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The document summarizes a study that investigated using hydrogen peroxide as an oxidant in conjunction with anaerobic digestion of excess municipal sludge. They tested different configurations including applying the oxidant to the influent, recycle stream, or between two digestion stages. The best improvement was 15.2% higher solid destruction achieved with 2.0 g H2O2/g volatile suspended solids added to the influent. Class A biosolids were obtained for all peroxide dosages tested when combined with two-stage anaerobic digestion.
The document summarizes a study that investigated using hydrogen peroxide as an oxidant in conjunction with anaerobic digestion of excess municipal sludge. They tested different configurations including applying the oxidant to the influent, recycle stream, or between two digestion stages. The best improvement was 15.2% higher solid destruction achieved with 2.0 g H2O2/g volatile suspended solids added to the influent. Class A biosolids were obtained for all peroxide dosages tested when combined with two-stage anaerobic digestion.
The document summarizes a study that investigated using hydrogen peroxide as an oxidant in conjunction with anaerobic digestion of excess municipal sludge. They tested different configurations including applying the oxidant to the influent, recycle stream, or between two digestion stages. The best improvement was 15.2% higher solid destruction achieved with 2.0 g H2O2/g volatile suspended solids added to the influent. Class A biosolids were obtained for all peroxide dosages tested when combined with two-stage anaerobic digestion.
1 Oxidative Co-Treatment Using Hydrogen Peroxide with
Anaerobic Digestion of Excess Municipal Sludge Cacho Rivero, Jesus A; Madhavan, Narain; Suidan, Makram T ; Ginestet, Philippe; Jean-Marc Audic. Water Environment Research78.7 (Jul 2006): 691-700. Active el subrayado de resultados para navegadores hablantes seleccionando el botn Entrar Ocultar subrayado Mostrar entradas duplicadas de otras bases de datos Resumen (resea) TraducirResumen The effect of an oxidative co-treatment on anaerobic digestion of a mixture of primary and waste activated sludge was investigated. The oxidant used in this study was hydrogen peroxide (H^sub 2^O^sub 2^). A maximum improvement in solid destruction of 15.2% was achieved in the overall process, with a dosage of 2.0 g H^sub 2^O^sub 2^/g influent volatile suspended solids (VSS^sub influent^). All configurations operated at this dosage also showed statistically significant increases in solids removal. A statistically significant enhancement in overall solids destruction was observed for the lower oxidant dosage (0.5 H^sub 2^O^sub 2^/gVSS^sub influent^). Surprisingly, for 1.0 g H^sub 2^O^sub 2^/gVSS^sub influent^, only one of the three configurations involving oxidative co-treatment showed significant increases in solids destruction. Special attention was paid to the performance of this process relative to fecal coliforms destruction. Class A biosolids were obtained for all the different hydrogen peroxide dosages used when oxidative co-treatment is combined with a two-stage anaerobic digestion process. [PUBLICATION ABSTRACT] Texto completo
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Headnote ABSTRACT: The effect of an oxidative co-treatment on anaerobic digestion of a mixture of primary and waste activated sludge was investigated. The oxidant used in this study was hydrogen peroxide (H^sub 2^O^sub 2^). A maximum improvement in solid destruction of 15.2% was achieved in the overall process, with a dosage of 2.0 g H^sub 2^O^sub 2^/g influent volatile suspended solids (VSS^sub influent^). All configurations operated at this dosage also showed statistically significant increases in solids removal. A statistically significant enhancement in overall solids destruction was observed for the lower oxidant dosage (0.5 H^sub 2^O^sub 2^/gVSS^sub influent^). Surprisingly, for 1.0 g H^sub 2^O^sub 2^/gVSS^sub influent^, only one of the three configurations involving oxidative co-treatment showed significant increases in solids destruction. Special attention was paid to the performance of this process relative to fecal coliforms destruction. Class A biosolids were obtained for all the different hydrogen peroxide dosages used when oxidative co-treatment is combined with a two-stage anaerobic digestion process. Water Environ. Res., 78, 691 (2006). KEYWORDS: anaerobic digestion, solid destruction, wet sludge disintegration, oxidative treatment, hydrogen peroxide. doi:10.2175/106143006X101647 Introduction Anaerobic digestion is a promising solution to the ever-increasing problems associated with disposal of excess municipal wastewater treatment plant sludge. It is a biological treatment process that reduces the volume and the environmental effects of waste sludge before disposal or land application. However, this process still suffers serious limitations associated with the long retention times needed to maintain stable operations and the fact that the maximum volatile suspended solids (VSS) destruction efficiency reported for this process is only approximately 60% (Parkin and Owen, 1986). Waste activated sludge is mainly composed of microorganisms, with the majority of organic matter either confined within the microbial cell wall or present in the form of extra-cellular biopolymers of low biodegradability. The containment of organic matter within a cell membrane structure renders waste activated sludge an unsuitable substrate for biological degradation (Weemaes and Verstraete, 1998). Therefore, hydrolysis and solubilization of the paniculate matter is considered to be the rate-limiting step in the anaerobic digestion of waste activated sludge. Wet sludge disintegration appears to hold some promise among the various technologies that have been proposed to improve solids hydrolysis and thus enhance subsequent anaerobic digestion (Weemaes and Verstraete, 1998). Oxidative pretreatment is one of the technologies included in this group. This pretreatment process considers the breaking down of the cell wall through an oxidation process. Several processes, such as the Zimpro process (Zimpro Environmental Inc. Rothschild, Wisconsin), Vertech process (VerTech Treatment System, Baarn, Netherlands), and Bayer Loprox process (Bayer Technologies, Leverkusen, Germany), consider oxidation of waste sludge under extreme operating conditions of pressure and temperature (500 kPa to 10 MPa; 200 to 260C). These processes are very efficient in terms of solid destruction. However, the extreme operating conditions are costly and may present safety challenges. Several studies have considered the use of ozone to enhance anaerobic digestion (Sakai et al., 1997; Weemaes et al., 2000; Yasui and Shibata, 1994; Yasui et al., 1996). These studies demonstrate that ozone, when used as an oxidant, can lead to significant improvements in solids solubilization, reduction in sludge generation, and increased methane (CH^sub 4^) production during subsequent anaerobic digestion. The success of ozone as an oxidant, coupled with the expense and complexity of its use, led us to evaluate hydrogen peroxide (H^sub 2^O^sub 2^) as an alternative oxidant. Mukherjee and Levine (1992) evaluated the solubilization of a waste from a com processing plant using Fenton's reagent (hydrogen peroxide + iron) and concluded that this procedure was viable for rapid solubilization of organic species. Benitez et al. (1996, 1997) successfully evaluated both ozone and hydrogen peroxide as oxidants for treating recalcitrant pollutants in agroindustrial wastewaters. The goal of this study was to investigate the use of hydrogen peroxide as the oxidant in an oxidative co-treatment with anaerobic digestion of excess municipal sludge. Different configurations of the anaerobicreactors were considered to evaluate the effect of the oxidative treatment, not only when applied to the influent stream, but also in other locations, such as in the recycle line or between two stages of digestion. Three different dosages were evaluated (0.5, 1.0, and 2.0 H^sub 2^O^sub 2^/g influent volatile suspended solids [VSS^sub influent^]). Methodology Anaerobic Digester and Stress Unit. The experiment was performed with seven well-mixed digesters, each with a liquid volume of 8 L. Each digester was a modified spinner flask (Coming, Corning, New York) equipped with liquid and gas sampling and feeding ports. Mixing was achieved using an air-driven mixer (March Manufacturing, Inc., Glenview, Illinois). The mixer was magnetically coupled to a shaft connected to a paddle that ensured complete mixing. All the digesters were placed in a constant temperature room (37C). The digesters were seeded with anaerobic sludge obtained from the anaerobic digesters at the Mill Creek Wastewater Treatment Plant (WWTP) in Cincinnati, Ohio. The stress unit consisted of a Pyrex (Corning) glass container with enough volume to provide headspace to retain any foaming of the sludge resulting from hydrogen peroxide addition. The hydrogen peroxide was introduced to the stress unit at a constant rate, using a glass syringe driven by a model 11 high-precision infusion pump (Harvard Apparatus Inc., South Natick, Massachusetts). This procedure was deemed necessary to control or minimize foaming during hydrogen peroxide addition and to increase the contact time between the reagent and the sludge. Sludge was held for 24 hours in the stress unit. Hydrogen peroxide was added to the stress unit over a period of 6 hours, and the remaining 18 hours were used for experimental convenience and to ensure that all the oxidant was consumed before introduction of the treated sludge to the digester. The stress units were also placed in the constant temperature room. Therefore, all the co-treatment was conducted at 37C. Configurations Studied. Five different configurations were evaluated in this study (Figure 1). Configuration A served as a control and was fed the raw sludge mixture. It consisted of a single- stage reactor with a solids residence time (SRT) of 30 days. Configuration B was also a single- stage reactor operated at an SRT of 30 days. The feed to configuration B was raw sludge mixture that was pretreated with hydrogen peroxide in the stress unit. Configuration C was a single-stage reactor operated at an SRT of 30 days and a daily recycle of 20% of the total reactor volume. The recycled sludge was treated with hydrogen peroxide in the stress unit before refeeding to the digester. Configuration D consisted of two stages in series, each operated at an SRT of 15 days. This configuration was fed the raw sludge mixture and served as a control for configuration E, which was a two-stage configuration, operated similarly to configuration D, except, in this case, a stress unit was situated between the two stages. Sludge exiting the first stage was treated with hydrogen peroxide before entering the second stage. Feed Sludge. All digesters were fed with the same mixture of primary and waste activated sludge (1:1 mass ratio) with a combined (VSS) concentration of 30 g/L. The sludge was obtained from municipal wastewater treatment plants operated by the Metropolitan Sewer District of Greater Cincinnati (Ohio). Activated sludge was collected from the Mill Creek WWTP, and the primary sludge was obtained from the Sycamore WWTP (Cincinnati, Ohio). The Sycamore WWTl* was originally selected as the source for both primary and waste activated sludge because of the fact that the incoming wastewater to the plant was primarily of household origin. The activated sludge portion of the plant was washed out twice during the early stages of this study, which forced the use of secondary sludge from the heavily industrial Mill Creek WWTP. This plant was equipped with storm bypass treatment, thus minimizing the effect on operation of storm events. The reactors were operated on a draw and fill basis (Farrell et al., 1988); that is, the effluent was withdrawn once a day from the reactor just before feeding. Analytical Methods. Analysis of both liquid and gas samples started after steady state was reached. Steady state was considered to have been attained after operating the digesters for three retention times of the higher SRT of all the reactors involved in the experiment (90 days). Gas composition was determined using an HP 5890 Series II gas chromatograph (Agilent Technologies, Palo Alto, California) equipped with a dual thermal conductivity detector and a 3- m (10-ft) column packed with molecular sieve BX-45/60 mesh (Supelco, Bellefonte, Pennsylvania). The biogas production rate was measured using wet-tip gas meters connected to the gas line of each reactor (Archae Press, Nashville, Tennessee). Liquid samples were analyzed on a weekly basis for the following parameters: pH; solids (total suspended solids [TSS], VSS, and mineral suspended solids); chemical oxygen demand (COD) (total and soluble); total Kjeldahl nitrogen (TKN); ammonia, and volatile fatty acids (VFAs). pH was measured using a combined glass electrode (Orion model 915600, Orion Research, Inc., Beverly, Massachusetts). Chemical oxygen demand was measured using the reactor digestion method (Jirka and Carter, 1975). This method is approved by the U.S. Environmental Protection Agency (Washington, D.C.) for wastewater analysis (Federal Register, April 21 1980). The determination is colorimetric, and the wavelength used was 620 nm for high-range COD and 420 nm for low- range COD. Total COD was measured using the high-range plus Hach kit (Hach Company, Loveland, Colorado). The range covered by this kit is O to 15 000 mgCOD/L. Soluble COD was measured with a low-range Hach kit that covers the range O to 150 mgCOD/L. Total and volatile suspended solids were measured following Standard Methods (APHA et al., 1995). Volatile fatty acids were analyzed using an Agilent 6890 Series gas chromatograph with a flame ionization detector. The chromatograph was equipped with an 80/120 Carbopack B-DA*/4% Carbowax 20M packed column (Supelco, Bellefonte, Pennsylvania). Total Kjeldahl nitrogen was analyzed using the Nessler method, method 8075 (Hach Company). The concentration of fecal coliforms was also monitored to classify the effluent biosolids. The Standards for the Use or Disposal of Sewage Sludge Rule (Subpart D of 40 CFR 503) (2004) establish the requirements for limiting the pathogens in sludge. It classifies sludge as Class A (1000 MPN/g dry basis of fecal coliforms) or Class B (2 000 000 MPN/g dry basis of fecal coliforms). Analysis for fecal coliforms was performed by using the Hach method 10028-MPN A-1 Medium Broth (Hach Company). Results Hydrogen peroxide dosages of 0.5, 1.0, and 2.0 g H^sub 2^O^sub 2^/ gVSS^sub influent^ were evaluated sequentially in this study. The results for each dosage are presented separately. Influent Characteristics. The average characteristics of the influent for the three different periods studied are given in Table 1. The values reported are the average values obtained for the influent sludge used during the period of the experiment for each of the three hydrogen peroxide dosages. The target feed VSS concentration of 30 g/L in the mixture of primary and waste activated sludge was not as exact as we intended because of difficulties in working with raw primary sludge and the determination of its solids content. The different parameters characterizing the influent sludge used for the three different experimental periods are similar, allowing for comparison of the three oxidant dosages. However, it is still important to keep in mind the seasonal effect on sludge characteristics. Gas Production. Average values for the daily volume of methane produced and the methane produced per gram of COD removed are shown in Table 2. Methane produced per gram of COD removed provides a measure on COD closure, with a theoretical value of 397.4 mL CH^sub 4^/g COD removed at 37C (Speece, 1996). The values obtained in most of the cases are lower than that value, although acceptably close. However, lower values than the theoretical are expected as a result of the conversion of a fraction of the organic matter to new bacterial cells (Parkin and Owen, 1986). Leaks and errors in the calibration of the measurement equipment can be also the reason for lower or higher values than expected. Solids. Average values for solids concentration and their removal in each configuration are given in Table 3. Data given for configuration A represent the performance of the control because they represent a single-stage reactor having an SRT of 30 days and involve no oxidative co- treatment. Configuration D represents a system consisting of two reactors in series, each having an SRT of 15 days, and having no oxidative co-treatment. This configuration serves as a control for configuration E, which is also a two-stage system, with oxidative co-treatment between the stages. Oxidative co-treatment with hydrogen peroxide was found to positively affect overall VSS destruction for all the cases considered in this experiment. The effect of the lower two dosages of hydrogen peroxide (0.5 and 1.0 gH^sub 2^O^sub 2^/g VSS^sub influent^) was very limited and similar for all the configurations (Figure 2), with observed increases in VSS destruction ranging between 1.5 and 4.6%. When the hydrogen peroxide dosage was increased to 2.0 g H^sub 2^O^sub 2^/g VSS^sub influent^, a different effect of co-oxidative treatment was observed. Configurations B and E showed marked increases in VSS destruction, averaging 15.2 and 12.9%, respectively, over what was observed for configuration A. When the performance of configuration E is compared with that of configuration D, the improvement in VSS destruction is reduced to 10.8%. Data in Table 4 represent a summary of statistical analyses of the measurements obtained for VSS concentrations for the three different dosages of hydrogen peroxide and for the different reactor configurations. A t test was performed to compare VSS concentration values measured for each configuration to the control configuration (configuration A). Configuration E was also compared with configuration D, which can be considered a control for that treatment scheme. Effluent Quality. Digester effluent quality was characterized by the measures of COD, TKN, ammonia, and VFA. Average values of these parameters for the three different experimental periods are shown in Tables 5, 6, and 7. Destruction of VSS and removal of COD during the anaerobic digestion of sludge are intimately related. Oxidative co-treatment mediated increases in COD removal over the control (configuration A) are shown in Figure 3, while the corresponding data on VSS destruction are given in Figure 2. The data in these two figures are combined in Figure 4, which shows the increase in removal of total and paniculate COD versus the corresponding increase in VSS removal. Paniculate COD is calculated as total COD minus soluble COD. For configurations C and E, the relationship between COD removal and VSS removal is close to 1, as expected. In the case of configuration B, however, a different trend is observed. The COD removal was practically constant for all hydrogen peroxide dosages studied, with this removal being identical to that observed for the control. However, VSS removal was significantly higher for configuration B when compared with the control. This is particularly true for the hydrogen peroxide dosage of 2.0 g/gVSS^sub influent^. Deviation from the equivalency line is significant when total COD was considered. Considering paniculate COD, the relationship observed between COD and VSS removal was significantly closer. This observation suggests the important role of hydrogen peroxide in solids solubilization, a fact that is confirmed by the increase in soluble COD (Figure 5). Configurations C and E exhibited the expected parallel behavior for both VSS and COD removal. Differences between the values can be easily explained with effluent values of soluble COD. Data obtained for ammonia and TKN followed expected behavior. Ammonia concentrations increased with increases in VSS destruction because the mineralization of biomass during anaerobic digestion generates ammonia. On the other hand, the TKN concentration remained constant during the anaerobic process. As for VFAs, it is important to point out two observations: (1) the relatively high concentration of VFA observed in configuration C for all three hydrogen peroxide dosages, and (2) the elevated concentration of propionic acid observed for configuration B when the dosage of hydrogen peroxide was 2.0 gH^sub 2^O^sub 2^/gVSS^sub influent^. Both these observations suggest that the corresponding digesters were operating under stressed conditions. Two reasons could explain this behavior. One is the presence of remaining hydrogen peroxide that interferes with normal operation of the reactor, although this is very unlikely because measurements done for hydrogen peroxide residual were always negative. Therefore, the most probable reason is generation during the oxidative treatment of a refractory compound that causes some inhibition, which reduces the rate of use of VFAs. These compounds were generated when raw sludge was treated with high dosages of hydrogen peroxide and also interfere with the normal operation of the reactor when treated sludge was mixed with raw sludge, although, in this case, the effect was smaller and constant for all dosages. Fecal Coliforms. The concentrations of fecal conforms measured for the three different experimental periods are shown in Figure 6. Configuration E resulted in class A biosolids for all hydrogen peroxide dosages studied. Configuration B generated class A biosolids only when the hydrogen peroxide dosage was 2.0 g/gVSS^sub influent^. All other configurations generated class B biosolids, regardless of hydrogen peroxide dosage. Discussion Methane Production. The methane produced per liter of sludge treated during anaerobic digestion provides a good measure of process performance. Separation of anaerobic sludge digestion into a series of stages increases the performance of the process relative to solids destruction and methane production. This was apparent from the performance of configuration D for all three experimental periods of the study. The use of oxidative co-treatment did not promote improvements in the performance of single- stage configurations for oxidant dosages of 0.5 and 1.0 gH^sub 2^O^sub 2^/gVSS^sub influent^. When the oxidant dosage was increased to 2.0 gH^sub 2^O^sub 2^/gVSS^sub influent^, configuration B exhibited a slight enhancement in the production of methane compared with configuration A (control). This was not the case with configuration C, however. Weemaes et al. (2000) reported an increase in methane production of approximately 100% when waste municipal sludge was preoxidized with 0.1g ozone/gCOD^sub influent^. In this study, much lower levels of enhancement were observed using hydrogen peroxide as the oxidant in dosages ranging from 0.5 to 2.0 g H^sub 2^O^sub 2^/gVSS^sub Influent^. In the case of two-stage configurations, an increase in methane production was observed as the dosage of hydrogen peroxide increased. The methane production in the first stage of both configurations (D and E) was similar. This was expected because the first stage in both configurations is comparable. Compare to the second stage of configuration D (control), methane production in the second stage of configuration E (after co-treatment) was the same for a dosage of 0.5 H^sub 2^O^sub 2^/gVSS^sub Influent^. slightly higher for a dosage of 1.0 H^sub 2^O^sub 2^/gVSS^sub Influent^, and significantly higher for a dosage of 2.0 H^sub 2^O^sub 2^/gVSS^sub Influent^. Therefore, the difference in the methane produced in the second stage of these two configurations increased as the dosage of hydrogen peroxide increased. When the oxidant dosage was increased to 2.0 H^sub 2^O^sub 2^/gVSS^sub Influent^, methane production in the second stage of configuration E was double that observed in the second stage of configuration D, where no cotreatment was practiced. These results are consistent with those reported by Weemaes et al. (2000), where sludge oxidation with ozone was observed to affect a doubling in methane production. However, it is important to note that Weemaes et al. (2000) consider treatment of a raw mixture of primary and waste activated sludge, while, in this study (configuration E), the co-treatment is applied to an already digested sludge that is exiting the first stage digester. The data observed for methane produced per gram of COD^sub removed^ obtained for the single-stage configurations are similar to those reported by Haug et al. (1983), with a single- stage mesophilic anaerobicreactor treating waste activated sludge with a hydraulic retention time of 21.9 days. The data in Table 8 summarize the performance of the anaerobic process expressed in terms of methane produced per gram of VSS removed (Li and Noike, 1992; Ward et al., 1998). The configurations without oxidative co-treatment resulted in higher methane production per gram of VSS destroyed than those with oxidative cotreatment, while this observation was not evident when methane production was assessed against COD^sub removed^ (Table 2). The lack of consistency observed in Table 2 may be a result of several factors, including the following: (1) some of the COD is satisfied by oxidation with hydrogen peroxide, and (2) some suspended solids resisted oxidation during the COD test, while oxidation with hydrogen peroxide resulted in the formation of smaller molecules that were more amenable to consumption in the COD test vials. Solids Removal. Addition of hydrogen peroxide at higher dosages resulted in significant increases in volatile solids removal in the overall process when the oxidative step was applied before digestion and in the case when a two-stage configuration was used. However, the effect of hydrogen peroxide is not linear. There appears to be a very limited advantage to hydrogen peroxide addition for dosages of 0.5 and 1.0 H^sub 2^O^sub 2^/gVSS^sub Influent^. In fact, statistical analysis of the data (Table 4) reveals, with the exception of configuration E, no significant difference between the data obtained for the configurations with oxidative co- treatment and the control for the hydrogen peroxide dosage of 1.0 g/g VSS^sub influent^. A decrease in VSS destruction was observed when the dosage was increased from 0.5 to 1.0 g/gVSS^sub influent^. Weemaes et al. (2000) observed maximum solids solubilization for an ozone dosage of 0.1 gO^sub 3^/ gCOD, with a decrease in solids solubilization when the dosage was increased. This decrease in solubilization may be a result of quenching of the oxidizing radical at the higher dosage or of differences in the characteristics of the sludge used for the different experimental periods. The extent of VSS destruction increases dramatically for configurations B and E when the hydrogen peroxide dosage was increased from 1.0 to 2.0 gH^sub 2^O^sub 2^/gVSS^sub influent^. This observation suggests the existence of a threshold hydrogen peroxide concentration in this concentration range that stimulates the process. No increase in VSS destruction was observed for configuration C, where the same mass of oxidant is added to a much larger volume of sludge (20% of the digester volume). The true oxidant concentration in the stress unit can affect the hydrolysis process, while the dosage rate affects the cost of the process. The true oxidant concentration in the stress unit is given in Table 9 for the different configurations studied. The concentration is express as grams hydrogen peroxide per liter sludge treated and per gram VSS in the stress unit. When the data are analyzed considering the concentration of hydrogen peroxide per liter of sludge treated in the stress unit, a significant increase in solids removal is observed when the dosage increases from 30 to 60 g H^sub 2^O^sub 2^/L^sub sludge^. On the other hand, if we consider the mass of hydrogen peroxide applied per gram VSS in the stress unit, a concentration of 1.95 gH^sub 2^O^sub 2^/gVSS^sub S.U.^ applied to configuration B resulted in maximum increase in VSS removal (15.2%) compare to the control. However, for configuration E, a similar concentration (1.99 g gH^sub 2^O^sub 2^/gVSS^sub S.U.^) only increases solids removal by 5.0%. The sludge treated in configuration B is raw sludge that is a mixture of primary and waste activated sludge, while the sludge treated in the stress unit in configuration E is anaerobic digested sludge. This suggests that the point of addition of the oxidant to a sludge handling stream has a strong influence on the resulting benefits. Figure 7 shows solids removal for the different stages of treatment for all configurations evaluated at an oxidant dosage of 2.0 g H^sub 2^O^sub 2^/g VSS^sub influent^. For configuration B, increased solids removal with respect to the control (configuration A) is a result of solids destruction achieved in the stress unit and not in the anaerobic digester. A VSS destruction of 33.6% was observed in the stress unit, while only 29.6% additional VSS destruction occurred in the digester. This is significantly lower than the 48.0% VSS destruction observed in the control reactor. There was no enhancement to the anaerobic digestion process itself. In configuration C, VSS destruction was the same as for the control. Hence, there was no enhancement in solids destruction during anaerobic digestion. In configuration E, the enhancement in solids destruction with respect to both controls (configurations A and D) was 12.9 and 10.8%, respectively. The enhancement achieved in the stress unit with respect to the first stage of configuration E was 12.0%. Therefore, the overall enhancement of the configuration is a result of the stress unit, and there is no indication of any enhancement to the biodegradation process. Examination of the data on solids removal also suggests that separation of the anaerobic digestion into a series of stages enhanced the performance of the process. Solids removal in configuration D was higher than that observed in configuration A (Table 3). However, statistical analysis of both sets of data (Table 4) shows no significant difference between them. Therefore, the enhancement observed in the gas production when the process is separated into multiple stages is not confirmed in the solids removal data. Effluent Quality. The effect of oxidative co-treatment on the removal of COD^sub total^ (Figure 3) was significantly lower than its effect on VSS removal (Figure 2). This is especially obvious in the case of configuration B, where VSS removal for the dosage 2.0 g H^sub 2^O^sub 2^/ gVSS^sub Influent^ was 15.2% higher than the control, while no difference was observed in total COD removal. This is an illustration of solubilization without subsequent use of particulate organic matter, which is confirmed by residual soluble COD measurements (Figure 5). However, is important to notice that the values of soluble COD do not account for the whole difference between VSS removal and total COD. This is a result of the analytical procedure used to measure VSS and soluble COD. The filter used for VSS analysis was a glass fiber filter, with 1m nominal diameter, while soluble COD was measured on samples filtered through a membrane filter of 0.45 m nominal pore diameter. Soluble COD in effluent from configuration B, when the oxidant dosage was 2.0 gH^sub 2^O^sub 2^/g VSS^sub Influent^, was unexpectedly high. This is directly related to the elevated concentration of propionic acid that was persistent in this system. Even though the concentration of fatty acids was elevated for this system, the pH remained in the neutral range, thus dispelling any fears of system failure. The fact that configuration B exhibited this elevated level of propionic acid, while all other systems resulted in acceptable levels of the fatty acid in their effluents, suggests that some inhibitory material was released from the raw sludge when treated with 2.0 gH^sub 2^O^sub 2^/g VSS^sub Influent^. Furthermore, the precursor to this material must be anaerobically biodegradable because this effect was not pronounced in the other configurations studied. The concentrations of reduced nitrogen, TKN, and ammonia are within the expected ranges for anaerobic digestion (Tables 5, 6, and 7). The TKN was constant in the influent and all effluents for all configurations and experimental periods. The ammonia concentrations increase as the VSS removal increases. The concentrations of the various VFAs (Tables 5, 6, and 7) provide an indicator of the status of the process. The VFA concentration should remain below 300 mg/L for the system to operate in a stable manner. The concentrations reported for configurations A, D, and E indicate good anaerobic digestion of the sludge. The case of configuration B represents the extreme condition observed in this study. In the case of configuration C, a constant relatively high VFA concentration was observed. This suggests that use of oxidative cotreatment in the recycle system and the corresponding daily destruction of 20% of the biomass within the reactor is a possible source of instability for the process. However, the pH of this configuration was within the normal range 6.8 to 7.2. Fecal Coliforms. Microbiological classification of biosolids is fast becoming a key parameter in selecting strategies for sludge disposal. Mesophilic anaerobic digestion of excess municipal sludge is reported to achieve only Class B biosolids (Farrell et al., 1988). The results from the present study (Figure 6) that were obtained for the configuration without oxidative co-treatment confirm these findings, with Class B sludge consistently obtained from configurations A and D. The use of oxidative co-treatment is expected to enhance the microbiological quality of sludge. Configuration B gives information about the effect of the oxidative co-treatment on the raw sludge mixture. No significant reduction in fecal coliforms was observed for oxidant dosages of 0.5 and 1.0 gH^sub 2^O^sub 2^/g VSS^sub influent^. When the oxidant dosage was increased to 2.0 gH^sub 2^O^sub 2^/g VSS^sub influent^, Class A biosolids resulted, suggesting a direct relationship between pathogen removal and hydrogen peroxide dosage. Therefore, the minimum hydrogen peroxide dosage required to achieve Class A biosolids is between 1.0 and 2.0 gH^sub 2^O^sub 2^/g VSS^sub Influent^. Configuration C showed no variation in terms of fecal coliform concentration with changes in hydrogen peroxide dosage. The fact that this configuration is fed raw sludge did not permit for effective reduction in fecal coliforms. On the other hand, configuration E consistently resulted in Class A biosolids for all oxidant dosages. The oxidative treatment of the full stream of anaerobically treated sludge resulted in very effective control of fecal coliforms. Economic Analysis. The cost of hydrogen peroxide for 50% technical grade (standard industrial grade) is $0.345/lb (1 lb = 0.4536 kg) (U.S. Peroxide, 2005). Therefore, the cost of hydrogen peroxide per metric ton of sludge would be $1521.2. This estimate only includes the cost of the bulk chemical. Additional costs that are not considered here include increased capital investment and transport. On the other hand, reduction in the mass of sludge destined for disposal and the benefits associated with the attainment of Class A biosolids should also be factored into the overall cost analysis on a case-by-case basis. Conclusions The use of oxidation with hydrogen peroxide combined with anaerobic digestion can, in some cases, enhance the performance of solids destruction in the overall treatment process. The effect of cotreatment is not linear with the oxidant dosage and, to achieve significant enhancement, the dosage of hydrogen peroxide has to be above a threshold dosage, which we estimate as being between 1.0 and 2.0 gH^sub 2^O^sub 2^/g VSS^sub Influent^. For a dosage of 2.0 gH^sub 2^O^sub 2^/g VSS^sub Influent^, it was observed that the best results are attainable when the oxidant is applied to the sludge before feeding into the digester. However, a high concentration of soluble COD, attributable to a high concentration of propionic acid, was observed in this experiment, making this treatment configuration less effective in total COD removal. No evidence of reactor instability was observed for this treatment configuration. The reduction of the fecal coliform concentration using pretreatment was closely related to hydrogen peroxide dosage, and Class A biosolids were achieved only when the oxidant dosage was 2.0 gH^sub 2^O^sub 2^/g VSS^sub Influent^. Placement of the oxidative co-treatment in the recycle line of a single-stage reactor did not result in significant improvements in any of the parameters of the overall treatment process. A two-stage configuration with an oxidative co-treatment placed between the two reactors exhibited significant improvement in solids removal when the oxidant dosage was 2.0 gH^sub 2^O^sub 2^/g VSS^sub Influent^; however, this improvement was less than that observed for the configuration where the oxidant was applied before digestion. Class A biosolids were achieved with this configuration, independent of the hydrogen peroxide dosages used. Overall, the two-stage configuration was the best performer when all process parameters and the microbiological characteristics of the treated sludge are considered. The cost of oxidative co-treatment may be prohibitive under the conditions treated in this manuscript. Work is ongoing to determine if lower dosages of oxidant coupled with higher oxidative treatment temperature can improve process economics and efficiency. References References American Public Health Association; American Water Works Association; Water Environment Federation (1995) Standard Methods for the Examination of Water and Wastewater, 19th ed.; American Public Health Association: Washington, D.C. Benitez, F. J.; Beltran-Heredia, J.; Acero, J. L.; Gonzalez, T. (1996) Degradation of Protocatechuic Acid by Two Advanced Oxidation Processes: Ozone/UV Radiation and H^sub 2^O^sub 2^/UV Radiation. Water Res., 30, 1597-1604. Benitez, F. J.; Beltran-Heredia, J.; Acero, J. L.; Pinilla, M. L. (1997) Simultaneous Photodegradation and Ozonatkm Plus UV Radiation of Phenolic Acids-Major Pollutants in Agro- Industrial Wastewaters. J. Chem. Technol. Biotechnol, 70, 253-260. Farrell, J. B.; Erlap, A. R; Rickabaugh, J.; Freedman, D.; Hayes, S. (1988) Influence of Feeding Procedure on Microbial Reductions and Performance of Anaerobic Digestion. J. Water Pollut. Control Fed., 60 (5), 635-644. Haug, R. T.; Le Brun, T. J.; Toitorici, L. D. (1983) Thermal Pretreatment of Sludges-A Field Demonstration. J. Water Pollut. Control Fed., 55, 23-34. Jirka, A. M.; Carter, M. J. (1975) Micro Semi-Automated Analysis of Surface and Wastewaters for Chemical Oxygen Demand. Anal. Chem., 47 (8), 1397-1402. Li, Y. Y.; Noike, T. (1992) Upgrading of Anaerobic Digestion of Waste Activated Sludge by Thermal Pretreatment. Water Sci. Technol, 26, 857-866. Mukherjee, S. R.; Levine, A. D. (1992) Chemical Solubilization of Particulate Organics as a Pretreatment Approach. Water Sci. Technol., 26, 9-11. Parkin, G. F.; Owen, W. F. (1986) Fundamentals of Anaerobic Digestion of Wastewater Sludges. J. Environ. Eng., 112, (5) 867-920. Sakai, Y.; Fukase, T.; Yasui, H.; Shibata, M. (1997) An Activated Sludge Process Without Excess Sludge Production. Water Sci. Technol., 36, 163-170. Speece, R. E. (1996) Anaerobic Biotechnology for Industrial Wastewaters. Archac Press, Nashville, Tennessee. Standards for the Use or Disposal of Sewage Sludge (2004) Code of Federal Regulations, Part 503, Title 40. U.S. Peroxide (2005) Frequently Asked Questions, http://www.h2o2.com (accessed April 4, 2005). Ward, A.; Stensel, H. D.; Ferguson, J. F.; Ma, G.; Hummel, S. (1998) Effect of Autothermal Treatment onAnaerobic Digestion in the Dual Digestion Process. Water Sci. Technol., 38,435- 442. Weemaes, M. P. J.; Verstraete, W. (1998) Evaluation of Current Wet Sludge Disintegration Techniques. J. Chem. Technol. Biotechnol., 73, 83-92. Weemaes, M.; Grootaerd, H.; Simoens, F.; Verstraete, W. (2000) Anaerobic Digestion of Ozonized Biosolids. Water Res., 34, 2330-2336. Yasui, H.; Shibata, M. (1994) An Innovative Approach to Reduce Excess Sludge Production in the Activated Sludge Process. Water Sci. Technol., 30, 11-20. Yasui, H.; Nakamura, K.; Sakuma, S.; Iwasaki, M.; Sakai, Y. (1996) A Full Scale Operation of a Novel Activated Sludge Process Without Excess Sludge Production. Water Sci. Technol., 34, 395- 404. AuthorAffiliation Acknowledgments Credits. The authors are grateful to James Baltzer and Brian Yates, both work-study students, and Mar Esperanza Quintana and Pablo Campo Moreno, graduate students, for their assistance in operation of the digesters. Authors. Jesus A. Cacho Rivero and Narain Madhavan are graduate students, and Makram T. Suidan is the Herman Schneider Professor of Environmental Engineering in the Department of Civil and Environmental Engineering, University Of Cincinnati, Ohio. Philippe Ginestet is a process engineer and Jean-Marc Audic is the department head of the Organic Effluent Department at SUEZ ENVIRONNEMENT, CIRSEE, Le Pecq-sur-Seine, France. Correspondence should be addressed to Makram T. Suidan, Department of Civil and Environmental Engineering, 765 Baldwin Hall, University Of Cincinnati, Cincinnati, Ohio 45221-0071; e-mail: makram.suidan@uc.edu. Submitted for publication August 17, 2004; revised manuscript submitted April 4, 2005; accepted for publication June 15, 2005. The deadline to submit Discussions of this paper is October 15, 2006. Link: http://search.proquest.com/docview/216087493/9504A1DBA9664346PQ/12?accountid=29068
Pregunta: la digestin anaerobia en que se basa en el sentido que reacciones lleva acabo, ya que la digestin anaerobia tiene como objetivo descomponer material en ausencia de oxigeno entonces, debo buscar la relacin de la digestion anaerobia y el sustrato lignocelulosico. ( es el proyecto de Mabel)