Hydrogen-dependent denitrification of water in an anaerobic submerged membrane bioreactor coupled with a novel hydrogen delivery system

Hydrogen-dependent denitrification has gained significant attention due to its potential economic advantage over heterotrophic denitrification. However, effective hydrogen delivery and biomass retention under anaerobic conditions are significant challenges to implementation of this process. An innovative hydrogenotrophic denitrification system, that addresses these challenges, consisting of an anaerobic submerged membrane bioreactor (MBR) and a novel hydrogen delivery unit, was evaluated for removal of nitrate from a synthetic groundwater feed. The hydrogen delivery unit was designed to release hydrogen-supersaturated water to the reactor and was efficient in hydrogen delivery, providing complete mass transfer. The anaerobic submerged MBR was successful in both reducing nitrate from 25 mg NO(3)-Nl(-1) to below detection and separating biomass from treated water to produce effluent free of suspended solids. Nitrogen gas produced during denitrification was internally recycled to effectively achieve membrane scouring and reactor mixing. The total organic carbon was similar to that of the incoming feed water, averaging approximately 6 mgl(-1).     

Microbial population in a hydrogen-dependent denitrification reactor

The bacterial population in an H2-dependent denitrification system was studied. The laboratory set-up was designed for the treatment of potable water and consisted of an electrochemical cell, where the water to be treated was enriched with H2 prior to entering a bioreactor. Bioreactors (columns packed with granulated active carbon) were inoculated with denitrifying bacterial strains isolated from a previous reactor, then sampled immediately after inoculation, or after 1 or 3 months of continuous operation. Total number of the bacteria and numbers of each different strain were determined at various levels of the bioreactor. The strains present in the inoculum were identified as Ochrobactrum anthropi, Pseudomonas stutzeri, Paracoccus panthotrophus and Paracoccus denitrificans. Numbers of the latter declined markedly with time with the other three strains being responsible for nitrate removal. A correlation was found between the relative abundance of each strain and its specific denitrification activity.     

Applying a novel autohydrogenotrophic hollow-fiber membrane biofilm reactor for denitrification of drinking water

We conducted a series of pseudo-steady-state experiments on a novel hollow-fiber membrane biofilm reactor used for denitrification of oligotrophic waters, such as drinking water. We applied a range of nitrate loadings and hydrogen pressures to establish under what conditions the system could attain three goodness-of-performance criteria: partial nitrate removal, minimization of hydrogen wasting, and low nitrite accumulation. The hollow-fiber membrane biofilm reactor could meet drinking-water standards for nitrate and nitrite while minimizing the amount of hydrogen wasted in the effluent when it was operated under hydrogen-limited conditions. For example, the system could achieve partial nitrate removals between 39% and 92%, effluent nitrate between 0.4 and 9.1 mg N/l, effluent nitrite less than 1 mg N/l, and effluent hydrogen below 0.1 mg H2/l. High fluxes of nitrate and hydrogen made it possible to have a short liquid retention time (42 min), compared with 1-13 h in other studies with hydrogen used as the electron donor for denitrification. The fluxes and concentrations for hydrogen, nitrate, and nitrite obtained in this study can be used as practical guidelines for system design.     

Nitrate removal by a combination of elemental sulfur-based denitrification and membrane filtration

In this paper, a new method for removal of nitrate from groundwater, in which elemental sulfur-based denitrification (autotrophic denitrification) and membrane separation are combined, is proposed. By using a membrane, autotrophic denitrifiers, whose growth rate is considerably low, can be kept at a high concentration. The performance of the proposed process was examined through a long-term experiment in the laboratory using synthetic feed water. A rotating membrane disk module equipped with UF membrane (750,000 Da) was used in this study. Complete removal of nitrate (25 mg N/L) was achieved under the conditions of a biomass concentration of about 1000 mg protein/L and HRT of 160 min. Dissolved oxygen concentration and sulfur/biomass ratio in the membrane chamber were found to be the key factors in maintenance of high-process performance. Deterioration in membrane permeability was insignificant. It was found that membrane filtration could be continued with a water flux of 0.5 m3/m2/day for about 100 days without any chemical membrane cleaning. The proposed process, however, caused a slight increase in assimilable organic carbon. Sulfide was not detected in the denitrified water.     

A novel sulfate reduction, autotrophic denitrification, nitrification integrated (SANI) process for saline wastewater treatment

This paper reports on a lab-scale evaluation of a novel and integrated biological nitrogen removal process: the sulfate reduction, autotrophic denitrification and nitrification integrated (SANI) process that was recently proposed for saline sewage treatment. The process consisted of an up-flow anaerobic sludge bed (UASB) for sulfate reduction, an anoxic filter for autotrophic denitrification and an aerobic filter for nitrification. The experiments were conducted to evaluate the performance of the lab-scale SANI system with synthetic saline wastewater at various hydraulic retention times, nitrate concentrations, dissolved oxygen levels and recirculation ratios for over 500 days. The system successfully demonstrated 95% chemical oxygen demand (COD) and 74% nitrogen removal efficiency without excess sludge withdrawal throughout the 500 days of operation. The organic removal efficiency was dependent on the hydraulic retention time, up-flow velocity, and mixing conditions in the UASB. Maintaining a sufficient mixing condition in the UASB is important for achieving effective sulfate reduction. For a typical Hong Kong wastewater composition 80% of COD can be removed through sulfate reduction. A minimum sulfide sulfur to nitrate nitrogen ratio of 1.6 in the influent of the anoxic filter is necessary for achieving over 90% nitrate removal through autotrophic denitrifiers which forms the major contribution to the total nitrogen removal in the SANI system. Sulfur balance analyses confirmed that accumulation of elementary sulfur and loss of hydrogen sulfide in the system were negligible.     

Hydrogen-dependent denitrification in a two-reactor bio-electrochemical system

An autotrophic biological process was developed for the treatment of nitrate-contaminated drinking water. The system comprised of two steps: the water to be treated was first enriched with hydrogen (energy source) in the cathodic chamber of an electrochemical cell, and then denitrified in the bioreactor. The bioreactor was a packed bed of granulated activated carbon, and the water flow was directed in an upward continuous mode. The system was operated for one year, at various water velocities and current intensities. Denitrification rates up to 0.25 kg N m-3 d-1 were obtained at the hydraulic residence time of 1 h. The system was stable. When detected in the effluent, the concentration of nitrite was low, even under conditions that resulted in the elution of very high concentrations of nitrate.     

Steady-state model-based evaluation of sulfate reduction, autotrophic denitrification and nitrification integrated (SANI) process

Recently we developed a process for wastewater treatment in places where part of the fresh water usage is replaced by seawater usage. The treatment of this saline sewage consists of sulfate reduction, autotrophic denitrification and nitrification integrated (SANI) process. The process consists of an up-flow anaerobic sludge bed (UASB) for sulfate reduction, an anoxic filter for autotrophic denitrification using dissolved sulfide produced in the UASB and an aerobic filter for nitrification. The system was operated for 500 days with 97% COD removal and 74% total nitrogen removal without withdrawal of sludge. To verify these results and to understand this novel process, a steady-state model was developed from the COD, nitrogen and sulfur mass and charge balances based on the stoichiometries of the sulfate reduction, the autotrophic denitrification and the autotrophic nitrification. The model predictions agreed well with measured data on COD, nitrate and sulfate removal, sulfide production, effluent TSS, and mass balances of COD, sulfur and nitrogen in the three reactors. The model explains why withdrawal of sludge from the SANI system is not needed through comparisons of the predictions and measurements of effluent TSS and phosphorus concentrations.     

Simultaneous removal of nitrate and arsenic from drinking water sources utilizing a fixed-bed bioreactor system

A novel bioreactor system, consisting of two biologically active carbon (BAC) reactors in series, was developed for the simultaneous removal of nitrate and arsenic from a synthetic groundwater supplemented with acetic acid. A mixed biofilm microbial community that developed on the BAC was capable of utilizing dissolved oxygen, nitrate, arsenate, and sulfate as the electron acceptors. Nitrate was removed from a concentration of approximately 50 mg/L in the influent to below the detection limit of 0.2 mg/L. Biologically generated sulfides resulted in the precipitation of the iron sulfides mackinawite and greigite, which concomitantly removed arsenic from an influent concentration of approximately 200 ug/L to below 20 ug/L through arsenic sulfide precipitation and surface precipitation on iron sulfides. This study showed for the first time that arsenic and nitrate can be simultaneously removed from drinking water sources utilizing a bioreactor system.     

Denitrification and neutralization treatment by direct feeding of an acidic wastewater containing copper ion and high-strength nitrate to a bio-electrochemical reactor process.

The feasibility of the direct denitrification treatment of copper metal pickling wastewater by using a bio-electrochemical reactor process was investigated experimentally. Carbon electrodes were installed in the reactor as the anode and cathode and denitrifying microorganisms were fixed on the surface of the cathode. The reactor was continuously operated by applying an electric current and feeding acetate. In this reactor, copper ion removal and denitrification proceeded simultaneously and the pH value of the treated water was increased almost to neutral. The electric current that passed through the cathode contributed to the removal of the copper ion and the generation of hydrogen gas. The generated hydrogen gas as well as the added acetate was effectively utilized for denitrification. A theoretical evaluation of pH in the effluent suggested that the pH increase was mainly caused by the generation of hydroxyl ion during denitrification. In addition, the inorganic carbon species generated during denitrification with acetate and by the electrochemical oxidation of anodic carbon acted as a buffer to minimize a further increase of pH at higher nitrate removal efficiencies. These results demonstrated that copper ion removal, denitrification and neutralization could be achieved simultaneously by using a single bioelectrochemical reactor.     

Removal of ammonia from contaminated air in a biotrickling filter - denitrifying bioreactor combination system

The removal of gaseous ammonia in a system consisting of a biotrickling filter, a denitrification reactor and a polishing bioreactor for the trickling liquid was investigated. The system allowed sustained treatment of ammonia while preventing biological inhibition by accumulating nitrate and nitrite and avoiding generation of contaminated water. All bioreactors were packed with cattle bone composite ceramics, a porous support with a large interfacial area. Excellent removal of ammonia gas was obtained. The critical loading ranged from 60 to 120 gm(-3)h(-1) depending on the conditions, and loadings below 56 gm(-3)h(-1) resulted in essentially complete removal of ammonia. In addition, concentrations of ammonia, nitrite, nitrate and COD in the recycle liquid of the inlet and outlet of each reactor were measured to determine the fate of nitrogen in the reactor, close nitrogen balances and calculate nitrogen to COD ratios. Ammonia absorption and nitrification occurred in the biotrickling filter; nitrate and nitrite were biologically removed in the denitrification reactor and excess dissolved COD and ammonia were treated in the polishing bioreactor. Overall, ammonia gas was very successfully removed in the bioreactor system and steady state operation with respect to nitrogen species was achieved.     

Evaluation of an MBR-RO system to produce high quality reuse water: microbial control, DBP formation and nitrate

A membrane bioreactor and reverse osmosis (MBR-RO) system was developed to assess potential reuse applications of municipal wastewater. The objective of the study was to examine the water quality throughout the system with a focus on waterborne pathogens, disinfection by-products (DBPs) and nitrate. This paper will discuss the presence of these contaminants in MBR effluent and focus on their subsequent removal by RO. This study has shown that high quality reuse water can be produced from municipal wastewater through the use of an MBR-RO system. The water meets California Title 22 reuse regulations for non-potable applications and US EPA drinking water limits for trihalomethanes (THM) (80 microg/L), haloacetic acids (HAA) (60 microg/L), chlorite (1.0 mg/L), total coliform (not detectable), viruses (not detectable), and nitrate/nitrite (10 mg N/L). However, THM formation (182-689 microg/L) attributed to cleaning of the MBR with chlorine and incomplete removal by subsequent RO treatment resulted in reuse water with THM levels (40.2+/-19.9 microg/L) high enough to present a potential concern when considering drinking water applications. Nitrate levels of up to 3.6 mg N/L, which resulted from incomplete removal by the RO membrane, are also a potential concern. A denitrification step in the MBR should be considered in potable water applications.     

Combined bioelectrochemical and sulfur autotrophic denitrification for drinking water treatment

A combined bioelectrochemical and sulfur autotrophic denitrification process for drinking water treatment was put forward and investigated extensively in this paper. In this new process, the bioelectrochemical denitrification was carried out in the upper part of the reactor while sulfur denitrification in the lower part. The H+ produced in Sulfur Part could be consumed by hydrogen denitrification in Bioelectrochemical Part. Therefore, the limestone for pH adjustment in Sulfur Part was not necessary in this combined process, which avoided the problem of hardness increase. The sulfate accumulation in this combined reactor was less than that of the sulfur limestone autotrophic denitrification system. The effluent from two parts was kept neutral at optimum operation conditions. When the influent nitrate was 30 mg-N/L, the reactor could be operated efficiently at the hydraulic retention time ranged from 1.9 to 5h (corresponding minimum current was 16-3 mA), i.e. the effluent NO3(-)-N removal ranged from 90% to 100% without nitrite accumulation and the effluent sulfate concentration was lower than 170 mg/L. The maximum volume-loading rate of the reactor was 0.381 kg NO3(-)-N/(m3d). The biomass and scanning electron microscope micrographs of Sulfur Part were also analyzed.     

进水N/S值对同步脱硫反硝化特性的影响

研究了不同进水N/S值条件下,不同接种物的厌氧体系的同步脱硫反硝化特性。结果表明:在N/S为0.6或0.4的条件下,3个体系对硫化物的去除率均达到90%以上,其中以进水N/S为0.4时产生的悬浮态硫最多;硝态氮的去除特性与硫化物不同,3个体系对硝态氮的去除率均在进水N/S为1.0时达到100%,且此时N2的产量也最大。可见,尽管同步脱硫反硝化工艺具备同时脱氮及除硫的能力,但其进水N/S的控制值却不相同。对于脱硫而言,最佳的进水N/S为0.4;对于脱氮而言,最佳的进水N/S为1.0。此外,研究发现3个不同接种物的厌氧体系对硫化物及硝态氮的去除途径不同,进水N/S值的影响也有差异。对于接种了厌氧污泥的体系,存在自养反硝化和异养反硝化的竞争,改变进水N/S值可调节二者的竞争,高N/S值会抑制硫化物自养反硝化过程,降低对硫化物的去除率;对于接种脱氮硫杆菌的纯菌体系,多硫自催化反应会与硫化物自养反硝化反应竞争硫化物,降低对硝态氮的去除率,高N/S值会导致出水硝态氮浓度较高;对于添加脱氮硫杆菌的强化厌氧污泥体系,以硫化物自养反硝化过程为主,最佳的N/S为0.4。     

Nitrogen transformation in a denitrification layer irrigated with dairy factory effluent

Adoption of land-based effluent treatment systems can be constrained by the costs and availability of land. Sufficient land area is needed to ensure nitrate leaching from applied effluent is minimised. One approach to decrease required land area is to enhance N removal by denitrification. Layers of organic matter (100 mm thick) were installed below topsoil of a site irrigated with dairy factory effluent. These "denitrification" layers were tested to determine whether they could decrease nitrate leaching by increasing denitrification. Four plots (10x10 m2 each) were constructed with a denitrification layer installed at 300 mm below the surface, and N losses were measured in leachate using suction cups every 3 weeks for 19 months. N in leachate was compared with 4 control plots. Denitrifying enzyme activity, nitrate concentrations, and carbon availability were measured in samples collected from the denitrification layers. These measurements demonstrated that denitrification occurred in the layer; however, denitrification rates were not sufficiently high to significantly decrease nitrate leaching. Total N leaching was 296 kg N ha(-1) from control plots and 238 kg N ha(-1) from plots with denitrification layers; a total of 798 kg N ha(-1) was applied in effluent. More than 50% of the leached N to 40 cm was as organic N, presumably due to bypass flow. Other studies have demonstrated that thicker denitrification layers (more than 300 mm) can reduce nitrate leaching from small-scale septic tank drainage fields but this study suggests that it is probably not practical to use denitrification layers at larger scales.     

Evidence of anoxic methane oxidation coupled to denitrification

Denitrification using methane as sole electron donor under anoxic condition was investigated. Sludge produced by a denitrifying reactor using acetate as electron donor was put in contact with methane at partial pressures from 1.8 to 35.7kPa. Nitrate depletion and gaseous nitrogen production were measured. The denitrification rate was independent of the methane partial pressure when superior or equal to 8.8kPa. The nitrate depletion was asymptotic. A denitrification rate of 0.25g NO(3)(-)-Ng(-1) VSSd(-1) was observed at the onset of culturing, followed by a slower and lineal denitrification rate of 4.9x10(-3)g NO(3)(-)-Ng(-1) VSSd(-1). Abiotic nitrate removal or the availability of another carbon source were discarded from control experiments made in the absence of methane or using sterilized inoculum.     

Five years of nitrate removal, denitrification and carbon dynamics in a denitrification wall

Denitrification walls are a useful approach for removing nitrate from shallow groundwater, but little is known about the sustainability of nitrate removal, which is dependent on the continued supply of organic carbon to denitrifying bacteria. To address this question, we monitored nitrate removal, denitrification and carbon dynamics in a pilot-scale denitrification wall for 5 yr. The wall continuously removed more than 95% of the incoming nitrate in groundwater, which ranged from 5 to 15 mg N L(-1). We did not detect decreases in total carbon during the 5-yr study. Available carbon declined for the first 200 days after the wall was constructed but has since remained relatively constant. While microbial biomass has varied between 350 and 550 microg C g(-1) there was no downward trend, suggesting that carbon availability was not limiting the size of the microbial population. However, there was a large decrease in denitrifying population, as indicated by declines in denitrifying enzyme activity. Despite this decrease, denitrification rates have remained high enough to remove nitrate from groundwater and denitrification was limited by nitrate rather than by carbon. Our data demonstrates that there was sufficient available carbon in this denitrification wall to support denitrification and nitrate removal for at least 5 yr.     

Removal of mono-valent oxyanions from water in an ion exchange membrane bioreactor: influence of membrane permselectivity

The ion exchange membrane bioreactor (IEMB) proved to be an effective technology for the removal of nitrate and perchlorate from polluted drinking water when using a mono-anion permselective membrane such as Neosepta ACS. Aiming at reducing the cost of the system, this study evaluates the use of a lower-cost anion exchange membrane, which exhibits no preferential mono-anion permselective properties. With this purpose an Excellion I-200 membrane was tested, for the removal of anionic micropollutants, such as nitrate and perchlorate from drinking water supplies. The impact of the lower anion permselectivity of this membrane on the quality of the treated water was determined. It was demonstrated that differences between the membrane properties are responsible for the different permselectivities observed towards multi-valent and mono-valent anions. The use of Excellion I-200 resulted in a less selective removal of perchlorate and nitrate, allowing anions such as sulphate and phosphate species to be transported. When treating 3.1l/m(2)h of water contaminated with 100microg/l of perchlorate and 60mg/l of nitrate, lower removal degrees were obtained (85% of perchlorate and 88% of nitrate), compared with 96% of perchlorate and 99% of nitrate achieved with the Neosepta ACS membrane, operating under the same conditions. However, the Excellion I-200 membrane shows no target anion flux decline during a relatively long period of operation (1 month) and no secondary contamination of the treated water by the carbon source used. These characteristics are essential for a membrane to be successfully used in the IEMB system. Additionally, the selection of the membrane depends on the latter characteristics and on the water quality requirements.     

Simultaneous heterotrophic and sulfur-oxidizing autotrophic denitrification process for drinking water treatment: control of sulfate production

A long-term performance of a packed-bed bioreactor containing sulfur and limestone was evaluated for the denitrification of drinking water. Autotrophic denitrification rate was limited by the slow dissolution rate of sulfur and limestone. Dissolution of limestone for alkalinity supplementation increased hardness due to release of Ca²⁺. Sulfate production is the main disadvantage of the sulfur autotrophic denitrification process. The effluent sulfate concentration was reduced to values below drinking water guidelines by stimulating the simultaneous heterotrophic and autotrophic denitrification with methanol supplementation. Complete removal of 75 mg/L NO₃-N with effluent sulfate concentration of around 225 mg/L was achieved when methanol was supplemented at methanol/NO₃-N ratio of 1.67 (mg/mg), which was much lower than the theoretical value of 2.47 for heterotrophic denitrification. Batch studies showed that sulfur-based autotrophic NO₂-N reduction rate was around three times lower than the reduction rate of NO₃-N, which led to NO₂-N accumulation at high loadings.     

Nitrate removal from ground water

A new technique is described for nitrate removal from ground water. This technique is a combination of ion exchange and biological denitrification. Nitrate is removed by ion exchange. Regeneration of the resin in a closed circuit is achieved with a denitrification reactor. In contrast with traditional denitrification procedures there is no direct contact between ground water and denitrifying bacteria. Also brine production and regeneration salt requirements are minimal as compared with conventional regeneration of ion exchange resins. The basic design criteria and the first pilot plant results are presented. The pilot plant results show that the process is very attractive when compared with ion exchange and biological denitrification as separate techniques. Ground water with a relatively high sulfate concentration can be treated when a nitrate selective resin is used.     

人工湿地的反硝化能力研究

利用人工湿地的反硝化作用进行去除硝态氮的试验,其反硝化碳源主要为植物根系的分泌物及湿地内腐败的死亡植株.结果表明,人工湿地内有着适宜反硝化的反应环境,反硝化茵能够很好地利用湿地内产生的碳源进行反硝化作用来去除硝态氮,且不会出现亚硝态氮的大量积累.在进水(NO3-)-N浓度为20-50 mg/L、水力停留时间为24 h的条件下,夏季运行时,湿地系统对硝态氮的去除率为20%～30%;冬季运行时,对硝态氮的去除率在10%左右.提供充足的反硝化碳源是硝态氮去除率进一步提高的瓶颈.