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STABILITY OF PARTIAL NITRITATION OF POULTRY SLAUGHTERHOUSE WASTEWATER IN A SEQUENTIAL BATCH REACTOR

ABSTRACT

The aim of this study was to monitor the stabilization of a sequential batch reactor (SBR) regarding the partial nitritation of poultry slaughterhouse wastewater, aiming at preparing it for a reactor with bacteria that promote anaerobic ammonia oxidation (anammox). A cylindrical reactor with a useful volume of 3.5 L, mechanical agitation (50 rpm), and suspended biomass was used in the experiment. The strategies adopted for nitrite-oxidizing bacteria (NOB) inhibition were cycle time (CT: 24, 16, 6, 5, 4 h and real-time monitoring), free ammonia accumulation, alkalinity restriction and low concentrations of dissolved oxygen (DO). The ammonification process, observed at all experimental phases, negatively influenced the control of partial nitritation process. Alkalinity restriction under low cycle times (4 and 5 h) conditions, together with low dissolved oxygen concentration, was a key factor for nitrite-oxidizing bacteria inhibition. Stability of partial nitritation was only reached by real-time monitoring, being the cycles stopped when 50% N–NH4+ and 50% N–NO2 were present in the reactor.

KEYWORDS:
anammox; deammonification; nitrite; nitrate; nitrafying

INTRODUCTION

Biological nitrogen removal can occur by conventional method from autotrophic nitrification processes in which nitrifying bacteria oxidize ammonia to nitrite and then nitrite to nitrate, followed by the heterotrophic denitrification process, with conversion of nitrate to nitrite and, subsequently, to nitric oxide (NO), nitrous oxide (N2O) and nitrogen gas (N2). Recently, faster methods have been studied such as partial nitritation followed by final nitrogen removal by microorganisms with anammox (anaerobic ammonia oxidation) activity or short-cut denitrification (MADIGAN, 2010MADIGAN, M.T.; MARTINKO, J.M.; PARKER, J. Microbiologia de Brock. 12th ed. São Paulo: Prentice Hall, 2010.).

Nitrogen removal by anammox is an interesting treatment possibility since the bacteria involved have a greater capacity of transforming nitrogenous forms present in wastewater into nitrogen gas (N2) (SCHEEREN et al., 2011SCHEEREN, MB.; KUNZ, A.; STEINMETZ, R.L.R.; DRESSLER, V.L. O processo ANAMMOX como alternativa para tratamento de águas residuárias, contendo alta concentração de nitrogênio. Revista Brasileira de Engenharia Agrícola e Ambiental, Campina Grande, v. 15, p. 1289-1297, 2011.). Researches on new nitrogen removal pathways are important because of the high cost of aeration systems, which are needed in wastewater with high loads (CHANG et al 2012). WANG et al (2011) indicated partial nitritation followed by denitrification, or anammox activity, as a viable solution regarding this aspect.

In order for the removal process to be possible via anammox, partial nitritation of wastewater is needed, so that the substrate presents in its composition a ratio of 1-mole ammoniacal nitrogen to 1.32-mole nitrite, i.e. 50% ammoniacal nitrogen and 50% nitrogen as nitrite (MADIGAN, 2010MADIGAN, M.T.; MARTINKO, J.M.; PARKER, J. Microbiologia de Brock. 12th ed. São Paulo: Prentice Hall, 2010.).

Partial nitritation of ammoniacal nitrogen to nitrite is promoted by nitrite-oxidizing bacteria (nitrafying) inhibition, which inhibits nitrate formation. The factors that exert a greater influence on this inhibition are pH, dissolved oxygen (DO), temperature and nitrifying bacteria (Nitrosomonas and Nitrobacter) doubling rate (PRA et al, 2012PRÁ, M.C.; KUNZ, A.; BORTOLI, M.; PERONDI, T.; CHINI, A. Simultaneous removal of TOC and TSS in swine wastewater using the partial nitritation process. Journal of Chemical Technology and Biotechnology, Oxford, v. 87, n. 12, p. 1641-1647, 2012.; VIANCELLI et al, 2011VIANCELLI, A.; KUNZ, A.; ESTEVES A.P.; BAUERMANN, F.V.; FURUKAWA, K.; FUJII, T.; ANTÔNIO, R.V.; VANOTTI, M. Bacterial biodiversity from an anaerobia it flow bioreactor with ANAMMOX activity inoculated with sludge swine. Brazilian Archives of Biology and Technology an International Journal, Curitiba, v. 54, n. 5, p. 1035-1041, 2011.; SUN et al 2010SUN, H.W.; YANG, Q.; HOU, H.X.; ZHANG, S.J.; YANG, Y.Y.; PENG, Y.Z. Achieving the nitrite pathway using FA inhibition and process control in UASB-SBR system removing nitrogen from landfill leachate. Sci China Chemistry, Beijing, v. 53, p. 1210–1216, 2010., ZHU et al 2008ZHU, G. et al. Biological Removal of Nitrogen from Wastewater. Reviews of Environmental Contamination and Toxicology, New York, v. 192, p. 159-195, 2008.).

The effect of pH on partial nitritation can be expressed in two ways, either the inhibitory action of the hydrogen [H+] and hydroxyl [OH] ions on microorganism growth rate or the inhibitory action of free ammonia. According to ZHU et al. (2008)ZHU, G. et al. Biological Removal of Nitrogen from Wastewater. Reviews of Environmental Contamination and Toxicology, New York, v. 192, p. 159-195, 2008., nitrite-oxidizing bacteria present a lower growth rate when submitted to a high pH condition than ammonia-oxidizing bacteria, which favors partial nitritation.

Dissolved oxygen acts as a regulator of ammonia to nitrite conversion since it is the final electron acceptor in nitritation. In studies by VIANCELLI et al. (2011)VIANCELLI, A.; KUNZ, A.; ESTEVES A.P.; BAUERMANN, F.V.; FURUKAWA, K.; FUJII, T.; ANTÔNIO, R.V.; VANOTTI, M. Bacterial biodiversity from an anaerobia it flow bioreactor with ANAMMOX activity inoculated with sludge swine. Brazilian Archives of Biology and Technology an International Journal, Curitiba, v. 54, n. 5, p. 1035-1041, 2011., in which partial nitritation and anammox activity occurred in the same reactor submitted to DO values lower than 0.5 mg L−1, process viability was confirmed under low dissolved oxygen concentration. In experiments with complete nitrification, ANDRADE et al. (2010)ANDRADE, L.; KUMMER, A.C.B.; FAZOLO, A.; DAMASCENO, S., HASAN, S.D.M. Influência de nitrogênio amoniacal e vazão de ar no processo de nitrificação, etapa de tratamento de efluente de abatedouro de peixe. Engenharia Agrícola, Jaboticabal, v.30, n.1, p.160-167, jan./fev. 2010. assessed the influence of DO on nitrification speed and observed that nitrification rate is directly proportional to DO concentration.

GERARDI (2006)GERARDI, M.H. Wastewater bacteria. Hoboken: John Wiley & Sons, 2006. observed that a difference in doubling time between the two nitrifying bacteria groups influences inhibition process. In treatment systems, Nitrosomonas (nitrifying) population size is greater than Nitrobacter (nitrafying) because Nitrosomonas obtain more energy from ammonium ion oxidation; on the other hand, Nitrobacter obtains its energy from nitrite ion oxidation. Therefore, nitrifying bacteria have a shorter generation time and are able to increase rapidly in number when compared to nitrafying bacteria. In order to reduce the growth rate of nitrafying bacteria, several authors have maintained the reactor temperature around 35 °C since high temperature reduces microorganism growth rate (ZHU et al, 2008ZHU, G. et al. Biological Removal of Nitrogen from Wastewater. Reviews of Environmental Contamination and Toxicology, New York, v. 192, p. 159-195, 2008.; WANG et al, 2011; PRÁ et al. Al, 2012PRÁ, M.C.; KUNZ, A.; BORTOLI, M.; PERONDI, T.; CHINI, A. Simultaneous removal of TOC and TSS in swine wastewater using the partial nitritation process. Journal of Chemical Technology and Biotechnology, Oxford, v. 87, n. 12, p. 1641-1647, 2012.).

Sequential batch reactor (SBR) has been shown a viable option in nutrient removal due to ease of operation and low cost (DALLAGO et al, 2012DALLAGO, R.C.; GOMES, S.D.; MEES, J.B.R.; ASSIS, T.M.; HASAN, S.D.M.; KUNZ, A. Nitrification and denitrification of a poultry slaughterhouse wastewater according to cycle time and ammoniacal nitrogen concentration using surface response Methodology. Journal of Food, Agriculture & Environment, v. 10, n. 2, p. 856-860, 2012.; ANDRADE et al 2010ANDRADE, L.; KUMMER, A.C.B.; FAZOLO, A.; DAMASCENO, S., HASAN, S.D.M. Influência de nitrogênio amoniacal e vazão de ar no processo de nitrificação, etapa de tratamento de efluente de abatedouro de peixe. Engenharia Agrícola, Jaboticabal, v.30, n.1, p.160-167, jan./fev. 2010.; MEES et al, 2013MEES, J.B.R.; GOMES, S.D.; HASAN, S.D.M.; GOMES, B.M.; BOAS, M.A.V. Nitrogen removal in a SBR operated with and without pre-denitrification: effect of the carbon:nitrogen ratio and the cycle time. Environmental Technology, London, v. 35, n. 1, p. 115-123, 2013. DOI: 10.1080/09593330.2013.816373, 2013.
https://doi.org/10.1080/09593330.2013.81...
).

In this context, the aim of this study was to assess the stability of partial nitritation of poultry slaughterhouse wastewater in a sequential batch reactor (SBR) using as variables the pH, presence of free ammonia, alkalinity supply, DO concentration and cycle time.

MATERIAL AND METHODS

Wastewater

Wastewater was collected at the exit of an anaerobic lagoon from the wastewater treatment system of a poultry slaughterhouse located in the western region of Paraná State. After collection, wastewater was homogenized, conditioned in 2 L polyethylene containers and stored in a freezer at −20 °C. Before storing process, wastewater was characterized according to physical and chemical parameters presented in Table 1.

TABLE 1
Characteristics of poultry slaughterhouse wastewater and respective methods used.

Free ammonia concentration in the reactor was determined by [eq. (1)], according to ANTHONISEN et al. (1976)ANTHONISEN, C.A.; LOEHR, R.C.; PRAKASAM, T.B.S.; SRINATH, E.G. Inhibition of nitrification by ammonia and nitrous acid. Journal of Water Pollution Control Federation, Washington, n. 48, p.835-852, 1976.:

(1) Free ammonia ( mg L 1 ) = ( 17 / 14 )* ( ( N–NH 4 + )* 10 pH ) / e ( 6.344 / 273 + ° C ) + 10 pH )

where,

  • N–NH4+ is the ammoniacal nitrogen concentration in the reactor;

  • pH is the pH value in the reactor, and

  • °C is the temperature in the reactor.

Inoculum

The reactor was inoculated with nitrifying biomass from a sequential batch reactor (SBR) operated with bovine slaughterhouse wastewater. In the reactor inoculation, 25% of inoculum and 75% poultry slaughterhouse wastewater (v/v) were used. Reactor biomass concentration expressed in volatile suspended solids (VSS), was maintained at 2700 mg L−1, according to the condition used by MEES et al. (2013)MEES, J.B.R.; GOMES, S.D.; HASAN, S.D.M.; GOMES, B.M.; BOAS, M.A.V. Nitrogen removal in a SBR operated with and without pre-denitrification: effect of the carbon:nitrogen ratio and the cycle time. Environmental Technology, London, v. 35, n. 1, p. 115-123, 2013. DOI: 10.1080/09593330.2013.816373, 2013.
https://doi.org/10.1080/09593330.2013.81...
.

Experimental apparatus and operating conditions

Experimental apparatus consisted of a reactor, an aerator coupled to a flow meter to control airflow rate, a heater, a temperature controller and a mechanical stirrer with rotating blades with rotation set at 50 rpm.

SBR reactor was assembled in bench scale and manufactured of cylindrical polyethylene (18.5 cm in diameter and 20.5 cm in height), with a total volume of 5.5 L and a working volume of 3.5 L. In each batch, 2.625 L of wastewater were added to the reactor, in which was maintained 875 mL of the previous batch as inoculum. The reactor was operated with suspended biomass.

Batch reactor operating cycle was composed of the following phases: feeding, reaction (aerobic), sedimentation and discharging. Between one and another cycle, the system was kept at rest for immediate analysis of N–NH4+ and alkalinity because, when necessary, initial alkalinity was adjusted to the next batch. Alkalinity correction was carried out with sodium bicarbonate solution at a ratio of 0.61 mg NaHCO3 per mg N–NH4+ to be oxidized, as described by LAMENGO NETO & COSTA (2011)LAMENGO NETO, L.G.; COSTA, R.H.R. da. Tratamento de esgoto sanitário em reator híbrido em bateladas sequenciais: eficiência e estabilidade na remoção de matéria orgânica e nutrientes (N, P). Engenharia Sanitária Ambiental, Campina Grande, 2011, v. 16, n. 4, p. 411-420. 2011. Disponível em: <http://dx.doi.org/10.1590/S1413-41522011000400013>.
http://dx.doi.org/10.1590/S1413-41522011...
. In addition to sampling for alkalinity correction, collected samples were analyzed for physical and chemical parameters, as presented in Table 1.

During the start-up, the reactor was operated with a 24-hour cycle time (CT), with a supply of 3.0 mg L−1 of oxygen and calcium bicarbonate to maintain a pH range between 7.0 and 8.0. The reactor was maintained under these conditions for 30 days.

At the end of reactor start-up period, strategies were adopted to inhibit nitrite-oxidizing bacteria, aiming at allowing the oxidation of only 50% N–NH4+ to N–NO2 (Table 2).

TABLE 2
Strategies of nitrite-oxidizing bacteria inhibition during sequential batch reactor operation.

In order to promote the oxidation of only 50% N–NH4+ to N–NO2, in the phases IV and V the alkalinity supply was calculated by [eq. (2)]

(2) Additional alkalinity ( mg ) = [ ( 7.14* A*X ) ( B*Y ) ] *V

where,

  • 7.14 is the mass of CaCO3 (mg) required for oxidation of 1.0 mg of ammoniacal nitrogen,

  • A is the N–NH4+ fraction to be oxidized (in this study, 0.5),

  • X is the initial concentration of ammoniacal nitrogen in the wastewater (mg L−1),

  • B is the alkalinity fraction required to oxidize A,

  • Y is the initial concentration of alkalinity (mg L−1), and

  • V is the reactor volume (L).

Each experimental phase lasted 14 days, seven of them for microorganism adaptation to the new conditions and the other seven days for taking samples in all operating cycles, thus justifying the different numbers of cycles occurred at each experimental phase.

At phase V, CT was not previously fixed as at the other phases. A differentiated strategy was chosen, which consisted of performing 12 cycles with real-time monitoring, closing each cycle until such time as the proportion of 50% N–NH4+ and 50% N–NO2 is reached.

In order to demonstrate the results, temporal profiles are presented, which allow visualizing the ammoniacal nitrogen conversion into nitrite and nitrate during the tests.

RESULTS AND DISCUSSION

During the start-up period, the reactor was operated with a 24-hour cycle time, presenting 99% average conversion from N–NH4+ to N–NO3, confirming that the biomass used in the experiment was active.

Phase I

Results concerning reactor operation under conditions established at experimental phase I (CT: 16 h; pH: 7.4 to 7.8; DO: 1.0 mg L−1) are shown in Table 3.

TABLE 3
Characterization of reactor affluent and effluent at phase I.

A nitrate increase in the reactor effluent can be observed, with the three combined nitrogen forms in the effluent higher than the N–NH4+ values in the affluent, indicating the existence of heterotrophic activity in the reactor (ammonification), in which organic nitrogen was converted into ammoniacal nitrogen, providing more substrate for nitrification during batching. MOREIRA et al. (2002)MOREIRA, M.P.; YAMAKAWA, C.S.; ALEGRE, R.M. Adição de fonte de carbono no início da fase anóxica na remoção de macronutrientes e DQO por Lodo ativado usando RBS no tratamento de água residuária avícola. Engenharia Sanitária e Ambiental, Campina Grande, v. 7, n. 1, p. 16-20, 2002. performed an experiment in an SBR reactor with nitrification and complete denitrification of poultry wastewater and observed ammonia production peaks during the cycles and COD consumption during aeration phases of the experimental cycle. In this study, COD consumption was also observed during aerobic phase.

At 16-hour cycle time (phase I), TKN and COD parameters presented average values in the affluent of 165.59 ± 40.60 and 40.38 ± 5.75 mg L−1, respectively, and 53.90 ± 11.07 and 29.16 ± 3.49 mg L−1 in the reactor effluent, proving the ammonification that was observed throughout the experiment. BRANDELERO et al. (2010)BRANDELERO, S.M.; SIQUEIRA, E.Q.; SANTIAGO, M.F. A cinética do nitrogênio em água superficial de ambiente lótico. Ambi-Agua, Taubaté, v. 5, n. 3, p. 147-156, 2010. DOI:10.4136/ambi-agua.159
https://doi.org/10.4136/ambi-agua.159...
performed a kinetic study of lotic environments and observed the possibility of simultaneous occurrence of ammonification and nitrification processes under low OD concentration conditions.

The complete nitrification observed in this stage can be justified by the cycle time value (16 h), which is considered relatively high for the oxidation of only 50% of the initial N–NH4+. In a kinetic study of nitrifying activity in a SBR reactor with poultry slaughterhouse wastewater, MEES et al. (2013)MEES, J.B.R.; GOMES, S.D.; HASAN, S.D.M.; GOMES, B.M.; BOAS, M.A.V. Nitrogen removal in a SBR operated with and without pre-denitrification: effect of the carbon:nitrogen ratio and the cycle time. Environmental Technology, London, v. 35, n. 1, p. 115-123, 2013. DOI: 10.1080/09593330.2013.816373, 2013.
https://doi.org/10.1080/09593330.2013.81...
observed average values for the constants k1 (nitritation) and k2 (nitratation) of 0.0043 ± 0.00315 min−1 and 0.02305 ± 0.00105 min−1, respectively, indicating that the conversion of ammoniacal nitrogen into nitrite is a limiting stage of the process since its speed is five times lower than the conversion rate from nitrite to nitrate, confirming the favoring of nitrate generation with cycle time increasing.

Phase II

In the Table 4 is shows the characterization of reactor affluent and effluent during the its operation under conditions established at experimental phase II (CT: 6h; pH: 7.4 to 7.8; DO: 1.0 mg L−1).

TABLE 4
Characterization of reactor affluent and effluent at phase II.

At phase II, a higher nitrate concentration was observed in the reactor affluent when compared to phase I due to nitrate accumulation from the previous batch. The occurrence of complete nitrification was also observed, demonstrating that cycle time reduction from 16 to 6 hours, while maintaining the other operating conditions, was insufficient to promote partial nitritation. TKN average values in reactor affluent and effluent were 252.68 ± 66.57 mg L−1 and 24.84 ± 10.76 mg L−1, respectively, and COD values were 45.26 ± 7.46 and 11.67 ± 7.69 mg L−1, respectively. BRESSAN et al. (2011)BRESSAN, C.R.; SOARES, H.M.; KUNZ, A. Limiting alkalinity to control partial nitritation in a sequencing batch reator (SBR) in order to adequate an effluent to ANAMMOX processes. In: II SIMPÓSIO INTERNACIONAL SOBRE GERENCIAMENTO DE RESÍDUOS AGROPECUÁRIOS E AGROINDUSTRIAIS, 2., 2011, Foz do Iguaçu. Anais… observed nitrate formation in the second month of reactor operation. The authors attributed nitrate accumulation to the cellular growth of nitrifying bacteria, making ammonia oxidation process faster. The authors worked around this situation with CT reduction, a measure also adopted in this study.

Phase III

At experimental phase III (TC: 5 h; pH: 8 to 9; DO: 1 mg L−1), pH range from 8 to 9 was used in order to inhibit nitrite-oxidizing bacteria by free ammonia (SUN et al, 2010SUN, H.W.; YANG, Q.; HOU, H.X.; ZHANG, S.J.; YANG, Y.Y.; PENG, Y.Z. Achieving the nitrite pathway using FA inhibition and process control in UASB-SBR system removing nitrogen from landfill leachate. Sci China Chemistry, Beijing, v. 53, p. 1210–1216, 2010.). In the Table 5 is show concentration values of nitrogenous forms in reactor affluent and effluent during the operation under phase III conditions.

TABLE 5
Results of nitrogenous forms in reactor affluent and effluent at phase III.

In the Table 5 can be observed free ammonia formation in the reactor. Inhibition of bacteria that oxidize nitrite to nitrate can occur at free ammonia concentrations from 0.1 mg L−1, but according to ANTHONISEN et al. (1976)ANTHONISEN, C.A.; LOEHR, R.C.; PRAKASAM, T.B.S.; SRINATH, E.G. Inhibition of nitrification by ammonia and nitrous acid. Journal of Water Pollution Control Federation, Washington, n. 48, p.835-852, 1976., this inhibition effectively manifests for Nitrosomonas at initial free ammonia concentration in the range from 10 to 150 mg L−1. Such concentration was not reached in this study.

At 5-hour cycle time (phase III), parameter values in reactor affluent and effluent were, respectively, 60.27 ± 7.36 and 30.94 ± 13.72 mg L−1 for TKN, 50.86 ± 9.75 and 37.26 ± 11.35 mg L−1 for COD, 8.58 and 8.72 for pH and 1367 and 1310 mg L−1 for alkalinity.

SUN et al. (2010)SUN, H.W.; YANG, Q.; HOU, H.X.; ZHANG, S.J.; YANG, Y.Y.; PENG, Y.Z. Achieving the nitrite pathway using FA inhibition and process control in UASB-SBR system removing nitrogen from landfill leachate. Sci China Chemistry, Beijing, v. 53, p. 1210–1216, 2010. obtained satisfactory results when using free ammonia as an inhibitor of nitrite-oxidizing bacteria in a study with sanitary sewage with an affluent concentration of 2444 mg L−1 of ammoniacal nitrogen and 15 mg L−1 of free ammonia. The authors aforementioned obtained partial nitritation efficiency of 76%. Comparing that result to those found in this study, the initial low ammoniacal nitrogen concentration in this study may promoted a negative influence on that inhibition strategy.

In a similar research, aiming at nitrification via nitrite, QUEIROZ et al. (2011)QUEIROZ, L.M.; AUN, M.V.; MORITA, D M.; ALEM SOBRINHO, P. Biological nitrogen removal over nitritation/denitritation using phenol as carbon source. Brazilian Journal of Chemical Engineering, São Paulo, v. 28, p. 197-207, 2011. worked with an initial free ammonia concentration of approximately 12 mg L−1, an internal reactor temperature of 35 °C and an initial concentration of ammoniacal nitrogen varying between 200 and 500 mg L−1. The authors observed that such free ammonia concentration was insufficient to inhibit nitrification, even though within the parameters recommended by the literature. Thus, these results were attributed to microorganism adaptation. Free ammonia concentrations present in this study also evidenced such adaptation behavior of bacteria to free ammonia concentrations present in the substrate.

Phase IV

In the Table 6 is shown the characterization of reactor affluent and effluent during the operation under experimental phase IV conditions (CT: 4 h; DO: 0.5 mg L−1).

TABLE 6
Characterization of reactor affluent and effluent at phase IV.

Nitrifying bacteria activity was inhibited from strategies used in this experimental phase (IV), in which additional alkalinity started being provided, calculated as Equation 2. However, such factors were still not sufficient to maintain stable partial nitritation, represented by 50% N–NH4+ and 50% N–NO2.

At four-hour cycle time (phase IV), affluent and effluent concentrations of TKN were 69.92 ± 29.50 and 35.93 ± 11.30 mg L−1, respectively, and 52.44 ± 10.24 and 28.53 ± 6.62 mg L−1 for COD, also demonstrating a heterotrophic activity in the reactor.

SCHREEN et al. (2011)SCHEEREN, MB.; KUNZ, A.; STEINMETZ, R.L.R.; DRESSLER, V.L. O processo ANAMMOX como alternativa para tratamento de águas residuárias, contendo alta concentração de nitrogênio. Revista Brasileira de Engenharia Agrícola e Ambiental, Campina Grande, v. 15, p. 1289-1297, 2011. and GALÍ et al. (2010), when carrying out studies with partial denitritation implementation, observed that high concentrations of ammoniacal nitrogen facilitated the process maintenance. The authors commented that the critical point for partial nitrification maintenance from ammonia to nitrite was low ammoniacal nitrogen concentration in the affluent. ZHU et al. (2008)ZHU, G. et al. Biological Removal of Nitrogen from Wastewater. Reviews of Environmental Contamination and Toxicology, New York, v. 192, p. 159-195, 2008. also reported difficulties in maintaining partial nitritation in affluents with low ammoniacal nitrogen concentrations (close to 50 mg L−1) due to low ammonia saturation coefficient.

When comparing the results of this study with those of other authors, a possible conclusion is that low ammonia concentration in the affluent may have promoted a negative influence on the establishment and maintenance of partial nitration in the reactor. SUN et al. (2010)SUN, H.W.; YANG, Q.; HOU, H.X.; ZHANG, S.J.; YANG, Y.Y.; PENG, Y.Z. Achieving the nitrite pathway using FA inhibition and process control in UASB-SBR system removing nitrogen from landfill leachate. Sci China Chemistry, Beijing, v. 53, p. 1210–1216, 2010. and PRÁ et al. (2012)PRÁ, M.C.; KUNZ, A.; BORTOLI, M.; PERONDI, T.; CHINI, A. Simultaneous removal of TOC and TSS in swine wastewater using the partial nitritation process. Journal of Chemical Technology and Biotechnology, Oxford, v. 87, n. 12, p. 1641-1647, 2012. were successful in partial nitritation when working with ammonia concentrations of 2444 mg L−1 and approximately 1343.56 mg L−1, respectively.

Phase V – Real-time monitoring of partial nitritation

At phase V (CT: variable; DO: 0.1 to 0.3 mg L−1), the last experimental phase and that which received alkalinity supplementation according to Equation 2, the ideal cycle time for wastewater partial nitritation was investigated. For this, 12 cycles were carried out, in which wastewater was sampled at each hour and performed analyses of ammoniacal nitrogen, nitrite, and nitrate. The cycle was stopped at the time the ratio of approximately 50% nitrite to 50% ammoniacal nitrogen (partial nitritation) was identified. Results of N–NH4+, N–NO2 and N–NO3 for reactor affluent and effluent at phase V cycles are shown in Figure 1.

FIGURE 1
Concentration of nitrogenous forms in reactor affluent and effluent at phase V cycles.

The cycle time of the 12 cycles performed at phase V presented variation, with an average of 6.03 hours and a modal value of 6.5 hours.

As demonstrated in this study, BLACKBURNE et al. (2007)BLACKBURNE, R.; YUAN, Z.; KELLER, J. Partial nitrification to nitrite using low dissolved oxygen concentration as the main selection factor. Biodegradation, Dordrecht, p. 303-312, 2007. also used low DO concentration in a nitrifying reactor operated under the continuous system. Enrichment of ammonia-oxidizing bacteria was achieved with DO concentration of 0.4 mg L−1.

SUN et al. (2010)SUN, H.W.; YANG, Q.; HOU, H.X.; ZHANG, S.J.; YANG, Y.Y.; PENG, Y.Z. Achieving the nitrite pathway using FA inhibition and process control in UASB-SBR system removing nitrogen from landfill leachate. Sci China Chemistry, Beijing, v. 53, p. 1210–1216, 2010. observed that in several studies partial nitritation was maintained from the application of real-time control in SBR reactors. GU et al. (2012)GU, S.; WANG, S.; YANG, Q.; YANG, P.; PENG, Y. Start up partial nitrification at low temperature with a real-time control strategy based on blower frequency and pH. Bioresource Technology. 34-41, 2012. assessed the performance of partial nitritation process under low-temperature conditions in a sequential batch reactor with real-time control and obtained 90% nitrite accumulation rate.

Results of TKN and COD obtained at this phase also reinforce ammonification occurrence in the reactor from COD consumption. TKN and COD concentrations in reactor affluent and effluent were 71.53 ± 6.05 and 41.06 ± 7.36 mg L−1 and 81.19 ± 11.39 and 43.05 ± 11.49 mg L−1, respectively.

In the Figure 2 is shown the nitrogenous species concentrations, total ammoniacal nitrogen (N–TAN) in reactor affluent and effluent, nitrite and nitrate in the effluent (Figure 2a) and N– NH4+:NO2 ratio values (Figure 2b) for all the tests carried out at experimental phases from I to V.

FIGURE 2
Reactor behavior for all cycles of phases from I to V: a) nitrogen species concentrations in reactor affluent and effluent; b) N–NH4+:NO2 ratio values at the end of each cycle.

To be considered partial nitritation, N–NH4+:NO2 ratio should have a value close to 1, as shown in Equation 3 (MADIGAN, 2010MADIGAN, M.T.; MARTINKO, J.M.; PARKER, J. Microbiologia de Brock. 12th ed. São Paulo: Prentice Hall, 2010.):

(3) NH 4 + + 1.32 NO 2 + 0.066 HCO 3 + 0.13 H + 1.02 N 2 + 0.26 NO 3 + 0.066 CH 2 O 0.5 N 0.15 + 2.03 H 2 O

According to the profiles presented in Figure 2, mainly regarding N–NH4+:NO2 ratio (Figure 2b), partial nitritation process stabilization was not reached during the study. However, cycles in which N–NH4+:NO2 ratio reached values close to 1 were observed at all studied phases, indicating that modifications in inhibition strategies reached their initial effect, followed by microorganism adaptation to the changes promoted. In addition, at phase V, in which real-time monitoring of partial nitritation was promoted, N–NH4+:NO2 ratio values were more stable and closer to those recommended.

CONCLUSIONS

Ammonification process, observed at all experimental phases, negatively influenced partial nitritation process control. Alkalinity restriction together with low dissolved oxygen concentration under low cycle time (4 and 5 h) conditions, was decisive factors for nitrite-oxidizing bacteria inhibition. Partial nitritation stability was only achieved by real-time monitoring, in which cycles were stopped when 50% N–NH4+ and 50% N–NO2 were present in the reactor.

ACKNOWLEDGEMENTS

To CAPES for granting a scholarship.

REFERENCES

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Publication Dates

  • Publication in this collection
    Mar-Apr 2017

History

  • Received
    03 May 2016
  • Accepted
    25 Sept 2016
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