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Front. Environ. Sci. Engin. China 2007, 1(1): 4952 DOI 10.

1007/s11783-007-0009-1

RESEARCH ARTICLE

Simultaneous nitrification and denitrification in activated sludge system under low oxygen concentration
ZHANG Peng1, ZHOU Qi ( )2
1 College of Environmental and Material Engineering, Yantai University, Yantai 264025, China 2 State key Laboratory of Pollution Control and Resources Reuse, Tongji University, Shanghai 200092, China

Higher Education Press and Springer-Verlag 2007

Abstract Simultaneous nitrification and denitrification (SND), which is more economical compared with the traditional method for nitrogen removal, is studied in this paper. In order to find the suitable conditions of this process, a mixed flow activated sludge system under low oxygen concentration is investigated, and some key control parameters are examined for nitrogen removal from synthetic wastewater. The results show that SND is accessible when oxygen concentration is 0.30.8 mg/L. The nitrogen removal rate can be obtained up to 66.7% with solids retention time (SRT) of 45 d, C/N value of 10, and F/M ratio of 0.1 g COD/ (g MLSS d). Theoretical analysis indicates that SND is a physical phenomenon and governed by oxygen diffusion in flocs. Keywords low oxygen concentration, simultaneous nitrification and denitrification (SND), aerobic nitrification, microenvironment theory

found that some principal factors predominantly influence SND. These are carbon supply, oxygen concentrations, and floc size [9,11]. Pochana et al. [9,10] proposed that the addition of readily biodegradable COD source resulted in a significant increase of SND activity. The increased dissolved oxygen concentrations in the reactor bulk liquid negatively affected SND and SND activities, which were increased in reactors with larger activated sludge floc size. Currently in China, most studies on the mechanisms of SND are focused on nitrification and denitrification as separate independent phases, spatially conducted in different reactors like traditional A/A/O, and A/O process or temporally conducted in a sequencing batch reactor or oxidation ditch under aerobic and anaerobic conditions. However, authentic mechanisms of SND have not been proposed. Therefore, in this study, a complete mixing activated sludge system was used to further explore the SND process to understand its mechanisms sufficiently.

Introduction

2
2.1

Materials and methods


Experimental set-up and reactor operation

There are a number of dominant mechanisms for simultaneous nitrification and denitrification (SND) such as the microenvironment theory [1], heterotrophic nitrification [2,3], aerobic denitrification [4,5], and short-cut nitrificationdenitrification [6,7]. Based on the micro-environment theory, SND occurs in a process when oxygen diffusion is limited within the micro-flocs, thus the anoxic micro-zone inside the flocs for heterotrophic denitrification is created. Rittmann et al. [8] and Pochana et al. [9,10] discovered the phenomenon of SND in an oxidation ditch and in a sequencing batch reactor (SBR), respectively. They suggested that SND would occur according to the micro-environment theory. It was
Translated from Environmental Pollution and Control, 2004, 26(1): 1113 [: ] E-mail: zhouqi@mail.tongji.edu.cn

Figure 1 shows the experimental set-up of this study. As shown in the figure, the aeration tank is aerated with diffused air by pore aeration, and gas flow meter is used to control the airflow to maintain the dissolved oxygen (DO) concentration within 0.30.8 mg/L. The maximum working volume of the aeration tank is 8.5 L. The top of the reactor is open to air. Reactors were kept in a room with constant temperature of 2328C. Bicarbonate buffer was added to supplement the exhausted alkalinity and maintain pH of 7.58.0 in the reactors. 2.2 Wastewater characteristics The synthetic wastewater used in the experiment consisted of glucose, ammonium chloride, and monopotassium phosphate

50 were selected as the variable factors, and three levels (states) had been picked for each factor. The orthogonal design table L4(34) is shown in Table 1.
Table 1 Design of orthogonal method
Item SRT/d(1) 1 2 3 4 5 6 7 8 9 60 60 60 45 45 45 30 30 30 Factors C/N(2) 10 5 2 10 5 2 10 5 2 F/M(3) 0.30 0.10 0.05 0.10 0.05 0.30 0.05 0.30 0.10

Fig. 1 Schematic diagram of the experimental equipment

as the carbon, nitrogen, and phosphorous in the wastewater, respectively. Bicarbonate, calcium chloride, ferrous sulphate, magnesium sulphate, and manganese sulphate as trace elements were added. 2.3 Sludge acclimation

Results and discussion

The results of orthogonal method are shown in Table 2. 3.1 The nitrification process Based on the traditional theory, successful nitrification requires autotrophic nitrifying bacteria under strict aerobic conditions. Dissolved oxygen (DO) concentration is usually above 0.5 mg/L in the mixing activated sludge system [12]. However, as shown in Table 2, high ammonia nitrogen removal efficiency went up to 93% under experimental conditions of 2, 3, 4, 5, and 7 where DO concentration was maintained at 0.30.8 mg/L. Nitrification also occurred to a certain extent in other experimental conditions. Many studies have observed the phenomenon of heterotrophic nitrification. In this study, when F/M ratio was 0.30 g COD/(g MLSS d), the removal rate of ammonia nitrogen was 55.4%, 7.3%, and 48.1% under experimental conditions of 1, 6, and 8, respectively, which were lower in all experimental conditions. When F/M ratio was as low as 0.05 g COD/(g MLSS d), ammonia nitrogen removal rate was

The activated sludge was obtained from the secondary sedimentation tank of the Quyang Waste Water Treatment Plant in Shanghai, China. After aerating for one day without extra nutrients, a certain amount of activated sludge was added into the aeration tank to maintain the initial mixed liquor suspended solids (MLSS) concentration at about 3.5 g/L. After operating for 12 d, the sludges settling characteristics was good when the sludge volume index (SVI) in the aeration tank was 88. At the time, COD removal rate was 89%, and ammonia nitrogen removal rate was 82%, indicating the ending of the sludge acclimation period. 2.4 Operational conditions

Orthogonal design method was used in this study. Organic load (F/M ratio), C/N ratio, and solids retention time (SRT)
Table 2 Results of orthogonal method
Item HRT/h Influent /(mg L1) 1 2 3 4 5 6 7 8 9 8 12 16 24 42 3.2 12 8 9.6 301.3 311.7 120.1 317.4 319.5 118.2 334.6 320.7 126.7 COD Effluent /(mg L1) 40.2 30(22) 20.7 28.9 15.5 31.6 37.3 62.9 46.7(33.5) Removal Influent rate/% /(mg L1) 86.7 89.5(93) 82.8 90.3 96.4 73.3 88.9 80.4 63.1(73.6) 27.0 62.4 62.4 26.9 60.5 68.9 25.7 56.6 60.9 NH4+-N Effluent /(mg L1) 12.4 1.0 0.0 0.0 4.1 57.0 0.0 29.4 21.4

TN Removal rate/% 55.4 98.5 100.0 100.0 93.2 17.3 100.0 48.1 64.9 Influent /(mg L1) 31.5 66.8 62.3 29.8 63.0 69.4 31.5 60.1 62.7 Effluent /(mg L1) 14.1 32.1 60.2 10.1 24.8 58.7 14.0 32.5 38.7 Removal rate/% 55.1 43.0 8.3 66.7 60.0 14.7 54.4 45.4 37.8

NO2-N Effluent /(mg L1) 1.15 7.0 0.1 0.7 0.3 1.5 1.2 0.1 11.6

NO3-N Effluent /(mg L1) 0.55 24.1 60.1 9.4 20.4 0.2 12.8 3.0 5.7

Note: The data showed within parenthesis were COD and COD removal rate after deducted by NO2-N. The deduction was calculated according to 1 mg/L NO2-N consuming 1.14 mg oxygen

51 above 93%, and the effluent ammonia nitrogen was lower than 5 mg/L under experimental conditions of 2, 5, and 7 indicating that the heterotrophic nitrification did not occur in this experiment. According to the traditional theory, nitrifiers are autotrophic aerobes, and their growth may be inhibited in conditions with high F/M ratio. Nitrogen-containing substrates will be utilized by the dominant heterotrophic microbes for synthetic metabolism while a large number of DO is consumed after the synthetic metabolisms by the dominant heterotrophic microbes using the nitrogen, suppressing the nitrification process. However, autotrophic nitrification was observed under low oxygen concentrations in this study. Three assumptions are provided to explain this. Firstly, the smaller biomass floc was observed through microscopic analysis, compared to those in general complete mixing systems, which facilitate the transfer of DO at low concentration through the small size flocs easily, and enlargement of the aerobic micro-zone inside the flocs to supply enough oxygen for the nitrifiers. Secondly, SRT in this study was long (30 d, 45 d, and 60 d, respectively) enough to reduce the degradation rate of carbon containing organics by heterotrophic aerobe. Therefore, a certain amount of DO inside the flocs could be maintained, and consumed by the nitrification process. Additionally, stronger competition of nitrifiers under the condition of longer SRT contributes to higher nitrogen removal rate. Thirdly, under the five experimental conditions, the organic loadings were very low, only 0.050.10 g CODcr/ (g MLSS d). Figure 2 schematically presents the ratio of aerobic zone/anoxic zone in activated sludge flocs under the influence of F/M ratio and DO concentration [13]. As shown in Fig. 2, the flocs could maintain aerobic condition under low F/M ratio and low DO concentration. Although the DO concentration was 0.30.4 mg/L, below 1.0 mg/L, the small flocs are attributable to oxygen penetration. Another experiment was conducted to further confirm that the nitrification that occurred in this study was an aerobic reaction. Experimental conditions were the same as the experimental condition 2 except that DO concentrations were 0.00.1 mg/L. The results (see Table 3) show that the ammonia nitrogen removal rate was reduced from 98.5% to 74.7% with decreasing DO concentration. To maintain normal activity of nitrifying bacteria, DO concentration should be no less than 0.3 mg/L. 3.2 The denitrification process The total nitrogen (TN) removal rate, as shown in Table 2, was mainly between 40%50% and the maximum was 66.7%, confirming the occurrence of simultaneous nitrification and denitrification. Under the experimental conditions of 3, 6, and 8, the TN removal rate was lower because of the uncompleted nitrification process. Under other experimental conditions, the concentration of nitrate in the effluent was higher, ranging from 10 to 60 mg/L. The DO concentration should not be a limiting factor for denitrification. As shown in Table 3, the denitrification performance was not improved with the decrease of DO concentration. The available carbon may be the potential reason. Insufficient carbon can inhibit the heterotrophic denitrifiers, which need organic carbon as electron donor under low oxygen concentration. In this study, organic load was 0.050.1 g COD/(g MLSS d) under some conditions, and most of the organic carbon was utilized by other heterotrophic aerobes, therefore limiting the denitrification process. An experiment was performed to confirm the influence of organic carbon on the denitrification process. Taking the experimental condition 4 as an example, the effluent from the secondary settling tank with the addition of glucose was rotated for 12 h in a rotary bed, and after that, concentrations of nitrite and nitrate were analyzed. Results (see Table 4) showed that nitriate was removed completely with the addition of carbon source, and the denitrification process was performed well, indicating that the process could be influenced by available carbon. 3.3
Fig. 2 Effects of F/M and DO on aerobic/anoxic zone ratio in schematic activated sludge floc Table 3 Effect of DO on the nitrification process
DO/(mgL1) Influent /(mg L1) 0.5 0. 311.7 (22) 298.1 (38.6) COD Effluent /(mg L1) 30 (93) 43.2 (87.1) Removal rate % 89.5 85.5 Ammonia nitrogen Influent /(mg L1) 62.4 66.5 Effluent Removal Influent /(mg L1) rate % /(mg L1) 1.0 16.8 98.5 74.7 66.8 70.3 Total nitrogen Effluent /(mg L1) 32.1 41.7 Removal rate % 43 40.8 Influent NO2-N /(mg L1) 7.0 4.04 Influent NO3-N /(mg L1) 24.1 20.81

Nitrate and nitrite in the effluent

Experimental results (see Table 2) showed that the effluent nitrite concentration was higher in the experimental

Note: The data showed within parenthesis were COD and COD removal rate after deducted by NO2-N. The deduction was calculated according to 1 mg/L NO2-N consuming 1.14 mg oxygen

52
Table 4 Effect of available carbon on nitrogen removal rate
Item Carbon concentration/(mg L1) Before adding NO2-N NO3-N TN P 0.25 8.41 8.65 13.17 After adding 0.06 0.10 0.16 6.9 76 98.8 98.2 47.6 Removal rate/%

References
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conditions of 7 and 9 with 7.0 and 1.6 mg/L, respectively. According to Hyungseok Yoos study [7], some factors can inhibit the nitrobacter bacteria activity and result in nitrite accumulation during nitrification. The factors were reported to be free ammonia (FA) concentration, free hydroxylamine (FH) concentration, pH, temperature, DO, and lag-time when changing from anoxic to aerobic condition. In this study, it was not the temperature, DO, and FA but the pH that resulted in nitrite accumulation since solution pH was above 8.0 under the conditions of 7 and 9, where formation of nitrate was suppressed.

Conclusions

First, the results showed that SND really occurred when oxygen concentration was 0.30.8 mg/L. Nitrogen removal rate was up to 60% with SRT of 45 d, C/N of 10, and F/M ratio of 0.1 g COD/(g MLSS d), Second, the nitrification process that occurred in this study belonged to aerobic nitrification by heterotrophic nitrifying bacteria. Third, theoretical analysis indicated that SND is a physical phenomenon and governed by oxygen diffusion in flocs. Further studies are needed to obtain a complete understanding of the mechanisms.

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