrial processes (Shuttleworth and Cerniglia 1995). Generally the half-lives of PAHs is increasing with increasing number of aromatic rings, though the degradation rates is dependent upon the test system. Due to the great adsorption abilities of PAHs they will precipitate with the particular material in the pre-clearing tank. The sludge originating from this step has a high content of easily degradable organic material, which is used for the production of methane. PAH are, however, not as easily anaerobically degradable as under aerobic conditions and they tend to accumulate in the digested sludge. Sewage sludge and compost contains relatively high concentrations of di(2ethylhexyl)phthalate (DEPH) and di-n-butylphthalate (DBP) (Danish Environmental Agency, 1996). It was reported that these compounds probably originate from both households and industries. DEHP accounts for 90% of the phthalate production worldwide. At least 95% of the DEHP produced is used as an additive in PVC plastics which are made into various products such as waterproof clothing, footwear, toys, bloodbags and heat-seal coatings on metal foils. Plastizisers are poorly soluble substances and will be removed in the waste water treatment plant by biodegradation, though also adsorption on sewage sludge is significant. Hence, plastizisers will be transferred to soil with application of sludge on agricultural land or landfilling of sludge. Biological treatment of wastes containing toxic compounds could be an effective and cheap method for detoxifying the wastes. In order to do so, microorganisms that can degrade the compounds are needed. In the present study we report results from a screening of microorganisms capable of degrading LAS, nonylphenols, nonylphenolethoxylates, PAH and phthalates. Materials and methods Description of the experimental set-up The tests were performed in batch serum vials where pressure and/or substance concentration was followed over time. Two different media were used, one for the anaerobic (Angelidaki et al. 1990) and one for the aerobic inocula, containing per liter of water (Milli-Q) 0.8 g K2HPO4, 0.2 g KH2PO4, 0.05 g CaSO4*2H2O, 0.5 g MgSO4*7H2O, 0.01 g FeSO4,*7H2O, 1.0 G (NH4)SO4. Three sets of control vials (sterile, substrate-unamended, and uninoculated) were made in triplicates. 40 Compounds tested Of PAHs naphthalene, 1-methylnapthalene, fluoranthene, phenanthrene and pyrene were chosen. The PAHs were added either as a mixture of the five PAHs mixed in equal amounts or as the individual compounds. Among the phthalates, DBP, and DEHP were selected. LAS was used as a mixture of LAS with an alkyl chain length of 9 to 13 units and among the nonylphenols 4-Nonylphenol and Nonylphenol mono and diethoxylate were used. For the mixture of PAH the concentration was counted as the sum of the five compounds. Inocula The inocula originated from several different Danish environments as shown in Table 1, along with redox conditions, and xenobiotics used during the screening test. Table 1: Inoculum identification (original environment), redox conditions for biotransformation studies, and xenobiotics used. Origin Activated Sludge Lundtofte Redox conditions Xenobiotics added Anaerobic, aerobic NPE, LAS, Napthalene, 1-Methylnapthalene, Fluoranthene, Phenanthrene, Pyrene, DBP, DEHP Activated Sludge Damhuså Anaerobic, aerobic NPE, LAS, Napthalene, 1-Methylnapthalene, Fluoranthene, Phenanthrene, Pyrene, DBP, DEHP Dewatered sludge Damhuså Anaerobic NPE, LAS Biosludge Lundtofte Anaerobic, aerobic NPE, LAS Sediment Damhuså stream Anaerobic NPE, LAS Sediment Lake Arresø Anaerobic, aerobic NPE, LAS, DBP, DEHP Soil Nr. Herlev, Hillerød Anaerobic, aerobic NPE, LAS, Napthalene, 1-Methylnapthalene, Fluoranthene, Phenanthrene, Pyrene, DBP, DEHP Soil Møllehøj, Arresø Anaerobic, aerobic NPE, LAS, DBP, DEHP Soil Colgate-Palmolive Anaerobic, aerobic NPE, LAS Soil Oil contaminated, Jutland Napthalene, 1-Methylnapthalene, Fluoranthene, Phenanthrene, Pyrene Soil Hjørring Gaswork Napthalene, 1-Methylnapthalene, Fluoranthene, Phenanthrene, Pyrene Compost AFAV, Hillerød Anaerobic, aerobic NPE, LAS, DBP, DEHP Granular sludge UASB reactor, Anaerobic, aerobic NPE, LAS Eerbeek Manure Mesophilic CSTR Anaerobic, aerobic NPE, LAS Landfill leachate DBP, DEHP 41 Reactor experiments Two reactors of total volume of 4.5l were operated with anaerobic digested sludge at a retention time of 15 days at 37 °C. After the reactors had been operated for a month with the sludge additional 4-NP or pyren was added to the feed at day 7 to the reactor R1 and R2 respectively. At day 28 the concentrations of the added compounds were increased from 50 ppm to 100 ppm. At day 38 was DEHP and LAS was additionally added to the reactors R1 and R2 respectively. Analysis Concentration of PAHs, phthalates, was made by GC-MS. While LAS and nonyl phenols were measured by HPLC analysis. Results and discussion Vials incubated under aerobic conditions showed a decrease of the initial pressure when degradation was present. In figure 1 the degradation of PAH is shown when inoculating with sludge amended soil. When PAH was added in a concentration of 20, 100 or 200 ppm the pressure in the vials decreased, indicating degradation of the added compounds (Fig. 1a). In the PAHs unamended controls the pressure slightly decreased relative to the sterile control due to digestion of ethanol, though the pressure remained higher then the PAH amended vials. In figure 1b the concentrations (in area counts) of the individual PAH are shown at the start and end of the experiment. There was a significant reduction of the concentrations of the measured PAH at the end of the experiments compared to the initial concentrations, confirming that the PAHs were biodegraded. In figure 2 degradation of DBP under anaerobic conditions is shown. When degradation occured the pressure in the vials increased due to production of methane and carbon dioxide. The pressure of the controls without DBP addition also increased due to mineralization of organics contained in the inoculum and ethanol added in a concentration corresponding to the DBP amended vials. However, the pressure increase in the vials with 20 and 100 ppm DBP was higher than in the controls, corresponding to biodegradation of DBP. Vials with 200 ppm DBP showed no increase of the pressure indicating that this concentration was toxic to bacteria preventing both degradation of DBP and of the organics contained in the inoculum. In figure 2b the concentration of DBP (20 ppm and 100 ppm) is reported and evidence of DBP biodegradation is given when evaluation the pressure increase together with the DBP concentration decrease. The results from the screening test are summarized in Table 2. Most compounds were degraded both under aerobic and anaerobic conditions. Some compounds were easily degradable with most inocula. Such compounds were naphthalene, DBP, while the rest compounds showed only degradation with only a few inocula. DEHP is a compound that has been reported as recalcitrant under anaerobic conditions. Ejlertson (1997) has reported that DEHP was unaffected, during anaerobic incubation, throughout an 42 16 14 Pressure (psi) 12 10 8 20 ppm PAHs 100 ppm PAHs 200 ppm PAHs 200 ppm PAHs sterile PAH unamended 6 4 2 0 0 2 4 Time (weeks) 6 8 10 8e+6 begining end 7e+6 Area counts 6e+6 5e+6 4e+6 3e+6 2e+6 1e+6 0 phenanthrene fluoranthrene pyrene Figure 1: Pressure depletion in PAHs amended aerobic vials and relative concentration in vials at the beginning and end of the experiment. 43 40 35 20 ppm DBP 100 ppmDBP 200 ppm DBP 200 ppm DBP 200 ppm DBP sterile DBP unamended Pressure (psi) 30 25 20 15 10 5 0 0 2 4 6 8 10 Time (weeks) 1e+7 Area counts 8e+6 beginning end 6e+6 4e+6 2e+6 0 DBP 20 DBP 100 Figure 2: Pressure increment in DBP amended anaerobic vials and relative concentration in vials at the beginning and end of the experiment. 44 12 Table 2: Results from the screenings test for degradation of xenobiotic compounds. Group LAS NPE PAH Phthalate Tested xenobiotic compound Linear Alkylbenzene Sulfonate 4-Nonylphenol Nonylphenolmonoethoxylate Nonylphenoldietoxylate Acenapthene Naphthalene Phenanthrene Fluoranthene Pyrene DEHP DBP Aerobic + – + + – + + + + + + Anaerobic + – + + + + + – + + + +: indicates degradation; -: indicates not degradation; experimental period of 330 days. However, in our screening experiments we found indication of degradation of DEHP with inoculum originating from leachate from a landfill. It is possible that deposition of plastics, and other materials containing DEHP has favoured the selection of organisms capable of degradation of DEHP. The landfill percolate did not show capability of aerobic degradation of DEHP. LAS is known to be easily degraded aerobically, e.g. in activated sludge reactors during waste water treatment, but is not degraded anaerobically in the waste water treatment (McEvoy and Giger 1985). In our screening experiments we found inocula showing anaerobic capability of LAS. Inoculum from lake sediment (Damhuså) showed capability of anaerobic degradation of LAS. In addition, also inocula that were found in aerobic environments such as compost and activated sludge (Lundtofte wastewater treatment plant) showed capability of anaerobic degradation of LAS. PAHs were found to be degradable under both aerobic and anaerobic conditions, though a higher number of inocula contained the relevant microorganisms for aerobic PAH degradation. From the reactor experiments it can be seen that all the tested compounds were transformed under anaerobic digestion of sludge. Reduction of the compounds to up to 100% were observed (Figure 3 and Fig. 4). After additions of the second xenobiotic compound in the reactors at day 38 initial disturbance of the process with temporary decrease of the transformation of the PAH and DEHP was observed. However, after approximately 10 days a good transformation of the compounds was reestablished. Conclusions The screening test showed that a range of inocula have a high capacity towards degradation of recalcitrant xenobiotic compounds. Especially the degradation of DEHP and LAS under anaerobic conditions is promising considering the importance 45 Figure 3: Anaerobic CSTR reactor experiment (Reactor 1). Feed with anaerobic sludge containing small concentrations of xenobiotics. At day 6 was the feed amended with 50 ppm 4-pyren which was increased to 100 ppm at day 28. At day 39 was additionally added 50 ppm LAS12. Figure 4: Anaerobic CSTR reactor experiment (Reactor 2). Feed with anaerobic sludge containing small concentrations of xenobiotics. At day 6 was the feed amended with 50 ppm 4-NP which was increased to 100 ppm at day 28. At day 39 was additionally added 100 ppm DEHP. of eliminating these compounds during waste water treatment. The discovery of new bacteria gives the possibility of bioprocessing waste containing toxic compounds by introducing the appropriate bacteria into, for instance, a biogas reactor system, where the organic matter of the waste will be converted into biogas with simultaneous degradation of organic contaminants. The effluent from such a process could then be applied on agricultural soil as a fertilizer and soil improver component. 46 Acknowledgements This work was supported by grants from The Strategic Environmental Research programme 1997-2000 (Subprogramme on sustainable land use). References Angelidaki, I., Petersen, S.P. and Ahring, B.K. (1990) Effects of lipids on thermophilic anaerobic digestion and reduction of lipid inhibition upon addition of bentonite. Appl. Microbiol. Biotecnol. 33, 469-472. Bodzek, D., Janoszka, B., and Dobosz, C., (1997) Determination of polycyclic aromatic compounds and heavy metals in sludge from biological sewage treatment plants. Journal of Chromatography A 774, 177-192. Brunner, P.H., Capri, S., Marcomini, A. and Giger, W. (1988) Occurrence and behaviour of linear alkylbenzenesulphonates, nonylphenol, nonylphenol mono- and nonylphenol diethoxylates in sewage and sewage sludge treatment. Water Res. 22, 1465-1472. Danish Environmental Protection Agency. (1998) Indsamling og anvendelse af organisk dagrenovation i biogasanlæg. Miljøprojekt 386 (in Danish). Henau, H. De, Matthijs, E. and Namkung, E. (1989) Trace analysis of linear alkylbenzene sulfonate (LAS) by HPLC. Detailed results from two sewage treatment plants. In Organic Contaminants in Waste Water, Sludge and Sediment. D. Quaghebeur, I. Temmerman and G. Angeletti editors. Elsevier Applied Science, London. Holt, M.S., Waters, J. and Comber, M.H.I., (1995) AIS/CESIO environmental surfactant monitoring programme. SDIA sewage treatment pilot study on linear alkylbenzene sulphonate (LAS). Water Res. 29, 2063-2070. Kiely, G., (1997) Environmental engineering. McGraw-Hill (ed.). pp. 574-583, 605-611. Mackay, D., di Guardo, A. and Paterson, S. (1996) Assessment of chemical fate in the environment using evaluative regional and local-scale models: illustrative application to Chlorobenzene and Linear Alkylbenzene sulfonates. Environm. Toxicol. and Chem. 15,1638-1648. Mahajan, M.C., Phale, P.S. and Vaidyanathan, C.S. (1994) Evidence for involvement of multiple pathways in the biodegradaton of 1- and 2-methylnaphthalene by Pseudomonas putida CSV86. Arch. Microbiol. 161, 425-433. McAvoy, D.C., Dyer, S.D. and Fendinger, N.J. (1998) Removal of alcohol ethoxylates ,alkyl ethoxylate sulfates, and linear alkylbenzene sulphonates in wastewater treatment. Environm. Toxicol. and Chem. 17, 1705-1711. McEvoy, J. and Giger, W. (1986). Determination of linear alkylbenzenesulfonates in sewage sludge by high-resolution gas chromatography/mass spectrometry. Environm. Sci. Technol. 20, 376-383. Quaghebeur, D., Temmerman, I. and Angeletti, G. (editors). Elsevier Applied Science, London. Pitter, P. (1968) Relation between degradability and chemical structure of nonionic polyethylene oxide compounds. Surf. Cong., 1, 115-123. Ruiz Bevia, F., Prats, D. and Rico C. (1989) Elimination of L.A.S. (linear alkylbenzene sulfonate) during sewage treatment, drying and compostage of sludge and soil amending processes. In Organic Contaminants in Waste Water, Sludge and Sediment. D. Quaghebeur, I. Temmerman and G. Angeletti editors. Elsevier Applied Science, London. Shuttleworth, K.L. and Cerniglia, C.E. (1995) Environmental aspects of PAH biodegradation. Appl. Bioch. and Biotechnol. 54, 291-302. 47 Smith, S.R., (1996) Agricultural recycling of sewage sludge and the environment. Wallingford. Steinle, E.C., Myerly, R.C. and Vath, C.A. (1964). Surfactants containing ethylene oxide: Relationship of structure to biodegradability. Jour. Amer. Oil Chemists Soc. 41, 804-807. Stringfellow, W.T. and Aitkin, M.D. (1995). Competitive metabolism of naphthalene, methylnaphthalene and flourene by phenanthrene-degrading pseudomonads. Appl. Environ. Microbiol. 61 357-362. Swisher, R.D. (1987). Surfactant Biodegradation. Marcel Dekker, New York. Volkering, F., Breure, A.M. and Andel, J.G. 1993. Effect of micro-organisms on the bioavailability and biodegradation of crystaline naphthalene. Appl. Microbiol. Biotechnol. 40, 535-540. 48 Thermal drying – microbiological quality of dried sludge Jean Paul Chabrier ENVIRO-CONSULT 32 rue de l’Est, F-68110 Illzach Tel : 00 33 3 89 53 54 71 - Fax : 00 33 3 89 53 19 20 Introduction The main use of urban sewage sludge for most European countries is the recycling to agriculture. Different pathogens such as viruses, bacteria, protozoa and parasites can be found in the sludge produced by the waste water treatments plants (Faust, 1976; Schwartzbrod et al., 1986; Yanko, 1988). The sanitary risk due to pathogens must be taken into account; however studies on the capacity of living of these pathogens and parasites (Engelberg, 1985) like Helminth eggs confirmed the resistance of the eggs to most biological treatments such as aerobic stabilisation, mesophilic anaerobic digestion and lagooning. After applying other biological and chemical treatments (composting, liming) the viability of the parasite eggs clearly shows the necessity of precisely defining the process parameters (temperature, pH, homogenisation, treatment time, end process heat value…) in order to efficiently destroy the Helminth eggs. It is generally demonstrated that heat is a powerful virus killer. The thermophilic aerobic digestion and pasteurisation remain attractive processes to inactivate viruses and other pathogens (60 °C for a treatment contact time superior or equal to an hour). The bacteria indicating faecal contamination are destroyed for processing temperature treatments superior or equal to 80 °C – that is always the case for drying. However the need to reach such a temperature involves important energetic costs (in thermal drying approximatively 900 to 1,200 kWh per tonne of evaporated water – ENVIROCONSULT measurements) if the route is only sludge recycling to agriculture. Does the sludge microbial quality on its own justify the application of thermal drying technologies? The author, through his experience, will bring elements to answer this question. Reminder of applicable legislation1 The applicable legal texts are very different from one country to another. They can be summarised as follows: 1Report Recommendations to preserve and extend sludge disposal routes, CEN/TC 308/WG3 N33. 49 Table 1: Regulations on sanitary sludge quality. Country Recommended treatments: legal guidelines and laws End product standards European Union Sludge treatment by biological, chemical, thermal treatment, storage or any other specific process Sewage Sludge Ordinance (AbfKlärV2) – Germany France Denmark Definition in the 97-1133 decree: Treatment by physical, biological, chemical or thermal process, for long chemical or thermal process, for long term storage, or by any other appropriate process, in order to significantly reduce its fermentation capacity and the correlated sanitary risks by using it - Thermal treatment at 70 °C during an hour or equivalent combinations of time and temperature - Composting at 55 °C during at least 15 days - Liming - Aerobic and anaerobic treatments Austria In the three following three Länder: - Burgenland - Ober Österreich - Salzburg Switzerland – Italy Luxembourg – – USA Application of EPA 92 40 CFR or PART 503 Process to further reduce pathogens: PFRP – class A Process to significantly reduce pathogens: PSRP – class B 2 Third 50 Only sewage sludge considered as safe from an epidemic-hygienic point of view and land for fodder cultivation Only for hygienised sludge: Salmonella: < 8 mpn/10 g dm Enteroviruses: < 3 cfumpn /10 g dm viable Helminths eggs: < 3 per 10 g dm Thermo-tolerant coliforms: none – Salmonellae: none in 1 g dm Enterobacteriacaee: < 1000 in 1 g dm Helminth eggs: none in 1g dm For the agricultural land producing fodder or vegetables: Enterobacteriacaee: < 100 in 1 g dm Infectious parasite eggs: none in 1 g dm Salmonellae: < 1000 in 1 g dm Enterobacteriacaee: < 100 in 1 g dm Viable parasite eggs: none in 1 g dm Salmonellae: < 3 mpn or PFU in 4 g dm Enteroviruses: < 1 PFU in 4 g dm Viable Helminth eggs: < 1 in 4 g dm Feacal coliforms: < 2 106 in 1 g dm Report of the ATV/VKS Working Group 3.2.2 on Disinfection of sewage sludge. The control of the sludge microbiological contamination can be considered in three ways: • Either by applying specific and homologated treatment processes to the sludge which leads to the non detection (in case of thermal treatment by drying) or the reduction of pathogenic germs concentration; • Or by making tests controlling the microbiological quality of the sludge; • Or else by simultaneously applying both preceding operations. Analysing the existing situation, we can divide the European countries into four groups: Table 2: Classification according to the microbiological quality. Group Definition of the rules N° 1 Slight recommended rules: Little compulsion on the stabilisation and microbiological processes N° 2 Authorised processes in terms of reduction or removal of pathogens N° 3 Conformity to a specified microbiological quality and for specific uses N° 4 Answers related to limited values and authorised processes through EPA 40 CFR – PART 503 Country European Union Germany Denmark Switzerland, Austria USA The French rules are placed between group 1 and group 3 because only microbiological limits are set up for sanitary quality (hygienised sludge). However, for the determination of pathogens limits, it applies the American analysis methods. Therefore, in front of these established facts, what is the best approach to consider? In France, what is the present situation for stabilisation and microbiological treatments? The situation is as follows: The use of mesophilic anaerobic digestion was little developed in the 1980s. Most of the treatment plants applying this process were built in the 1970s and for thirty years a few new plants have been equipped. From this specific situation, two major problems appeared: the lack of sludge stabilisation (smells , harmful effects during storage) and of microbiological quality even though that one is only partial for the already settled processes. To improve the situation, the sludge post-treatment with lime was largely applied in medium-size plants of 20-150 000 p.e. or even bigger. In 1997, Article 7 of the 97-1133 decree introduced by a compulsory point of view a physical, biological, chemical or thermal treatment of the sludge as well as a long 51 storage in order to significantly reduce its fermentation and sanitary risks when used. The decree application continued to boost the liming process. Lime is generally well accepted by farmers who actively participate in sludge recycling. When comparing the French situation of sludge spreading to the US EPA rules on ≤vector reduction” – i.e. management practices that reduce the attraction of insects, animals, etc – the following table can be made: Table 3: Process limiting the vector attraction. Often applied treatments Treatments sometimes applied Ploughing in the soil within - anaerobic digestion 24 to 48 hours after spreading - lime conditioning (97-1133 Decree) Treatments rarely or not yet applied - aerobic thermophilic digestion - soil injection - increase of dm content to more than 75 or 90% Graph 1: Thermal drying in Europe (source: Enviro-Consult). Note: the thermal drying is in great development in the United Kingdom. Up to now in France drying is not much developed in comparison with most of other European countries (number of 'drying lines' in Europe: approx. 400 – in France: 30 of which 20 in operations and 10 in construction – ENVIRO-CONSULT Data). 52 Present techniques used in France A last point on the French situation concerns the present methods used in the laboratories to determine the parasites. According to the opinion of many French experts, the analysis methods of EPA cannot guarantee that the results obtained will be validated. Eight techniques are available to enumerate and test the Helminth eggs viability and the technique which would lead to the most important number of eggs would be the one identified by AES3. In France a big question is being discussed nowadays by experts, which is : “Do we have to move towards an experimental norm and therefore question the regulatory texts?” Parameters and treatments to be used in the control of the microbiological contamination The reduction or removal of pathogens is influenced by different factors and by the applied treatments: • Setting velocity: for Helminth eggs it varies from 0.65 m/s for Ascaris eggs to 12.5 m/s for Schistosoma (Shuval, 1986). • Heat and exposition time: graphs 2, 3 and 4 (taken from Sanitation and diseases: Health aspects of excreta and waste water management) show the influence of temperature and exposition time for the destruction of - Ascaris eggs (Feachem et al., 1983) - Salmonellae (Feachem et al., 1983) - Enteroviruses (Feachem et al., 1983) • physical treatments: irradiation, ultrasounds, long term storage • biological treatments: thermophilic aerobic and anaerobic digestion, composting • chemical treatments: fertilisers effects and lime conditioning 3 AES = Antiformine, ethylacetate, zinc sulphate: method developed by Gaspard and Schwartzbrod (1995). 53 Graphs 2: Effect of the relation temperature/time on the destruction of Ascaris eggs. Graphs 3: Effect of the relation temperature/time on the destruction of Enteroviruses. Graph 4: Effect of the relation temperature/time on the destruction of Salmonella. Thermal drying: heat and exposure time The thermal drying is a physical operation which consists in draining all or part of the water contained in the dewatered sludge. Drying is made at the atmospheric pressure and the evaporated vapours are condensed into a condenser installed on the line (vapour circuit). There are three main types of thermal drying technologies: • Indirect drying or by contact: the heat is transferred to the wet sludge which is deposited on a hot plate, thus allowing the evaporation of the water. • Direct drying or by convection: the heat is transferred directly from the energy carrier (flue gas) to the wet prepared sludge, thus the flue gas absorbs the humidity of the sludge. • Mixed drying: it is a combination of drying by contact and by convection. The used heating medium depends on the applied technologies: For the indirect drying: saturated steam, thermal-oil. For the direct drying: exhaust flue gas, warm air or gas. 54 The reached temperatures vary according to the processes and the sludge drying phase. Black (thin) curve: thermogravimetric curve Grey (thick) curve: sludge temperature increasement curve Graph 5: ENVIRO-CONSULT Data. 55 Table 4: Temperature of sludge and gas (source: ENVIRO-CONSULT). Drying technology Drum dryer Fluidized bed dryer Thin film dryer* Discs dryer** Temperature of dried sludge 84 °C 87 °C 95 – 100 °C 112 – 118 °C Heat of vapours or flue gas 140 °C > 110 °C 100 °C 120 °C End sludge dryness % 95 95 65 95 *very high transmission coefficient λ = 100 W/mK. ** residence time in dryer: 1h30mn maximum Microbiological quality results The following values were found on samples of pre-dried sludge (55% dryness) and full dried sludge up to 90 % dryness. Table 5: Results on the sludge microbiological quality – data collected by ENVIRO-CONSULT. Pathogens Legal requirements French EPA 503 Decree of 8.01.98 Salmonellae < 8 mpn/10 g MS Enterovi- < 3 mpn PFU/ ruses 10 g MS Enterobacteriaceae Viable < 3/10 g MS Helminth eggs Thermo– tolerant coliforms * < 4 mpn/4 g MS < 1 PFU/4 g MS < 1/4 g MS < 1000 mpn/g MS Experimental data Digested Digested dried sludge predried UWWTP sludge Brugges* UWWTP Zurich** Absence /25 g Absence / 10 g Absence / 25 g < 1 Digested dried sludge UWWTP Baltimore Digested dried sludge UWWTP Nancy Digested dried sludge UWWTP Zurich*** <1 Undetermined Absence Undetermined Undetermined Undetermined before thermal treatment Absence/25 g Absence/10 g Undetermined < 1 <1 < 10 Undetermined < 10 <1 <1 Digested dried sludge have been stored in bags during one year. One analysis sample was taken from the storage (Seghers Better Technology Company). ** Indirect drying during 5 minutes residence time at 95-100 °C from sludge side and 160 °C from heat side. This drying conditions fullfills the EPA rules for class A, however the end dryness is very low (55%) and a recontamination is always possible except for parasites like Ascaris eggs (Buss AG, Basel). *** Indirect drying with a residence time of 45 minutes (Buss AG, Basel). 56 CONCLUSIONS Important studies on the sanitary quality of the dried sludge have not been made up to now in France and neither were we able to find data for Germany. Results obtained were supplied by various dryers and process manufacturers during specific tests but very few information were given on the methods of making the sampling or the analysis methods used. No presence of viable Helminth eggs is established after drying; according to biologists, their survival is impossible and therefore it can be assumed that the dried sludge cannot be contaminated again because of the storage conditions, even though this one can be long. If the thermal drying is interesting in the stabilisation or microbiological quality, nonetheless its first advantage is the reduced volume and mass of the sludge in order to find out new energy and materials routes for recycling in which the microbiological quality is of little interest. REFERENCES CEN/TC 308/WG 3 Report 1999 – 09: Recommendations to preserve and extend sludge utilisation and disposal 3rd Report of the ATV/VKS Working Group 3.2.2 «disinfection of Sewage Sludge». ENVIRO CONSULT data board – European sludge drying market analysis – 1998. Gaspard (1995) THESIS : Environmental parasites contamination : prospective for a sanitary risks management - .NANCY France. Richard G. Feachem, David J. Bradley, Hemda Garelick and D. Ducan Mara Sanitation and disease - Health aspects of excreta and wastewater management. Schwartzbrod J, Gaspard P, Thiriat L -Volume 1, number 2, 1998 European Water Management, Pathogenic micro-organisms in sludge and effect of various treatment processes for their removal. A survey of E.coli in UK sludges: UK water industry research limited – examples given by Tim EVANS. 57
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