Study of a combined sulfur autotrophic with proton-exchange membrane electrodialytic denitrification technology: sulfate control and pH balance

A novel combined system established for nitrate removal from aqueous solution consisted of two parts: sulfur autotrophic denitrification and bio-electrochemical denitrification based on proton-exchange membrane electrodialysis (PEMED). The system was operated at various hydraulic retention times (HRT) and current intensities. Its optimum operation condition was also determined. The combined process had pH adjustment thus generating less nitrite than PEMED process. The denitrification rate of sulfur autotrophic part was dependent on HRT, while shorter HRT could reduce the sulfate generated by the sulfur autotrophic process. The denitrification rate of PEMED process depended on the applied current. For 32 ± 1 mg-N/L nitrate in influent, the optimum operation parameters of combined process were: HRT 2 h; applied current 350 mA. The combined reactor could achieve 95.8% nitrate removal without nitrite accumulation, the pH of effluent kept neutral and the sulfate of effluent was 202.1 mg/L, lower than the drinking water standard in China.     

Columnar denitrification of water by immobilized Pseudomonas denitrificans cells

Summary Whole cells of Pseudomonas denitrificans, immobilized in alginate gel, were used for columnar denitrification of ground water. Ethanol was selected as a suitable carbon source and the C/N-ratio necessary for satisfactory nitrate reduction was established (1.6 mg ethanol-C/mg nitrate-N). The course of the reaction and the diffusional limitations were investigated during columnar denitrification. The mechanical integrity of the gel matrix, as judged from leakage of cells was studied. The release of cells into the effluent was effectively inhibited (<10² cells/ml) by the use of different filter devices. The operational characteristics were determined by studying a column operating for nearly four months. Theoretically, the alginate gel column should, from high nitrate drinking water (22 mg NO ₃ ^– -N/1), produce 3 1 of denitrified water/kg gel/h (wet wt.) during a period of two months. The regeneration of nitrate reduction activity by means of activation in nutrient media proved a useful tool for restoring initial activity, the gel column having shown no loss in activity at the end of the operation period.     

Hydrogenotrophic denitrification of synthetic aquaculture wastewater using membrane bioreactor

A hydrogenotrophic denitrification system was evaluated in removing nitrate from synthetic aquaculture wastewater for recirculation purposes. Two membrane bioreactor (MBR) systems, namely, aeration–denitrification system (ADS) and denitrification–aeration system (DAS) were studied with 50 mg/L of influent concentrations for both organic matter and nitrate nitrogen. The DAS achieved better removal efficiency of 91.4% total nitrogen (T-N) and denitrification rate of 363.7 mg/L.day at a HRT of 3 h compared to ADS. Further, there was no nitrite accumulation in the DAS effluent. The nitrite accumulation in ADS effluent was lesser when CO₂ was used as buffer rather than K₂HPO₄ and KH₂PO₄. Estimation of kinetic parameters of hydrogenotrophic bacteria indicated lesser sludge production compared to heterotrophic denitrification. In the DAS, membrane fouling was nonexistent in the aeration reactor that was used to produce the recirculating effluent. On the contrary, membrane fouling was observed in the denitrification reactor that supplied hydrogen to the mixed liquor. Thus, this study demonstrated DAS capability in maintaining the acceptable water quality appropriate for aquaculture, in which a closed recirculating system is typically used.     

以纸为碳源去除地下水硝酸盐的研究

研究了以纸为碳源和反应介质的生物反应器对水中硝酸盐的去除。结果表明,以纸为碳源的反应器启动快．反硝化反应受温度及水力停留时间影响大。25℃的反硝化速率是14℃的1．7倍。在室温25±1℃,进水硝酸盐氮浓度为45．2mg·L^-1、水力停留时间8．6h时,反应器对硝酸盐氮的去除率在99．6％以上,当水力停留时间为7．2h,氮去除率只有50％。反硝化反应受pH值和溶解氧的影响小,反应进行过程中,纸表面形成了生物膜,纸也被消耗了．采用反应器出水再经活性炭吸附的工艺流程处理高硝酸盐氮地下水,<33．9mg·L^-1的硝酸盐氮完全去除,没有出现NC2-N,最终出水水质DOC<11mg·L^-1。     

Nitrate removal from the effluent of a fertilizer industry using a bioreactor packed with immobilized cells of <Emphasis Type="Italic">Pseudomonas stutzeri</Emphasis>and<Emphasis Type="Italic">Comamonas testosteroni</Emphasis>

A bioreactor for the removal of nitrate nitrogen (NO₃-N) from industrial effluent is described which is comprised of a glass column (60 cm × 6 cm) packed with alginate beads containing denitrifying organisms Pseudomonas stutzeri and Comamonas testosteroni. The effluent containing high concentrations of nitrate (600–950 mg l^–1) from the fertilizer industry and fusel oil (methanol as a major component) as organic carbon were used in the process. The reactor is operated in the continuous mode by injecting the pretreated nitrate-containing effluent at the top of the column. The Hydraulic retention time (HRT) was adjusted by changing the flow rates. When nitrate-containing wastewater was treated with immobilized cells, the nitrate removal rate reached a maximum 1.66 ± 0.07 Kg NO₃-N m^–3d^–1 at an influent NO₃-N concentration of 850 mg NO_3M-N l^–1within 12 h. The denitrification activity of the immobilized cells was compared with that of the free cells.     

Biological denitrification by <Emphasis Type="Italic">Pseudomonas stutzeri</Emphasis> immobilized on microbial cellulose

This study demonstrated the feasibility of a biological denitrification process using immobilized Pseudomonas stutzeri. The microbial cellulose (MC) from Acetobacter xylinum was used as the support material for immobilization of the bacterium. Nitrate removal took place mainly in the anoxic system. The effects of various operating conditions such as the initial nitrate concentration, pH, and carbon source on biological denitrification were demonstrated experimentally. The system demonstrated a high capacity for reducing nitrate concentrations under optimum conditions. The denitrification rate increased up to a maximal value of 1.6 kg NO₃-N m⁻³ day⁻¹ with increasing nitrate loading rate. Because of its porosity and purity, MC may be considered as appropriate supports for adsorbed immobilized cells. The simplicity of immobilization and high efficiency in operation are the main advantages of such systems. To date, the immobilization of microorganisms onto MC has not been carried out. The results of this research shows that a pilot bioreactor containing P. stutzeri immobilized on MC exhibited efficient denitrification with a relatively low retention time.     

Membrane bioreactor for drinking water denitrification

The aim of this study is to evaluate the performance of a membrane bioreactor with cell recycle to be used for drinking water denitrification, when operated with a high nitrate load (up to 7.68?kgNO₃ ^?/m³?day) and low hydraulic retention time (down to 0.625?h). Nitrate and nitrite were always completely removed for all the operational conditions used. The effluent's nitrite concentration kept below 0.1?mg NO₂ ^?/l with exception of a short period, during the reactor start-up, when it accumulates. The performance of the membrane bioreactor was also evaluated using a groundwater containing 148?mg NO₃ ^?/l. Nitrate and nitrite concentration in the effluent were below the recommended values for drinking water when the reactor was controlled at pH 7.0. The membrane flux decreases during operation as a consequence of membrane fouling. The flux decrease was more severe during operation with synthetic medium than with contaminated groundwater due to the existence of molecular complexes in the synthetic broth. A backshock technique was used to reduce the surface fouling of the membrane. Combining this technique with the use of a reserve asymmetric structured membrane it was found that the membrane flux remains nearly unchanged.     

Autotrophic denitrification using hydrogen generated from metallic iron corrosion

Hydrogenotrophic denitrification was demonstrated using hydrogen generated from anoxic corrosion of metallic iron. For this purpose, a mixture of hydrogenated water and nitrate solution was used as reactor feed. A semi-batch reactor with nitrate loading of 2000 mg m⁻³ d⁻¹ and hydraulic retention time (HRT) of 50 days produced effluent with nitrate concentration of 0.27 mg N L⁻¹ (99% nitrate removal). A continuous flow reactor with nitrate loading of 28.9 mg m⁻³ d⁻¹ and HRT of 15.6 days produced effluent with nitrate concentration of ∼0.025 mg N L⁻¹ (95% nitrate removal). In both cases, the concentration of nitrate degradation by-products, viz., ammonia and nitrite, were below detection limits. The rate of denitrification in the reactors was controlled by hydrogen availability, and hence to operate such reactors at higher nitrate loading rates and/or lower HRT than reported in the present study, hydrogen concentration in the hydrogenated water must be significantly increased.     

Nitrate-dependent salicylate degradation by Pseudomonas butanovora under anaerobic conditions

Nitrate-dependent salicylate degradation by the denitrifying Pseudomonas butanovora was investigated and the molar ratio of the cometabolism under anaerobic circumstances was determined. The bacterium was able to utilize salicylate as an electron donor for the reduction of nitrate. Salicylate was eliminated via catechol, which is degraded by means of catechol 2,3-oxygenases (meta-cleavage), forming 2-hydroxymuconic semialdehyde. The molar ratios of NO(3)(-)-N:salicylate existing during the experiment accorded well with the assumed 1:1 molar ratio. The tolerances of the growth, the salicylate degradation and the denitrification of P. butanovora to various heavy metal ions were also studied. Although the strain was tolerant to Pb(2+) and Cu(2+) up to 1 mM in complete medium, salicylate utilization took place only up to a concentration of 0.1 mM for both heavy metal ions. Of the heavy metal ions investigated, Cd(2+) (at a concentration of 0.05 mM) displayed the highest inhibitory effect on salicylate degradation by P. butanovora.     

Treatment of hydroponic wastewater by denitrification filters using plant prunings as the organic carbon source

This study investigated the feasibility of using pre-treated plant liquors as organic carbon sources for the treatment of hydroponic wastewater containing high nitrate-N (>300 mg N/L). The waste plant material was pre-treated to extract organic carbon-rich liquors. When this plant liquor was used as an organic carbon source in denitrification filters at the organic carbon:nitrogen dose rate of 3C:N, nitrate removal efficiencies were >95% and final effluent nitrate concentrations were consistently <20mg N/L. However, at this dose rate, relatively high concentrations (>140 mg/L) of organic carbon (fBOD5) remained in the final effluents. Therefore, a 'compromise' organic carbon:nitrogen dose rate (2C:N) was trialled, at which nitrate removal efficiencies were maintained at >85%, final effluent nitrate concentrations were consistently below 45 mg N/L, and effluent fBOD5 concentrations were <25mg/L. This study has demonstrated that waste plant material is a suitable carbon source for the removal of nitrate from hydroponic wastewater in a denitrification filter.     

Autotrophic denitrification via a novel membrane-attached biofilm reactor

AIMS: A laboratory-scale autotrophic membrane-attached biofilm reactor was developed to remove nitrate from drinking water. METHODS AND RESULTS: Hydrogen and carbon dioxide flowed together into the lumem side of a gas-permeable silicone tube. The gases diffused through the membrane wall to feed Alcaligenes eutrophus that formed a biofilm on the surface of the silicone tube for autotrophic denitrification. Hydrogen provided the energy source, and carbon dioxide, besides serving as the carbon source, was employed to neutralize the alkalinity from denitrification. The optimal carbon dioxide concentration in the silicone tube was between 20% and 50%. CONCLUSION: This study has demonstrated that a gas-permeable silicone tube is a convenient and efficient method to feed A. eutrophus for autotrophic denitrification. Supplying a suitable amount of carbon dioxide together with hydrogen into the silicone tube solved the problem that alkalinity formation caused during denitrification. The pH of the bioreactor was maintained at about 7 to avoid nitrite accumulation, and then the nitrogen removal rate was increased. A high specific nitrogen removal rate (1.6-5.4 g Nm(2)d(-1-1) of surface area of silicone tube) was achieved. SIGNIFICANCE AND IMPACT OF THE STUDY: In addition to combining the advantages of the hydrogenotrophic denitrification process and a membrane feeding substrate bioreactor (MFSB), this bioreactor achieved a high nitrogen removal rate and is simple to operate. It therefore is highly promising in drinking-water treatment.     

Removal of highly elevated nitrate from drinking water by pH-heterogenized heterotrophic denitrification facilitated with ferrous sulfide-based autotrophic denitrification

The performance of acetic acid-supported pH-heterogenized heterotrophic denitrification (HD) facilitated with ferrous sulfide-based autotrophic denitrification (AD) was investigated in upflow activated carbon-packed column reactors for reliable removal of highly elevated nitrate (42 mg NO₃-N l⁻¹) in drinking water. The use of acetic acid as substrate provided sufficient internal carbon dioxide to completely eliminate the need of external pH adjustment for HD, but simultaneously created vertically heterogenized pH varying from 4.8 to 7.8 in the HD reactor. After 5-week acclimation, the HD reactor developed a moderate nitrate removal capacity with about one third of nitrate removal occurring in the acidic zone (pH 4.8–6.2). To increase the treatment reliability, acetic acid-supported HD was operated under 10% carbon limitation to remove >85% of nitrate, and ferrous sulfide-based AD was supplementally operated to remove residual nitrate and formed nitrite without excess of soluble organic carbon, nitrite or sulfate in the final effluent.     

Denitrification of high strength nitrate waste

The aim of the present work was to study the treatment of high strength nitrate waste (40000 ppm NO(3) i.e., 9032 ppm NO(3)-N) by acclimatizing sludge initially capable of degrading dilute streams (100-200 ppm NO(3)-N). Sludge from an effluent treatment plant of a fertilizer industry was acclimatized for 15 d each at 1694, 3388, 6774 and 9032 ppm NO(3)-N in a 4 L sequencing batch reactor. Complete denitrification of extremely concentrated nitrate waste (9032 ppm NO(3)-N) using acclimatized sludge was achieved in just 6 h. During the acclimatization period, increase in nitrite peak value from zero to 5907 ppm NO(2)-N was observed, as the concentration was increased from 1694 to 9032 ppm NO(3)-N. Kinetic analysis of the nitrate and nitrite profile could reasonably support microbiological explanations for nitrite build up and changes in sludge composition.     

Removal of ammonium via simultaneous nitrification-denitrification nitrite-shortcut in a single packed-bed batch reactor

A polyurethane packed-bed-biofilm sequential batch reactor was fed with synthetic substrate simulating the composition of UASB reactor effluents. Two distinct ammonia nitrogen concentrations (125 and 250 mg l(-1)) were supplied during two sequential long-term experiments of 160 days each (320 total). Cycles of 24h under intermittent aeration for periods of 1h were applied, and ethanol was added as a carbon source at the beginning of each anoxic period. Nitrite was the main oxidized nitrogen compound which accumulated only during the aerated phases of the batch cycle. A consistent decrease of nitrite concentration started always immediately after the interruption of oxygen supply and addition of the electron donor. Removal to below detection limits of all nitrogen soluble forms was always observed at the end of the 24h cycles for both initial concentrations. Polyurethane packed-bed matrices and ethanol amendments conferred high process stability. Microbial investigation by cloning suggested that nitrification was carried out by Nitrosomonas-like species whereas denitrification was mediated by unclassified species commonly observed in denitrifying environments. The packed-bed batch bioreactor favored the simultaneous colonization of distinct microbial groups within the immobilized microbial biomass. The biofilm was capable of actively oxidizing ammonium and denitrification at high ratios in intermittent intervals within 24h cycles.     

Simultaneous nitrification and denitrification using an autotrophic membrane-immobilized biofilm reactor

AIMS: To develop a laboratory-scale autotrophic membrane-immobilized biofilm reactor to remove nitrogen from drinking water. METHODS AND RESULTS: A polyvinyl alcohol (PVA) immobilized biofilm, attached to the surface of a silicone tube, was used as the basis of a bioreactor for simultaneous nitrification and denitrification of water. The bioreactor was aerated with air to supply oxygen for nitrification. Pure hydrogen was supplied to the silicone tube and diffused through the membrane wall to feed the biofilm for autotrophic denitrification. The bioreactor was effective for the simultaneous nitrification and denitrification of water after a short period of acclimation, while the biofilm exhibited good resistance to the inhibition of denitrification by dissolved oxygen; the denitrification rate decreased by only 8% as the dissolved oxygen increased from 2 mg l(-1) to saturation. CONCLUSIONS: By using PVA crosslinked with sodium nitrate to entrap nitrifying and denitrifying sludge on the surface of a silicone tube, a novel bioreactor for simultaneous nitrification and denitrification was developed. In addition to performing as an immobilizing agent to strengthen the biofilm, PVA protected the denitrifying microorganisms to reduce the inhibition by dissolved oxygen under aerobic condition. Therefore, nitrification and denitrification occurred simultaneously within the biofilm. Furthermore, the immobilization technique shortened the acclimation period of the bioreactor. SIGNIFICANCE AND IMPACT OF THE STUDY: The described space saving and simple to operate bioreactor for nitrogen removal performed autotrophic denitrification to solve the problem of residual carbon in heterotrophic denitrification, and thus is suitable for removing nitrogen from drinking water.     

Biological treatment of ammonium-rich wastewater by partial nitritation and subsequent anaerobic ammonium oxidation (anammox) in a pilot plant

In wastewater treatment plants with anaerobic sludge digestion, 15-20% of the nitrogen load is recirculated to the main stream with the return liquors from dewatering. Separate treatment of this ammonium-rich digester supernatant would significantly reduce the nitrogen load of the activated sludge system. Some years ago, a novel biological process was discovered in which ammonium is converted to nitrogen gas under anoxic conditions with nitrite as the electron acceptor (anaerobic ammonium oxidation, anammox). Compared to conventional nitrification and denitrification, the aeration and carbon-source demand is reduced by over 50 and 100%, respectively. The combination of partial nitritation to produce nitrite in a first step and subsequent anaerobic ammonium oxidation in a second reactor was successfully tested on a pilot scale (3.6 m(3)) for over half a year. This report focuses on the feasibility of nitrogen removal from digester effluents from two different wastewater treatment plants (WWTPs) with the combined partial nitritation/anammox process. Nitritation was performed in a continuously stirred tank reactor (V=2.0 m(3)) without sludge retention. Some 58% of the ammonium in the supernatant was converted to nitrite. At 30 degrees C the maximum dilution rate D(x) was 0.85 d(-1), resulting in nitrite production of 0.35 kg NO(2)-N m(-3)(reactor) d(-1). The nitrate production was marginal. The anaerobic ammonium oxidation was carried out in a sequencing batch reactor (SBR, V=1.6 m(3)) with a nitrogen elimination rate of 2.4 kg N m(-3)(reactor) d(-1) during the nitrite-containing periods of the SBR cycle. Over 90% of the inlet nitrogen load to the anammox reactor was removed and the sludge production was negligible. The nitritation efficiency of the first reactor limited the overall maximum rate of nitrogen elimination.     

Development of model simulation based on BioWin and dynamic analyses on advanced nitrate nitrogen removal in deep bed denitrification filter

A pilot-scale deep bed denitrification filter using quartz sand as the filter media was operated under filtration velocity of 5.23 m/h. Nitrate, nitrite, ammonia, and total nitrogen removal rates were relatively high at influent C/N ratios of 4:1 and 5:1. A model was developed using software to simulate the processes operating in the filter and improve the related parameters in the actual operations. The normalized sensitivity coefficient and the mean square sensitivity measure were used for the sensitivity analysis. Results showed that the stoichiometric parameters were the most sensitive, which were related to methylotrophs and biofilm. Measured data were consistent with the simulations. Moreover, the order of significance of factors affecting nitrate nitrogen removal was as follows: influent chemical oxygen demand, influent nitrate nitrogen, and hydraulic retention time. Last, the denitrification dynamic model was obtained at influent C/N ratio of 5:1.

     

The integration of methanogenesis with shortcut nitrification and denitrification in a combined UASB with MBR

A combined system consisting of an up-flow anaerobic sludge blanket (UASB) and an aerobic membrane bioreactor (MBR) was operated at 28-30 degrees C and pH 7.8-8.1 for the treatment of low-strength synthetic wastewater enriched with organic carbon and NH4Cl. The MBR slurry was recirculated into the UASB with a ratio of 50-800%. It was found that nitrite was able to accumulate steadily during the nitrification step in the MBR at a low TOC/NH4+-N ratio. The mixed liquid containing NOX(-)-N in the MBR was recirculated to the UASB, and denitrification rather than methanogenesis became the preferred pathway. Whereas, the less carbon requirement for denitrification via nitrite rather than nitrate allowed methanogenesis to proceed simultaneously in the same reactor. The combination of membrane filtration and partial nitrification in the MBR with simultaneous denitrification and methanogenesis in the UASB could stably reach 98% TOC removal and 48.1-82.8% TN removal with recirculation ratio increasing from 50% to 800%.     

Nitrate removal in a packed bed reactor using volatile fatty acids from anaerobic acidogenesis of food wastes

A packed bed reactor (PBR) was fed with nitrate containing synthetic wastewater or effluent from a sequencing batch reactor used for nitrification. The C source introduced into the PBR consisted of volatile fatty acids (VFAs) produced from anaerobic acidogenesis of food wastes. When nitrate loading rates ranged from 0.50 to 1.01 kg N/m³·d, the PBR exhibited 100∼98.8% NO₃ ⁻-N removal efficiencies and nitrite concentrations in the effluent ranged from 0 to 0.6 NO₂ ⁻-N mg/L. When the PBR was further investigated to determine nitrate removal activity along the bed height using a nitrate loading rate less than 1.01 kg N/m³·d, 100% nitrate removal efficiency was observed. Approximately 83.2% nitrate removal efficiency was observed in the lower 50% of the packed-bed height. When reactor performance at a C/N ratio of 4 and a C/N ratio of 5 was compared, the PBR showed better removal efficiency (96.5%) of nitrate and less nitrite concentration in the effluent at the C/N ratio of 5. VFAs were found to be a good alternative to methanol as a carbon source for denitrification of a municipal wastewater containing 40 mg-N/L.     

Removal of organic pollutants and of nitrate from wastewater from the dairy industry by denitrification

The aim of this work was to remove nitrate-N and organic pollutants from wastewater of the dairy industry by denitrification. An artificially prepared wastewater, containing 250 mg/l nitrate-N and 1.5 g/l whey powder, was completely denitrified with removal of 90%–93% of the chemical oxygen demand (COD) of the whey powder by suspended or immobilized mixed cultures and by a suspended or immobilized pure culture that was isolated from the mixed culture inoculum. For the above COD/nitrate-N ratio of 6:1, the results indicated that the organic compounds of the wastewater served as electron donors for complete denitrification and that there was no need to add an external carbon source. In batch denitrification assays the suspended or immobilized mixed cultures proved to be more active and reacted faster than the isolated pure cultures. In continuous denitrification processes with immobilized pure or mixed cultures, the alginate beads, used for immobilization, were not stable for more than 12 days of incubation. The mixed free cultures removed the nitrate-N and COD continuously with no change of their activity for at least 15 days at an optimum hydraulic retention time of 0.27 days with a loading rate of 900 mg nitrate-N l⁻¹ day⁻¹. Received: 13 October 1997 /  Received revision: 16 December 1997 / Accepted: 19 December 1997