Bio-reduction of soluble chromate using a hydrogen-based membrane biofilm reactor

Hexavalent chromium (Cr(VI)) is a mutagen and carcinogen that is a significant concern in water and wastewater. A simple and non-hazardous means to remove Cr(VI) is bioreduction to Cr(III), which should precipitate as Cr(OH)3(s). Since Cr(VI)-reducing bacteria can use hydrogen (H2) as an electron donor, we tested the potential of the H2-based membrane biofilm reactor (MBfR) for chromate reduction and removal from water and wastewater. When Cr(VI) was added to a denitrifying MBfR, Cr(VI) reduction was immediate and increased over 11 days. Short-term experiments investigated the effects of Cr(VI) loading, H2 pressure, and nitrate loading on Cr(VI) reduction. Increasing the H2 pressure improved Cr(VI) reduction. Cr(VI) reduction also was sensitive to pH, with an optimum near 7.0, a sharp drop off below 7.0, and a gradual decline to 8.2. Cr(III) precipitated after a small upward adjustment of the pH. These experiments confirm that a denitrifying, H2-based MBfR can be used to reduce Cr(VI) to Cr(III) and remove Cr from water. The research shows that critical operational parameters include the H2 concentration, nitrate concentration, and pH.     

Kinetics of nitrate and perchlorate reduction in ion-exchange brine using the membrane biofilm reactor (MBfR)

Several sources of bacterial inocula were tested for their ability to reduce nitrate and perchlorate in synthetic ion-exchange spent brine (30-45 g/L) using a hydrogen-based membrane biofilm reactor (MBfR). Nitrate and perchlorate removal fluxes reached as high as 5.4 g N m⁻² d⁻¹ and 5.0 g ClO₄ m⁻² d⁻¹, respectively, and these values are similar to values obtained with freshwater MBfRs. Nitrate and perchlorate removal fluxes decreased with increasing salinity. The nitrate fluxes were roughly first order in H₂ pressure, but roughly zero-order with nitrate concentration. Perchlorate reduction rates were higher with lower nitrate loadings, compared to high nitrate loadings; this is a sign of competition for H₂. Nitrate and perchlorate reduction rates depended strongly on the inoculum. An inoculum that was well acclimated (years) to nitrate and perchlorate gave markedly faster removal kinetics than cultures that were acclimated for only a few months. These results underscore that the most successful MBfR bioreduction of nitrate and perchlorate in ion-exchange brine demands a well-acclimated inoculum and sufficient hydrogen availability.     

Fluidized bed reactor for the biological treatment of ion-exchange brine containing perchlorate and nitrate

The removal of perchlorate and nitrate from contaminated drinking water using regenerable ion-exchange processes produces a high salt brine (3-10% NaCl) laden with high concentrations of perchlorate and nitrate. This bench-scale research describes the operation of acetate-fed granular activated carbon (GAC) based fluidized bed reactors (FBR) for perchlorate-only, and combined nitrate and perchlorate removal from synthetic brine (6% NaCl). The GAC was inoculated with a salt-tolerant culture developed by the authors and used previously in batch systems. An FBR was an effective design for perchlorate reduction and exhibited first-order degradation kinetics with respect to perchlorate concentrations. Nitrate was also removed by the organisms in the column and had no negative effects on the removal of perchlorate using the FBR design. However, at higher concentrations of nitrate the FBR was more difficult to operate due to loss of carbon and biomass from the formation of nitrogen bubbles and the high recycle flow rates needed.     

Simultaneous removal of perchlorate and nitrate from drinking water using the ion exchange membrane bioreactor concept

This work evaluates the feasibility of the ion exchange membrane bioreactor (IEMB) concept for the simultaneous removal of perchlorate and nitrate from drinking water, when nitrate is present in the ppm range and perchlorate in the ppb range. The IEMB concept combines Donnan dialysis and simultaneous biological degradation of both pollutants. Membrane transport studies showed that Donnan dialysis is suitable for obtaining water with concentrations of perchlorate and nitrate below the recommended levels. However, the pollutants were accumulated in a receiving stream, thus requiring additional treatment before disposal. On the other hand, the IEMB process operated with hydraulic retention times ranging from 1.4 to 8.3h in the water compartment, proved to remove effectively perchlorate and nitrate while preserving the water composition with respect to other ions, thus avoiding secondary contamination of the treated water. For a polluted water stream containing 100 ppb of ClO(4)(-) and 60 ppm of NO(3)(-), the concentrations of both ions in the treated stream were kept below the recommended levels of 4 ppb for ClO(4)(-) and 25 ppm for NO(3)(-). The IEMB system was operated under ethanol limitation, but even under these conditions, an increase of the perchlorate and nitrate concentrations in the treated water was not observed for up to 6 days.     

Achieving biofilm control in a membrane biofilm reactor removing total nitrogen

Membrane biofilm reactors (MBfR) utilize membrane fibers for bubble-less transfer of gas by diffusion and provide a surface for biofilm development. Nitrification and subsequent autotrophic denitrification were carried out in MBfR with pure oxygen and hydrogen supply, respectively, in order to remove nitrogen without the use of heterotrophic bacteria. Excessive biomass accumulation is typically the major cause of system failure of MBfR. No biomass accumulation was detected in the nitrification reactor as low-level discharge of solids from the system balanced out biomass generation. The average specific nitrification rate during 250 days of operation was 1.88 g N/m² d. The subsequent denitrification reactor, however, experienced decline of performance due to excessive biofilm growth, which prompted the implementation of periodic nitrogen sparging for biofilm control. The average specific denitrification rate increased from 1.50 g N/m² d to 1.92 g N/m² d with nitrogen sparging, over 190 days thus demonstrating the feasibility of stable long-term operation. Effluent suspended solids increased immediately following sparging: from an average of 2.5 mg/L to 12.7 mg/L. This periodic solids loss was found unavoidable, considering the theoretical biomass generation rates at the loadings used. A solids mass balance between the accumulating and scoured biomass was established based on the analysis of the effluent volatile solids data. Biofilm thickness was maintained at an average of 270 μm by the gas sparging biofilm control. It was concluded that biomass accumulation and scouring can be balanced in autotrophic denitrification and that long-term stable operation can be maintained.     

Effect of backwashing on perchlorate removal in fixed bed biofilm reactors

The influence of backwashing on biological perchlorate reduction was evaluated in two laboratory scale fixed bed biofilm reactors using 1- or 3-mm glass beads as support media. Influent perchlorate concentrations were 50 microg/L and acetate was added as the electron donor at a concentration of 2 mg C/L. Perchlorate removal was evaluated at various influent dissolved oxygen (DO) concentrations. Complete perchlorate removal was achieved with an influent DO concentration of 1mg/L resulting in bulk phase DO concentrations below the detection limit of 0.01 mg/L. The influence of increasing influent DO concentrations for 12 h periods was evaluated before and after individual backwash events. Partial perchlorate removal was achieved with an influent DO concentration of 3.5 mg/L before a strong backwash (bulk phase DO concentrations of approximately 0.2mg/L), while no perchlorate removal was observed after the strong backwash at the same influent DO level (bulk phase DO concentrations of approximately 0.8 mg/L). The immediate effect of backwashing depended on influent DO concentrations. With influent DO concentrations of 1 mg/L, strong backwashing resulted in a brief (<12 h) increase of effluent perchlorate concentrations up to 20 microg/L; more pronounced effects were observed with influent DO concentrations of 3mg/L. Daily weak backwashing had a small and, over time, decreasing negative influence on perchlorate reduction, while daily strong backwashing ultimately resulted in the breakdown of perchlorate removal with influent DO concentrations of 3 mg/L.     

Multidimensional modeling of biofilm development and fluid dynamics in a hydrogen-based,membrane biofilm reactor (MBfR)

A two-dimensional, particle-based biofilm model coupled with mass transport and computational fluid dynamics was developed to simulate autotrophic denitrification in a spiral-wound membrane biofilm reactor (MBfR), where hydrogen is supplied via hollow-fiber membrane fabric. The spiral-wound configuration consists of alternating layers of plastic spacer net and membrane fabric that create rows of flow channels, with the top and bottom walls comprised of membranes. The transversal filaments of the spacer partially obstruct the channel flow, producing complex mixing and shear patterns that require multidimensional representation. This study investigated the effect of hydrogen and nitrate concentrations, as well as spacer configuration, on biofilm development and denitrification fluxes. The model results indicate that the cavity spacer filaments, which rest on the bottom membranes, cause uneven biofilm growth. Most biofilm resided on the bottom membranes, only in the wake of the filaments where low shear zones formed. In this way, filament configuration may help achieve a desired biofilm thickness. For the conditions tested in this study, the highest nitrate fluxes were attained by minimizing the filament diameter and maximizing the filament spacing. This lowered the shear stress at the top membranes, allowing for more biofilm growth. For the scenarios studied, biomass limitation at the top membranes hindered performance more significantly than diffusion limitation in the thick biofilms at the bottom membranes. The results also highlighted the importance of two-dimensional modeling to capture uneven biofilm growth on a substratum with geometrical complexity.     

Simultaneous removal of organic matter and nitrogen compounds by an aerobic/anoxic membrane biofilm reactor

The hydrogen-based membrane biofilm reactor (MBfR) has been well studied and applied for denitrification of nitrate-containing water and wastewater. Adding an oxygen-based MBfR allows total-nitrogen removal when the input nitrogen is ammonium. However, most wastewaters also contain a significant concentration or organic material, measured as chemical oxygen demand (COD). This study describes experiments to investigate the removal of organic and nitrogenous compounds in the combined Aerobic/Anoxic MBfR, in which an Aerobic MBfR (Aer MBfR) precedes an Anoxic MBfR (An MBfR). The experiments demonstrate that the Aer/An MBfR combination accomplished COD oxidation and nitrogen removal for a total oxygen demand flux (i.e., from COD and NH(4) oxidations) in the range of 1.2-7.2gO(2)/m(2)-d for 4.5psi (0.3atm) oxygen pressure to the Aer MBfR, but was overloaded and did not accomplish nitrification for the total oxygen demand load higher than 14gO(2)/m(2)-d. Total-nitrogen removal was controlled by nitrification in the Aer MBfR, because the An MBfR denitrified all NO(3)(-) provided to it by the Aer MBfR. The overload of total oxygen demand did not affect COD oxidation in the Aer MBfR, but caused a small increase of COD in the An MBfR due to net release of soluble microbial products (SMP).     

Kinetics of nitrate and perchlorate removal and biofilm stratification in an ion exchange membrane bioreactor

The biological degradation of nitrate and perchlorate was investigated in an ion exchange membrane bioreactor (IEMB) using a mixed anoxic microbial culture and ethanol as the carbon source. In this process, a membrane-supported biofilm reduces nitrate and perchlorate delivered through an anion exchange membrane from a polluted water stream, containing 60 mg/L of NO₃⁻ and 100 μg/L of ClO₄⁻. Under ammonia limiting conditions, the perchlorate reduction rate decreased by 10%, whereas the nitrate reduction rate was unaffected. Though nitrate and perchlorate accumulated in the bioreactor, their concentrations in the treated water (2.8 ± 0.5 mg/L of NO₃⁻ and 7.0 ± 0.8 μg/L of ClO₄⁻, respectively) were always below the drinking water regulatory levels, due to Donnan dialysis control of the ionic transport in the system.Kinetic parameters determined for the mixed microbial culture in suspension showed that the nitrate reduction rate was 35 times higher than the maximum perchlorate reduction rate. It was found that perchlorate reduction was inhibited by nitrate, since after nitrate depletion perchlorate reduction rate increased by 77%. The biofilm developed in the IEMB was cryosectioned and the microbial population was analyzed by fluorescence in situ hybridization (FISH). The results obtained seem to indicate that the kinetic advantage of nitrate reduction favored accumulation of denitrifiers near the membrane, whereas per(chlorate) reducing bacteria were mainly positioned at the biofilm outer surface, contacting the biomedium. As a consequence of the biofilm stratification, the reduction of perchlorate and nitrate occur sequentially in space allowing for the removal of both ions in the IEMB.     

Feasibility and kinetics study on the direct bio-regeneration of perchlorate laden anion-exchange resin

Anion exchange is one of the most promising treatment technologies for the removal of low levels of perchlorate. The spent anion-exchange resins, however, need to be disposed of or regenerated because they contain high contents of perchlorate. This study investigated the feasibility and kinetics of a direct bio-regeneration method. The method accomplished resin regeneration and biological perchlorate destruction concurrently, by directly contacting the spent resin with the perchlorate-reducing bacteria (PRB). The results indicated that the method was effective in regeneration of perchlorate and nitrate loaded resin and the resin could be repeatedly regenerated with the method. The regenerated resin was effective, stable, and durable in the filtration treatment of perchlorate in well water from the Saddle River area, NJ. Moreover, the method was also effective in regeneration of the spent A-530E resin, which had high perchlorate affinity and was yet very difficult for regeneration with the conventional brine desorption technique. Besides, the results further suggested that the perchlorate and nitrate desorption from the loaded resin coupling with their subsequent biological reduction could be the direct bio-regeneration mechanism. No biofilm was formed on the regenerated resin surface according to a scanning electron microscopy (SEM) analysis.     

Non-agricultural sources of groundwater nitrate: a review and case study

Nitrate is often seen as an agricultural pollutant of groundwater and so is expected to be at higher concentrations in the groundwaters surrounding a city than in those beneath it. However the difference between rural and urban nitrate concentrations is often small, due to the non-agricultural sources of nitrogen that are concentrated in cities. This paper illustrates the source and significance of non-agricultural nitrogen for groundwater and presents a case study of nitrate loading in the city of Nottingham. Major sources of nitrogen in urban aquifers are related to wastewater disposal (on-site systems and leaky sewers), solid waste disposal (landfills and waste tips). The major sources of nitrogen in the Nottingham area are mains leakage and contaminated land with approximately 38% each of a total load of 21 kg N ha(-1) year(-1).     

Factors affecting filtration characteristics in membrane-coupled moving bed biofilm reactor

Factors affecting filtration characteristics in submerged hollow fiber membrane were investigated in membrane-coupled moving bed biofilm reactor (M-CMBBR). The trend of membrane biofouling in M-CMBBR was quite different from that in a conventional membrane bioreactor (MBR). The M-CMBBR showed much lower biofouling rate than a conventional MBR. Whereas the membrane biofouling in conventional MBR system is known to be dependent mostly on biochemical effects of mixed liquor (soluble COD, EPS, etc.), the extent of biofouling in M-CMBBR was largely dependent on the potential collision energy of biofilm carriers (media) moving freely and colliding with surfaces of submerged hollow fibers. The collisions between circulating media and hollow fiber membranes gave rise to frictional forces which mitigated the formation of biofilms on the outer surface of hollow fibers. Consequently, the membrane permeability was greatly enhanced. The potential collision energy of moving media was dependent on the media volume fraction as well as the air flow rate. The membrane permeability was found to be proportional to the relative potential collision energy of the biofilm carriers. The frictional effect on the morphology of biofilms formed on the surface of organic membrane under various operating condition was also examined and identified through their visualization with SEM and AFM.     

Mass transfer in a membrane aerated biofilm

We present experimental results of mass transfer of a non reactive tracer gas (neon) measured in aerobic heterotrophic biofilm developed from activated sludge. Biofilms are grown in various hydrodynamic conditions and the effective diffusivity is used to quantify the mass transfer through the biofilm. Beyond some cross-flow conditions, the effective diffusivity through the biofilm seems larger than in the bulk. This can be explained by a dispersion generated by convection inside the biofilm, as supported by an analytical flow model and in accordance to the numerical simulation proposed by Aspa et al. (2011).     

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.     

Nitrogen dynamics and removal in a horizontal flow biofilm reactor for wastewater treatment

A horizontal flow biofilm reactor (HFBR) designed for the treatment of synthetic wastewater (SWW) was studied to examine the spatial distribution and dynamics of nitrogen transformation processes. Detailed analyses of bulk water and biomass samples, giving substrate and proportions of ammonia oxidising bacteria (AOB) and nitrite oxidising bacteria (NOB) gradients in the HFBR, were carried out using chemical analyses, sensor rate measurements and molecular techniques. Based on these results, proposals for the design of HFBR systems are presented.The HFBR comprised a stack of 60 polystyrene sheets with 10-mm deep frustums. SWW was intermittently dosed at two points, Sheets 1 and 38, in a 2 to 1 volume ratio respectively. Removals of 85.7% COD, 97.4% 5-day biochemical oxygen demand (BOD₅) and 61.7% TN were recorded during the study.In the nitrification zones of the HFBR, which were separated by a step-feed zone, little variation in nitrification activity was found, despite decreasing in situ ammonia concentrations. The results further indicate significant simultaneous nitrification and denitrification (SND) activity in the nitrifying zones of the HFBR. Sensor measurements showed a linear increase in potential nitrification rates at temperatures between 7 and 16 °C, and similar rates of nitrification were measured at concentrations between 1 and 20 mg NH₄-N/l. These results can be used to optimise HFBR reactor design. The HFBR technology could provide an alternative, low maintenance, economically efficient system for carbon and nitrogen removal for low flow wastewater discharges.     

Nitrate removal and biofilm characteristics in methanotrophic membrane biofilm reactors with various gas supply regimes

Aerobic methanotrophs can contribute to nitrate removal from contaminated waters, wastewaters, or landfill leachate by assimilatory reduction and by producing soluble organics that can be utilized by coexisting denitrifiers. The goal of this study was to investigate nitrate removal and biofilm characteristics in membrane biofilm reactors (MBfR) with various supply regimes of oxygen and methane gas. Three MBfR configurations were developed and they achieved significantly higher nitrate removal efficiencies in terms of methane utilization (values ranging from 0.25 to 0.36 mol N mol⁻¹ CH₄) than have previously been observed with suspended cultures. The biofilm characteristics were investigated in two MBfRs with varying modes of oxygen supply. The biofilms differed in structure, but both were dominated by Type I methanotrophs growing close to the membrane surface. Detection of the nitrite reductase genes, nirS and nirK, suggested genetic potential for denitrification was present in the mixed culture biofilms.     

Present limitations and future prospects of stable isotope methods for nitrate source identification in surface- and groundwater

Nitrate (NO₃⁻) contamination of surface- and groundwater is an environmental problem in many regions of the world with intensive agriculture and high population densities. Knowledge of the sources of NO₃⁻ contamination in water is important for better management of water quality. Stable nitrogen (δ¹⁵N) and oxygen (δ¹⁸O) isotope data of NO₃⁻ have been frequently used to identify NO₃⁻ sources in water. This review summarizes typical δ¹⁵N- and δ¹⁸O-NO₃⁻ ranges of known NO₃⁻ sources, interprets constraints and future outlooks to quantify NO₃⁻ sources, and describes three analytical techniques (“ion-exchange method”, “bacterial denitrification method”, and “cadmium reduction method”) for δ¹⁵N- and δ¹⁸O-NO₃⁻ determination. Isotopic data can provide evidence for the presence of dominant NO₃⁻ sources. However, quantification, including uncertainty assessment, is lacking when multiple NO₃⁻ sources are present. Moreover, fractionation processes are often ignored, but may largely constrain the accuracy of NO₃⁻ source identification. These problems can be overcome if (1) NO₃⁻ isotopic data are combined with co-migrating discriminators of NO₃⁻ sources (e.g. ¹¹B), which are not affected by transformation processes, (2) contributions of different NO₃⁻ sources can be quantified via linear mixing models (e.g. SIAR), and (3) precise, accurate and high throughput isotope analytical techniques become available.     

Fatty acids production from hydrogen and carbon dioxide by mixed culture in the membrane biofilm reactor

Gasification of waste to syngas (H₂/CO₂) is seen as a promising route to a circular economy. Biological conversion of the gaseous compounds into a liquid fuel or chemical, preferably medium chain fatty acids (caproate and caprylate) is an attractive concept. This study for the first time demonstrated in-situ production of medium chain fatty acids from H₂ and CO₂ in a hollow-fiber membrane biofilm reactor by mixed microbial culture. The hydrogen was for 100% utilized within the biofilms attached on the outer surface of the hollow-fiber membrane. The obtained concentrations of acetate, butyrate, caproate and caprylate were 7.4, 1.8, 0.98 and 0.42 g/L, respectively. The biomass specific production rate of caproate (31.4 mmol-C/(L day g-biomass)) was similar to literature reports for suspended cell cultures while for caprylate the rate (19.1 mmol-C/(L day g-biomass)) was more than 6 times higher. Microbial community analysis showed the biofilms were dominated by Clostridium spp., such as Clostridium ljungdahlii and Clostridium kluyveri. This study demonstrates a potential technology for syngas fermentation in the hollow-fiber membrane biofilm reactors.