DEAMOX--new biological nitrogen removal process based on anaerobic ammonia oxidation coupled to sulphide-driven conversion of nitrate into nitrite

This paper reports about the successful laboratory testing of a new nitrogen removal process called DEAMOX (DEnitrifying AMmonium OXidation) for treatment of typical strong nitrogenous wastewater such as baker's yeast effluent. The concept of this process combines the recently discovered anammox (anaerobic ammonium oxidation) reaction with autotrophic denitrifying conditions using sulphide as an electron donor for the production of nitrite from nitrate within an anaerobic biofilm. To generate sulphide and ammonia, a Upflow Anaerobic Sludge Bed (UASB) reactor was used as a pre-treatment step. The UASB effluent was split and partially fed to a nitrifying reactor (to generate nitrate) and the remaining part was directly fed to the DEAMOX reactor where this stream was mixed with the nitrified effluent. Stable process performance and volumetric nitrogen loading rates of the DEAMOX reactor well above 1000 mgN/l/d with total nitrogen removal efficiencies of around 90% were obtained after long-term (410 days) optimisation of the process. Important prerequisites for this performance are appropriate influent ratios of the key species fed to the DEAMOX reactor, namely influent N-NO(x)/N-NH(4) ratios >1.2 (stoichiometry of the anammox reaction) and influent S-H(2)S/N-NO(3) ratios >0.57 mgS/mgN (stoichiometry of the sulphide-driven denitrification of nitrate to nitrite). The paper further describes some characteristics of the DEAMOX sludge as well as the preliminary results of its microbiological characterisation.     

Electrochemical process combined with UV light irradiation for synergistic degradation of ammonia in chloride-containing solutions

An electrochemical process combined with ultraviolet light irradiation (UPE) using nonphotoactive dimensionally stable anodes (DSAs) like RuO₂/Ti and IrO₂/Ti in the presence of chlorides was investigated for ammonia degradation. In this process, the in situ electrogenerated active chlorine and in situ photogenerated chlorine radicals were responsible for the high efficiency of ammonia degradation. More than 97% of ammonia was converted to nitrogen and a significantly synergistic effect was confirmed. Compared with the single electrochemical (E) and photochemical (P) process, the degradation rates of ammonia and the average current efficiencies (ACEs) of the UPE process increased by 1.5 and 1.7 times using RuO₂/Ti and IrO₂/Ti electrodes, respectively. On the basis of the linear voltammograms, Electrochemical Impedance Spectra (EIS), UV-vis spectra, Electron Spin Resonance (ESR) analysis and a series of experiments designed, the synergistic mechanism was investigated. In addition, this unique process succeeded in transferring the reaction from the electrode surface to the bulk of the solution compared with the conventional photoelectrocatalytic (PEC) process. The loss of chloride decreased from 21.0% to 7.2% and the recycle of chloride was accelerated in the UPE process. Finally the effects of initial pH, current density and ammonia-nitrogen concentration were discussed. Results indicated that pH and ammonia concentration exerted little influences on the degradation rates and current density was the “rate-determining” factor.     

Electrochemical denitrificaton of simulated ground water

Electrochemical denitrification of ground water was studied with an objective to maximize nitrate transformation to nitrogen gas. Aluminum, graphite, iron and titanium were selected as electrode materials. While aluminum, iron and titanium electrodes showed 70-97% nitrate reduction, with graphite electrode the removal was only 8%. Nitrate was transformed to ammonia with iron and aluminum electrodes but with titanium electrodes nitrogen was apparently the major end product. Iron electrodes exhibited the maximum reducing condition (ORP=-463mV) and titanium showed the minimum (ORP=-206mV). Nitrate reduction with titanium electrodes was retarded in the presence of chloride ions possibly due to formation of hypochlorite ions. The first-order nitrate transformation rate constant with respect to time decreased with decrease in current density. However, when the rate constant was expressed with respect to charge passed (Coulomb/l) it was nearly same under different experimental conditions (current density and pH). The study indicates that the process might be suitable for denitrification of drinking water.     

Short-term harmful effects of ammonia nitrogen on activated sludge microfauna

The response of activated sludge microfauna in terms of abundance and diversity has been analysed to evaluate both the toxic effect of ammonia nitrogen and the acclimatisation capacity of these microorganisms to its toxicity. The harmful effect of ammonia nitrogen was studied by means of two toxicological tests. The ammonia concentrations tested were: 9, 20, 30 and 50mg NH4+-N/l in the first toxicological test and 30, 40, 50 and 80 mg NH4+-N/l in the second. The results suggest that ammonia nitrogen causes a clear but reversible toxic effect on microfauna abundance when its concentrations are around three times higher than that which the microfauna is used to. Chilodonella uncinata and Acineria uncinata were the ciliates least affected by the ammonia nitrogen toxicity. Furthermore, the majority of microfauna groups analysed (gymnamoebae and ciliates) showed capability for acclimatisation to ammonia nitrogen in terms of abundance.     

Study on a discrete-time dynamic control model to enhance nitrogen removal with fluctuation of influent in oxidation ditches

The aim of study was proposed a new control model feasible on-line implemented by Programmable Logic Controller (PLC) to enhance nitrogen removal against the fluctuation of influent in Carrousel oxidation ditch. The discrete-time control model was established by confirmation model of operational conditions based on a expert access, which was obtained by a simulation using Activated Sludge Model 2-D (ASM2-D) and Computation Fluid Dynamics (CFD), and discrete-time control model to switch between different operational stages. A full-scale example is provided to demonstrate the feasibility of the proposed operation and the procedure of the control design. The effluent quality was substantially improved, to the extent that it met the new wastewater discharge standards of NH₃-N < 5 mg/L and TN < 15 mg/L enacted in China throughout a one-day period with fluctuation of influent.     

Appropriate conditions or maximizing catalytic reduction efficiency of nitrate into nitrogen gas in groundwater

This study focused on the appropriate catalyst preparation and operating conditions for maximizing catalytic reduction efficiency of nitrate into nitrogen gas from groundwater. Batch experiments were conducted with prepared Pd and/or Cu catalysts with hydrogen gas supplied under specific operating conditions. It has been found that Pd-Cu combined catalysts prepared at a mass ratio of 4:1 can maximize the nitrate reduction into nitrogen gas. With an increase in the quantity of the catalysts, both nitrite intermediates and ammonia can be kept at a low level. It has also been found that the catalytic activity is mainly affected by the mass ratio of hydrogen gas to nitrate nitrogen, and hydrogen gas gauge pressure. Appropriate operating values of H(2)/NO(3)-N ratio, hydrogen gas gauge pressure, pH, and initial nitrate concentration have been determined to be 44.6g H(2)/g N, 0.15 atm, 5.2 (-), 100 mg x L(-1) for maximizing the catalytic reduction of nitrate from groundwater.     

Ammonia-oxidizing archaea involved in nitrogen removal

Ammonia oxidation is critical to global nitrogen cycling and is often thought to be driven only by ammonia-oxidizing bacteria. The recent finding of new ammonia-oxidizing organisms belonging to the archaeal domain challenges this perception. Two major microbial groups are now believed to be involved in ammonia oxidation: chemolithotrophic ammonia-oxidizing bacteria (AOB) and ammonia-oxidizing archaea (AOA). Candidatus “Nitrosopumilus maritimus”, the first isolated ammonia-oxidizing archaeon from a tropical marine aquarium tank, representative of the ubiquitous marine group 1 Crenarchaeota, contains putative genes for all three subunits (amoA, amoB, and amoC) of ammonia monooxygenase, the key enzyme responsible for ammonia oxidation. In this article, important concepts of the nitrogen cycle, ammonia oxidation processes, ammonia-oxidizing organisms, and their physiology are described. AOA are found to thrive in various habitats including hot/thermal springs, marine and fresh waters, soils, and wastewater treatment systems, where they may outnumber their counterpart, AOB. Various molecular tools have been applied to study AOB and AOA and determine their abundance and community structure changes from natural and engineered systems. The presence of AOA in activated sludge opens new opportunities for elucidating its role of ammonia removal in wastewater treatment plants and wetlands. Several significant questions related to AOA research have been raised to evoke reader involvement for broadening future studies.     

Enhanced ammonia nitrogen removal using consistent biological regeneration and ammonium exchange of zeolite in modified SBR process

The modified zeo-SBR is recommended for a new nitrogen removal process that has a special function of consistent ammonium exchange and bioregeneration of zeolite-floc. Three sets of sequencing batch reactors, control, zeo-SBR, and modified zeo-SBR were tested to assess nitrogen removal efficiency. The control reactor consisted of anoxic-fill, aeration-mixing, settling, and decanting/idle phases, meaning that nitrogen removal efficiency was dependent on the decanting volume in a cycle. The zeo-SBR reactor was operated in the same way as the control reactor, except for daily addition of powdered zeolite in the SBR reactor. The operating order sequences in the zeo-SBR were changed in the modified zeo-SBR. Anoxic-fill phase was followed by aeration-mixing phase in the zeo-SBR, while aeration-mixing phase was followed by anoxic-fill phase in the modified zeo-SBR to carry NH4(+)-N over to the next operational cycle and to reduce total nitrogen concentration in the effluent. In the modified zeo-SBR, nitrification and biological regeneration occurred during the initial aeration-mixing phase, while denitrification and ammonium adsorption occurred in the following anoxic-fill phase. The changed operational sequence in the modified zeo-SBR to adapt the ammonium adsorption and biological regeneration of the zeolite-floc could enhance nitrogen removal efficiency. As a result of the continuous operation, the nitrogen removal efficiencies of the control and zeo-SBR were in 68.5-70.9%, based on the 33% of decanting volume for a cycle. The zeo-SBR showed a consistent ammonium exchange and bio-regeneration in the anoxic-fill and aeration-mixing phases, respectively. Meanwhile, the effluent total nitrogen of the modified zeo-SBR showed 50-60 mg N/L through ammonium adsorption of the zeolite-floc when the influent ammonium concentration was 315 mg N/L, indicating the T-N removal efficiency was enhanced over 10% in the same HRT and SRT conditions as those of control and zeo-SBR reactors. The ammonium adsorption capacity was found to be 6-7 mg NH4(+)-N/g FSS that is equivalent to 40 mg NH4(+)-N/L of ammonium nitrogen removal.     

Electrochemical oxidation of organics in water: Role of operative parameters in the absence and in the presence of NaCl

The electrochemical oxidation of organics in water was investigated theoretically and experimentally to determine the role of several operative parameters on the performances of the process in the presence and in the absence of sodium chloride. Theoretical considerations were used to design the experimental investigation and were confirmed by the results of the electrochemical oxidation of oxalic acid (OA) at boron doped diamond (BDD) or IrO₂-Ta₂O₅ (DSA-O₂) anodes in a continuous batch recirculation reaction system equipped with a parallel plate undivided electrochemical cell. Polarization curves and chronoamperometric measurements indicated that, in the presence of chlorides, the anodic oxidation of OA is partially replaced by an indirect oxidation process. This result was confirmed by electrolyses experiments that show that, in the presence of suitable amount of chlorides, oxidation of OA takes place mainly by a homogeneous process. Interestingly, a very different influence of the nature of the anodic material, the flow rate and the current density on the performances of the process arises in the absence and in the presence of chlorides so that optimization of the two processes requires very different operative conditions. In the absence of chlorides, high current efficiency (CE) is obtained at BDD when most part of the process is under charge transfer controlled kinetics, i.e. when low current densities and high flow rates are imposed. On the other hand, in the presence of NaCl, higher CE are generally obtained at DSA anode when high current densities and low flow rates are imposed, i.e. when a high concentration of chemical oxidants is obtained as a result of the chloride oxidation. The effect of other operative parameters such as the OA concentration and the pH were further investigated.     

Fire smoke toxicity: The effect of nitrogen oxides

Measurements of the toxic potency of fire effluents are required for fire-safety engineering and fire-hazard assessments. Toxic potency values may be generated using chemical analysis data and/or by animal protocols. The current ISO methods of calculating toxic potency values from chemical analysis data assume that the nitrogen oxides present in inhaled fire effluents are nitrogen dioxide, a highly irritant acid gas. Observations from real scale fire tests and bench scale tests which simulate the different fire stages show that, in some situations and particularly in proximity of the fire, the nitrogen oxides will be predominately nitric oxide but this can gradually change to nitrogen dioxide as the effluent moves away from the fire. Nitric oxide has a very different toxic potency and effect when compared to nitrogen dioxide. This paper considers the formation of nitric oxide and nitrogen dioxide in fire effluents, their potential toxic effects and the consequential need to reconsider the methods of calculating toxic potency values.     

Inhibition of biohydrogen production by ammonia

Ammonia inhibition of biohydrogen production was investigated in batch and continuous flow reactors with glucose as a substrate. In batch tests, biohydrogen production rate was highly dependent on pH and ammonia (defined as the sum of NH3 of NH4+ species) concentrations above 2 g N/L. At pH = 6.2, the maximum production decreased from 56 mL/h at 2 g N/L to 16 mL/h at 10 g N/L. At pH = 5.2, production decreased from 49 mL/h (2g N/L) to 7 mL/h (16 g N/L). Hydrogen yield remained relatively constant in batch tests, varying from 0.96 to 1.17 mol-H2/mol-glucose. In continuous flow tests, both hydrogen production rates and yields were adversely affected by ammonia. When the reactor (2.0 L) was first acclimated under batch conditions to a low nitrogen concentration (<0.8 g N/L), H2 production and yields under continuous flow mode conditions were 170 mL/h and 1.9 mol-H2/mol-glucose, but decreased with increased ammonia concentrations up to 7.8 g N/L to 105 mL/h and 1.1 mol-H2/mol-glucose. There was no hydrogen production under continuous flow conditions if the reactor was initially operated under batch flow conditions at ammonia concentrations above 0.8 g N/L. It is concluded that the hydrogen production is possible at high concentrations (up to 7.8 g N/L) of ammonia in continuous flow systems as long as the reactor is initially acclimated to a lower ammonia concentration (<0.8 g N/L).     

Electrochemical oxidation of olive oil mill wastewaters

The electrochemical oxidation of olive oil mill wastewaters over a titanium-tantalum-platinum-iridium anode was investigated. Batch experiments were conducted in a flow-through electrolytic cell with internal recycle at voltage of 5, 7 and 9 V, NaCl concentrations of 1%, 2% and 4%, recirculation rates of 0.4 and 0.62 L/s and initial chemical oxygen demand (COD) concentrations of 1475, 3060, 5180 and 6545 mg/L. The conversion of total phenols and COD as well as the extent of decolorization generally increased with increasing voltage, salinity and recirculation rate and decreasing initial concentration. In most cases, nearly complete degradation of phenols and decolorization were achieved at short treatment times up to 60 min; this was accompanied by a relatively low COD removal that never exceeded 40% even after prolonged (up to 240 min) times. The consumption of energy per unit mass of COD removed after 120 min of treatment was found to be a strong function of the operating conditions and was generally low at high initial concentrations and/or reduced salinity. The acute toxicity to marine bacteria Vibrio fischeri decreased slightly during the early stages of the reaction and this was attributed to the removal of phenols. However, as the reaction proceeded toxicity increased due to the formation of organochlorinated by-products as confirmed by GC/MS analysis. The toxicity to Daphnia magna increased sharply at short treatment times and remained quite high even after prolonged oxidation.     

沸石处理高氨氮景观水吸附特性实验研究

以景观水体为实验对象,阐述了沸石去除氨氮的吸附特性,实验结果表明:使用沸石处理高氨氮景观水,氨氮去除率超过90%;等温吸附试验研究结果显示所选用的沸石去除氨氮符合经典等温吸附模型朗格缪尔(Langmuir)等温模型,吸附极限值为4.642 3 mg/g;在25℃时,沸石对氨氮的去除率为93.4%。     

Modeling of ammonia speciation in anaerobic digesters

Anaerobic digestion of high-nitrogen wastes such as animal manure can be inhibited by high concentrations of un-ionized ammonia, NH₃ (aq). Understanding the toxicity of NH₃ (aq) to anaerobic digestion requires a method for determining its concentration. Previous work on ammonia toxicity in anaerobic digesters has utilized a simple equilibrium calculation for estimating NH₃ (aq) concentration from total ammonia, temperature, and pH. This approach is not appropriate for concentrated solutions. In this work, a speciation model for major solutes in anaerobic digesters, based on Pitzer's ion-interaction approach, is presented. Model simulations show that the simple equilibrium calculation (without corrections for non-ideal behavior) substantially overestimates NH₃ (aq) concentration for all but dilute digesters. This error in concentration determination increases with total solids content and is estimated to be greater than 40% for a digester fed dairy manure with 5% total solids or swine manure with 3% total solids. However, including an estimate of the activity coefficient for NH₄⁺ in the simple equilibrium calculation results in much more accurate estimates of NH₃ (aq) concentration. In this case, the estimated error is less than 10% in the absence of struvite precipitation at the highest total solids contents considered.     

Removal of low-concentration ammonia in water by ion-exchange using Na-mordenite

Removal of low-concentration ammonia (2-10ppm) in water by ion exchange with Na-form zeolites was investigated using a flow system at 278-333K. Results indicated that Na-mordenite was the most efficient cation-exchanger (compared with Na-ferrierite, Na-ZSM-5, Na-beta, and Na-Y, as well as the K- and H-form mordenite) for the removal of low-concentration ammonia. The ammonia uptake and the ion-exchange level achieved using mordenite with NH(4)(+) for removal of 10ppm ammonia at 333K were 1.21mmolg(-1) and 79.1%, respectively. The high efficiency of Na-mordenite for removal of low-concentration ammonia in water is due to the strong acidity of the corresponding H-form mordenite as demonstrated by ammonia temperature-programmed desorption. Ammonia uptake on the Na-mordenite was minimally influenced by operating temperature in the range of 278-333K. The coexistent K(+) and Na(+) in water had little influence on ammonia uptake of the Na-mordenite. In contrast, coexistent Ca(2+) and Mg(2+) significantly lowered the efficiency of the Na-mordenite for ammonia removal.     

Lethal and sublethal toxicity of ammonia to native, invasive, and parasitised freshwater amphipods

In lethal and sublethal ammonia toxicity tests, we examined differences in tolerance of three species of freshwater amphipods, one native and two invasive in Ireland. The native Gammarus duebeni celticus was slightly less tolerant to ammonia than the invasive G. pulex (96 h LC50= 1.155 and 1.544 mg l(-1), respectively), while another invader, Crangonyx pseudogracilis, had the lowest tolerance (LC50= 0.36 mg l(-1)). Parasitism of G. pulex by the acanthocephalan Echinorhynchus truttae greatly reduced the tolerance of the invader to ammonia (LC50= 0.381 mg l(-1)). Further, precopula pair disruption tests indicated that G. d. celticus was more sensitive to ammonia than G. pulex at sublethal levels. We discuss these results in the context of the ecological replacements of native by invader amphipods.     

Influence of relative humidity and gaseous ammonia on the nicotine sorption to indoor materials

Sorption of nitrogen-containing organic constituents of environmental tobacco smoke may be influenced by ammonia, a common indoor gas, and relative humidity (RH). We quantified sorption kinetics and equilibria of nicotine with stainless steel, cotton-polyester curtain, and polypropylene carpet at 0%, 50%, and 90% RH and in the presence of ammonia using a 10-l stainless steel chamber. Nicotine was introduced into the chamber by flash evaporating 50 μl of pure liquid. Kinetic sorption parameters were determined by fitting a mass balance model to experimental results using a nonlinear regression. Results show that an equilibrium partition coefficient, k(e) , of nicotine tended to increase as the RH increased for the curtain and carpet. Adsorbed water may contribute to an increase in available sites for nicotine sorption on the surface. In the presence of 20- and 40-ppm NH(3) , the values of k(e) for carpet were decreased by 14-40% at 50% and 90% RH, but the effect of NH(3) was not observed at 0% RH. The values of k(e) ranged from 54 to 152 m. Our findings indicate the relative importance of nicotine sorption to surfaces is dependent on the relative humidity and the presence of ammonia. PRACTICAL IMPLICATIONS: This research demonstrates that relative humidity and gaseous ammonia can influence nicotine sorption to common indoor surfaces, i.e., curtains and carpets. Increasing the relative humidity from dry to modest appears to enhance the sorptive capacity. Presence of the typical range of gaseous ammonia concentrations can reduce the nicotine sorption in a humid environment but does not affect the sorptive capacity in the absence of added water. Thus, studies on the dynamic sorption of other alkaloids or amine constituents of environmental tobacco smoke to indoor surfaces should consider the impact of water vapor concentration because of the interaction of water with the surface and sorbates. Furthermore, the mixture of gaseous amines may participate in adsorption site competition.     

Electrochemical mineralization of anaerobically digested olive mill wastewater

A novel approach was developed for the energetic valorisation and treatment of olive mill wastewater (OMW), combining anaerobic digestion and electrochemical oxidation. The electrochemical treatment was proposed as the final step to mineralize the remaining OMW fraction from the anaerobic reactor. The electrooxidation of anaerobically digested OMW was investigated over dimensionally stable anodes (DSAs). RuO₂ based anode was significantly more efficient than IrO₂-type DSA, mainly for the COD removal. IrO₂ based anode promoted a selective oxidation of phenols and colour removal. For instance, after an electrolysis charge of 10.4 × 10⁴ C L⁻¹, COD removals of 14 and 99%, phenols removals of 91 and 100% and colour removals of 85 and 100% were obtained for IrO₂ and RuO₂ DSAs-type, respectively. The electrochemical post-treatment was effectively performed without using a supporting electrolyte and in the presence of the solids that remained from the anaerobic process. The achievement of the required effluent quality for sewer systems disposal depends on the operating conditions of the anaerobic process. Consequently, special care must be taken with the chloride and nitrogen levels that may surpass the legal discharge limits. The electrochemical oxidation over RuO₂ based DSA is an appropriate second-step treatment for OMW disposal, after the recovery of its energetic potential.