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Reduction of the content of organic micropollutants in digested sludge by a post-aeration process a full-scale demonstration

L. Knudsen*,, G.H. Kristensen*, P.E. Jrgensen*,, S-E. Jepsen**


*DHI, Department of Wastewater and Process Technology, Agern All 11, DK 2970 Hrsholm, Denmark **Danish Environmental Protection Agency, Department of Household Waste, Strandgade 29, DK 1401 Copenhagen K, Denmark Abstract Surplus wastewater sludge reused for agricultural purposes must observe certain limit values with respect to different xenobiotic substances. The latest revision of the statutory order in Denmark includes for the rst time a list of limit values on organic micropollutants in sludge. Four groups of micropollutants are included in the list (LAS, PAH, NPE, and DEHP). The limit values will be revised in June 2000, at which time up to 50% of the sludge used for agricultural purposes, will not comply with the standards. It has been observed that the level of organic micropollutants is much higher in anaerobically digested sludge than in aerobically stabilised sludge. This indicates that the organic micropollutants in question can be partly or fully degraded under aerobic conditions but not under anaerobic conditions. The observations have formed the basis of the development of a post-aeration process for biological degradation of organic micropollutants in anaerobically digested sludge with the aim of enabling continued reuse of the sludge for agricultural purposes. The process is presented in this paper together with a description of a full scale demonstration experience on a Danish wastewater treatment plant. Keywords Anaerobic sludge; biological degradation; complete mixed reactors; organic micropollutants, post-aeration

Water Science and Technology Vol 42 No 9 pp 111118 IWA Publishing 2000

Introduction

The latest revision of the Danish statutory order regulating the utilisation of sludge for agricultural purposes includes for the first time limit values for a list of organic micropollutants (Danish EPA, 1996a). Four groups of micropollutants are included in the list: LAS (linear alkylbenzenesulphonates), PAH (acenaphthene, penanthrene, fluoranthrene, pyrene, benzo(b+j+k)fluoranthenes, benz(a)pyrene, benz(ghi)perylene, indenol(1,2,3-cd)pyrene and fluorene), NPE (nonylphenol and nonylphenolethoxylates with 1 and 2 ethoxygroups), and DEHP (bis(2-ethylhexyl)phthlate). In the statutory order two sets of limit values are laid down. The first set of values remains in force until 30th June 2000, after which date the second set of values takes over as shown in table 1. As will appear from Table 1, the limit values for LAS, DEPH, and PAH will be halved in the year 2000, whereas the limit value for NPE will be reduced by 80%. With the present limit values for the parameters, in force (until 30th June 2000), it is estimated that about 20% of the wastewater sludge in Denmark, which is used for agricultural purposes, cannot comply with the standards. It is estimated that when the stricter values come into force on 1st July 2000, up to 50% of the sludge will not comply with the new standards. LAS, NPE, and DEHP in particular will be present in amounts above the limit values. It has been clear for some time that the concentration level of the organic micropollutants in question is considerably higher in digested primary sludge than in aerobically stabilised secondary sludge. It is found that most anaerobically digested sludge can comply
To whom all correspondence should be directed NIRAS Consulting Engineers, Sortemosevej 2, DK 3450 Allerd, Denmark

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Table 1 Danish limit values for organic micropollutants in wastewater sludge for agricultural purposes
Limit values in force until Micropollutant compounds 30.06.2000 mg/kg TS Limit values in force after 01.07.2000 mg/kg TS

LAS NPE DEHP PAH

2,600 50 100 6

1,300 10 50 3

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with the present limit values, and that aerobically stabilised sludge can comply with the 2000 limit values. Hence, in terms of limit values for organic micropollutants, anaerobically digested sludge has been brought into focus. Methods for reduction of the content of organic micropollutants are needed if anaerobically digested sludge is to be used for agricultural purposes in the future. The present know-how described in the literature on the potential biodegradation of the four groups of micropollutant compounds in wastewater treatment plants is rather limited. Especially information on degradation under post-aerating conditions seems to be very rare. The most relevant literature describes the results of mass balances for e.g. LAS (Berna et al., 1989), and for NPE, and DEHP (Siegrist et al., 1989) in wastewater treatment plants. In Denmark some examinations on the reduction of organic micropollutants in wastewater treatment plants have been carried out (Danish EPA, 1990, Danish EPA, 1996a, Danish EPA, 1996b). In addition one examination evaluated the fate of LAS in a wastewater treatment plant and included the development of a mass balance for this compound (Knudsen et al., 1997). The examination showed that about 75% of the total amount of LAS in the wastewater, entering the plant, passed the primary sedimentation tank and ended up in the aerobic activated sludge plant. 25% of the amount of LAS was captured by the primary sludge and was transferred with the sludge to the anaerobic digestion tank. More than 98% of the amount of LAS, which was treated in the aerobically activated sludge plant, was degraded while 1.2% left the plant with the effluent and 0.25% ended up in the surplus sludge. The amount of LAS, which was transferred with the primary sludge to the anaerobic digester, could be quantitatively found in the digested sludge. No degradation was found in the anaerobic process. Regarding degradation of NPE and DEPH both Danish and foreign examinations seem to show that degradation is possible under aerobic conditions but not under anaerobic conditions. However, NPE found in wastewater is typically a degradation product of high molecular weight nonylphenolethoxylates, and therefore it is difficult to establish mass balances for this group of compounds in wastewater treatment plants. On several treatment plants it has been found that the content of NPE increases over the anaerobic digester tank, due to fragmentation of ethoxy groups from nonylphenolethoxylates under anaerobic conditions. Practically no information on degradation of PAH in wastewater treatment plants was found in the literature. Further development of mass balances will be difficult, as the single PAHs can change from one form to another during aerobic and anaerobic treatment. Finally, a large number of PAH compounds will be present in wastewater which are very similar to the compounds included in the statutory order. The observations showing that the level of organic micropollutants, except for PAH, is much higher in digested sludge than in aerobically stabilised sludge, indicate that the above-mentioned organic micropollutants can be partly or fully degraded under aerobic conditions but not under anaerobic conditions.

These above observations formed the basis of a project, which was carried out in 1998 and 1999. The purpose of the project was to evaluate the possibilities of using post-aeration for anaerobically digested sludge as a biological method for removal of organic micropollutants. If post-aeration of anaerobically digested sludge is possible and results in satisfying degradations, it may form the basis of simple technical solutions, which will allow a continued high reuse of wastewater sludge in agriculture. The project was sponsored by the Danish Environmental Agency and the Danish Council for Reuse and Less Pollutant Technology (Danish EPA, 1999).
Process description

L. Knudsen et al.

In the project the post-aeration process was tested in two modifications. One modification included a batch process where anaerobic digested sludge was mixed with aerobic activated sludge and aerated for several time periods. The other modification included a semicontinuous process where anaerobic sludge was aerated in separate tanks with varying hydraulic retention times. During the project the two modifications of the process were tested in laboratory scale as well as in full-scale. However, only the experience and results from the semi-continuous process in full scale are presented in this paper. In the continuous process, digested sludge is pumped from the digester to a separate tank. The tank is equipped with an aerator. At the same time an equal amount of sludge leaves the tank through the effluent. The process is started by inoculation with activated sludge, but is then dependent on the growth of bacteria, which can degrade the micropollutants. The original bacteria from the inoculation will eventually die or leave the tank by the effluent. Due to the dilution of suitable bacteria there is a need for a certain hydraulic retention time in order to maintain an amount of active bacteria, which can degrade the micropollutants. Another issue, which is important in connection with the process, is the fact that anaerobically digested sludge is easier to dewater than aerobically stabilised sludge. It is therefore to be expected that the post-aeration process will have a negative effect on the dewaterability of the sludge. In order to examine changes of the sludge character and the resulting content of dry solids in the dewatered sludge it was decided to include different sludge test methods in the project. Also several polymers for conditioning of the sludge have been tested, as there are differences in the effect of adding polymers depending on the type of sludge to be treated. The full-scale demonstration plant was placed at the Usserd wastewater treatment plant (50,000 PE) located near Copenhagen, Denmark. As post-aeration tank, an existing sludgeholding tank with an active volume of 225 m3 was used. The tank was connected to an equalising tank prior to the sludge press. In order to be able to control the sludge loading of the post-aeration tank, the connecting pipes were constructed so it was possible to bypass the tank and lead the sludge directly to the equalisation tank. This option was required as sludge was pumped in a semi-continuous way from the anaerobic digester. Further, there was only a small equalisation volume between the primary clarier and the post-aeration tank. The post-aeration tank was equipped with a combined mixer/aerator enabling complete mixing, and an oxygen concentration in the range of 13 mg O2/l. The content of ammonia in the digested sludge was 600700 mg N/l. At the determined hydraulic retention time, oxygen concentration and process temperature the process was operated at full nitrification. This resulted in a consumption of alkalinity exceeding the alkalinity content of the sludge. To keep the pH at a range of 6.57.5 it was necessary to add alkalinity, and this was done by adding sodium hydroxide. A flowchart of the plant is shown in Figure 1.
Full-scale test

At the beginning of the test, 75 m3 anaerobically digested sludge and 150 m3 pre-dewatered surplus activated sludge from the secondary step of the treatment plant were added to the

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L. Knudsen et al. Figure 1 Flowchart of the full-scale test plant

post-aeration tank. In order to acclimate the biomass to the process conditions and to obtain full nitrification, no further sludge was led to the tank during the two first weeks of the test period. During the following three weeks the sludge loading was gradually increased until all sludge from the anaerobic digester could be led to the post-aeration tank. Thereafter the flow was typically in the range of 30 to 50 m3 per day, equal to a hydraulic retention time of 4.57.5 days. The oxygen concentration in the tank was maintained at a level of 12 mgO2/l. Sodium hydroxide (28% NaOH) was added continuously to the tank. As control parameters for increasing the sludge loading, the nitrate and the ammonia concentrations were measured daily. The object of this control procedure was to maintain full nitrification in the process. To obtain steady-state conditions in the aeration tank, a running-in period corresponding to 3-4 times the average retention time was conducted. After the steady-state conditions were reached, samples of the digested sludge at the inlet to the tank and of the treated sludge in the effluent from the tank were taken 23 times a week for a period corresponding to 34 retention times. The samples were stored at a temperature of 18C until analyses of the content of organic micropollutants were performed. To control the process in the post-aeration tank, a number of operation parameters were measured in samples taken twice a week. The operation parameters included pH, dry solids, volatile dry solids, ammonia, nitrate, total-phosphorus, and ortho-phosphate. Sludge flow, oxygen concentration, temperature, and sodium hydroxide flow were measured continuously. To examine the effect of the post-aeration process on the dewaterability of the sludge, samples were frequently taken for analyses and for performing further tests in the laboratory.
Method of analysis

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The methods of analysis of the four groups of organic micropollutants are specified in the statutory order (Danish EPA, 1996a) and further specified in a statutory order of the Danish Plant Directorate (Danish Plant Directorate, 1997). The methods of analysis include two separate procedures: 1. GC-MS method for detection of polycyclic aromatic hydrocarbons ( PAH), di(2ethylhexyl)phthalate (DEHP) and nonylphenols as well as their mono- and diethoxylates (NPE)

2. HPLC method for detection of linear alkylbenzenesulphonates (LAS). The methods of analysis can be used for measurement of the following compounds in sludge: PAH (acenaphthene, flourene, phenanthrene, fluoranthene, pyrene, benzo(b+j+k)fluoranthenes, benzo(a)pyrene, indeno(1,2,3-cd)pyrene and benzo(ghi)perylene), DEHP, NPE (measured as the sum of isomers of nonylphenol and their mono- and diethoxylates) and LAS (measured as the sum of isomers in the range of C10C14). The detection limits of the method are 0.02 mg/kg TS for the individual PAH compounds and 0.2 mg/kg TS for the sum, 0.5 mg/kg TS for DEHP, 0.6 mg/kg TS for total NPE, and 50 mg/kg TS for total LAS. The oxygen concentration, pH, and temperature in the post-aeration tank were measured by means of ordinary on-line instruments. All other running parameters were measured in the laboratory. Nitrite was measured by use of semi-quantitative nitrite sticks whereas nitrate and ammonia were measured by means of the Dr. Lange quick analyser. Dry solids and volatile dry solids were measured by use of standard methods. Measurements of dry solids were supplemented with laboratory dewaterability tests including Capillary Suction Time, CST (Baskerville et al., 1968) and Specific Resistance to Filtration, SFR (Kavanagh, 1980).
Results and discussion

L. Knudsen et al.

The content of dry solids in the anaerobically digested sludge was typically in the range of 23.426.7 g DS/kg, whereas the content of dry solids in the post-aerated sludge was 16.820.3 g/kg. The observed reduction of the dry solids content by the process was 18% in mean. The temperature in the anaerobically digested sludge was 3335C, and the temperature in the post-aeration tank was 2530C. A high temperature in the post-aeration tank is wished for the biological processes, however, the efficiency of the aerator decreases with a rising temperature. The oxygen concentration in the post-aerated tank varied considerably and was nearly zero after the anaerobic sludge had been added. The rise in the oxygen concentration was slow, and it took 0.51 hour to regain the determined oxygen concentration level of 13 mg O2/l. The content of ammonia in anaerobically digested sludge was typically in the range of 650700 mg N/l. After the upstart period of the process it was possible to obtain full nitrification, and with a few exceptions the concentration of ammonia was low (<4 mg/l). During the test period the ammonium was quantitatively transformed into nitrate, and the concentration of ammonia in the influent was practically equal to the concentration of nitrate in the effluent. Due to the large nitrification, a pH drop was expected, and as mentioned above this was compensated by adding sodium hydroxide. It was possible to maintain pH in the range of 78 during the entire test period. A considerable part of the content of soluble phosphorus in the digested sludge was precipitated during the post-aeration process. The concentration of soluble phosphorus in the influent was 1525 mg P/l whereas the content in the effluent was 25 mg P/l. Figure 2 shows the concentration of the selected organic micropollutants in anaerobically digested sludge and in the sludge after post-aeration. During the first 44 days of the test period, upstart was carried out and steady-state conditions of the plant were obtained. During this period no samples for analyses of micropollutants were collected. The following comments can be added in connection with the individual graphs in Figure 2:

PAH: The concentration of (PAH in anaerobically digested sludge was in the range of 35 mg/ kg TS, which was below the present limit value (6 mg/kg TS) but above the future limit

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L. Knudsen et al. Figure 2 Concentration of PAH, NPE, DEHP, and LAS in anaerobically digested sludge and in post-aerated sludge

value of year 2000 (3 mg/kg TS). By means of the post-aeration process a reduction of 3050% was achieved which was sufficient in order to observe the future limit value. NPE: The concentration of NPE in anaerobically digested sludge, except for one sample, was in the range of 3545 mg/kg TS, which was below the present limit value (50 mg

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NPE/kg TS) but above the future limit value (10 mg NPE/kg TS). The post-aeration process achieved an advanced reduction of NPE equal to 7595%. The post-aerated sludge can in most cases observe the future limit value, as shown in the above graph. DEHP: The concentration of DEHP in anaerobically digested sludge varied considerably in the range of 20100 mg/kg TS. However, the concentration was in any case below the present limit value (100 mg DEHP/kg TS) but in some cases above the future limit value (50 mg DEHP/kg TS). By means of the post-aeration process, a reduction in the DEHP concentration of 3040% was achieved. This reduction was sufficient to observe the future limit value. LAS: The concentration of LAS in anaerobically digested sludge was 1,8001,900 mg/kg TS, which was below the present limit value (2,600 mg LAS/kg TS) but above the future limit value (1,300 mg LAS/kg TS). By means of the post-aeration processes a reduction of more than 95% of LAS was obtained, and this reduction was sufficient to observe the future limit value of year 2000. During the nine months period before the implementation of the post-aeration process at the treatment plant, the mean value of the weekly dry solid analysis of the dewatered sludge was 25%. During the test period the similar parameter of dewatered sludge was 23% in mean. Apparently, this result indicates a smaller reduction in the content of dry solids after dewatering. However, the results of dewaterability tests showed, that for most types of polymers, the dewaterability of the post-aerated sludge was equal to the anaerobic sludge in terms of CST and SRF. This indicates that a change in the type of polymers used for fullscale dewatering may result in a dry solid content of the dewatered post-aerated sludge equal to what was observed for the anaerobically digested sludge.
Conclusion

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It was demonstrated that by applying a post-aeration process on anaerobically digested sludge, it is possible to reduce the content of selected organic micropollutants to a level which allows the sludge to be used for agricultural purposes, according to Danish regulations. The result of the analysis showed the following typical percentage reductions: +95% for LAS, 7595% for NPE, 3040% for DEHP, and 3050% for (PAH. Furthermore, it was demonstrated that the dewaterability of the post-aerated sludge was nearly as efficient as for digested sludge. It is, therefore, possible to use this process as a simple method for post treatment of the sludge in order to obtain a continued reuse of anaerobically digested wastewater sludge for agricultural purposes, even after imposition of stricter values as e.g. presented in the Danish regulations. Based on the experience with the full-scale post-aeration plant at Usserd wastewater treatment plant, the following observations seem to be important in connection with the possible use of the process: considerable improvement of the permeate from the sludge press with respect to the content of ammonia and soluble phosphorus; a reduction of 1520% in the amount of dry solid in the resulting sludge for dewatering; a considerable consumption of electricity for the aerator, however about 70% will be compensated by less consumption in the biological part of the treatment facility; a considerable consumption of alkalinity in the post-aeration process in order to maintain the pH in the process tank. In the actual case there is a need for addition of about 27 equivalents/m3 anaerobically digested sludge. The costs of running the plant can roughly be separated into aeration (20%) and in adding alkalinity (80%). In order to reduce costs, the plan is to perform tests where lime is

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added instead of sodium hydroxide. If this is a success the total running costs can be reduced by approximately 50% according to the Danish price level for chemicals. Furthermore, this approach is expected to result in an additional improvement of the sludge dewaterability resulting in savings in transport charges for dewatered sludge. It can be concluded that the post-aeration process of anaerobically digested sludge will result in both advantages and disadvantages, which must be evaluated at the wastewater treatment plants, both technically and economically in each individual case.
References
Baskerville, R.C. and Gale, R.S. (1968). A simple automatic instrument for determining the filterability of sewage sludge. Journal of the Institute of Water Pollution Control, 2. Berna, J.L., Ferrer, J., Moreno, A., Prats, D. and Ruiz Bevia, F. (1989). The fate of LAS in the environment. Tenside Surfactants Detergents, 26 (1998) 2. Kavanagh, B.V. (1980). The dewatering of activated sludge: Measurement of specific filtration to resistance and capillary suction time. Wat. Pollut. Control, 79. Knudsen, T.B., Christensen, L.B., Srensen, J., Jepsen, S.E. and Lind, S. (1997). LAS-massebalance p et dansk renseanlg (LAS mass balance on a Danish wastewater treatment plant). Stads- og havneingeniren, 11 (in Danish). Miljstyrelsen (Danish EPA) (1990). Miljfremmede stoffer i kommunalt spildevand (Micropollutants in municipal wastewater). Miljprojekt (Environmental Project), 127 (in Danish). Miljstyrelsen (Danish EPA) (1996a). Use of waste products for agricultural purposes. Statutory order, 823, September 1996 (in Danish). Miljstyrelsen (Danish EPA) (1996b). Miljfremmede stoffer i spildevand og slam (Micropollutants in wastewater and sludge). Miljprojekt (Environmental Project), 325 (in Danish). Miljstyrelsen (Danish EPA) (1996c). Anvendelse af affaldsprodukter til jordbrugsforml (Use of waste products for agricultural purposes). Miljprojekt (Environmental Project), 328 (in Danish). Miljstyrelsen (Danish EPA) (1999). Biologisk nedbrydning af organiske mikroforureninger i spildevand (Biological Degradation of Organic Micropollutants in Wastewater). Miljprojekt (Environmental Project), 506 (in Danish). Plantedirektoratet (Danish Plant Directorate) (1997). Inspection of the quality of municipal wastewater sludge and composted household waste etc. for agricultural use. Statutory order, 528, June 1997. Siegrist, H., Alder, A., Brunner, P.H. and Giger, W. (1989). Pathway analysis of selected organic chemicals from sewage to agriculture soil. Sewage Sludge Treatment and Use. A.H. Dirkzwager and P. LHermite (eds.). Elsevier Science, pp. 133144.

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