The contribution of exopolysaccharides induced struvites accumulation to ammonium adsorption in aerobic granular sludge

Aerobic granular sludge from a lab-scale reactor with simultaneous nitrification/denitrification and enhanced biological phosphorus removal processes exhibited significant amount of ammonium adsorption (1.5 mg NH₄⁺-N/g TSS at an ammonium concentration of 30 mg N/L). Potassium release accompanied ammonium adsorption, indicating an ion exchange process. The existence of potassium magnesium phosphate (K-struvite) as one of potassium sources in the granular sludge was studied by X-ray diffraction analysis (XRD). Artificially prepared K-struvite was indeed shown to adsorb ammonium. Alginate-like exopolysaccharides were isolated and their inducement for struvite formation was investigated as well. Potassium magnesium phosphate proved to be a major factor for ammonium adsorption on the granular sludge. Struvites (potassium/ammonium magnesium phosphate) accumulate in aerobic granular sludge due to inducing of precipitation by alginate-like exopolysaccharides.     

Ammonium adsorption in aerobic granular sludge, activated sludge and anammox granules

The ammonium adsorption properties of aerobic granular sludge, activated sludge and anammox granules have been investigated. During operation of a pilot-scale aerobic granular sludge reactor, a positive relation between the influent ammonium concentration and the ammonium adsorbed was observed. Aerobic granular sludge exhibited much higher adsorption capacity compared to activated sludge and anammox granules. At an equilibrium ammonium concentration of 30 mg N/L, adsorption obtained with activated sludge and anammox granules was around 0.2 mg NH₄-N/g VSS, while aerobic granular sludge from lab- and pilot-scale exhibited an adsorption of 1.7 and 0.9 mg NH₄-N/g VSS, respectively. No difference in the ammonium adsorption was observed in lab-scale reactors operated at different temperatures (20 and 30 °C). In a lab-scale reactor fed with saline wastewater, we observed that the amount of ammonium adsorbed considerably decreased when the salt concentration increased. The results indicate that adsorption or better ion exchange of ammonium should be incorporated into models for nitrification/denitrification, certainly when aerobic granular sludge is used.     

Utilisation de la clinoptilolite en potabilisation des eaux—elimination de l'ion NH4+Clinoptilolite in drinking water treatment for NH4+ removal

The objective of this study is to develop a technique to remove ammonium ion from water intended for potable purposes. An ion exchange method is used with a selective ion exchanger, a natural cation zeolite, clinoptilolite. Glass columns (Fig. 1) are used for laboratory experiments. These experiments show that the NH₄⁺ exchange capacity is very small compared to its total capacity 2.17 meq g^?1; its value depends essentially on the NH₄⁺ initial concentration and less on the Ca²⁺ concentration in the influent water. Figure 3 illustrates the practical exchange capacity relative to the initial concentration of ammonium ion for a soft water (Ca²⁺ = 35–50 mg l^?1). We were particularly interested in waters weak in ammonium ion concentration (NH₄⁺ = 1–3 mg l^?1). In this case and for ～1 and 2 mg l^?1 NH₄⁺ concentration in water, the practical capacity is only 0.06 and 0.108 meq g^?1 respectively. The leakage is smaller than the ECC limit (European Community Council) for drinking waters (NH₄⁺ ? 0.5 mg l^?1) and the treated volume of water to breakthrough, defined at 0.5 mg l^?1 of NH₄⁺, is ?720 BV (BV = bed volume) in both cases.In another way Fig. 6 shows that hard waters (due to Ca²⁺ ions) are more difficult to treat than soft waters. The practical capacity is smaller than before and the NH₄⁺-leakage is greater. To lessen NH₄⁺-leakage to less than 0.5 mg l^?1 for soft waters down-flow and up-flow, regeneration is used. Figure 7 shows that up-flow regeneration is more attractive than down-flow regeneration.Cycle reproducibility (Figs 4 and 5) shows that the regeneration conditions satisfied our requirements: in this case, the salt consumption is 180 eq of salt per eq of NH₄⁺ eliminated. This prompted us to try to reuse the regenerant (with NH₄⁺ ion). An increase of NH₄⁺-leakage is noticed in the presence of an NH₄⁺-residual in the regenerant. This increase is more significant with down-flow regeneration.After these laboratory experiments, we carried out a semi-industrial pilot-plant. Our objective was first to verify the laboratory results and secondly to study clinoptilolite behaviour relative to the time it was used. Two plexiglass columns comprise the pilot-plant shown in Fig. 9; soft water is used for these experiments. The first column is regenerated with fresh salt solution. The cycles obtained, considering their initial NH₄⁺-concentration, are reproduced in Fig. 10. For 2 mg l^?1 NH₄⁺ in the influent water, the leakage is about 0.2 mg l^?1 and the treated volume to breakthrough (0.5 mg l^?1 of NH₄⁺) is about 750 BV. The second column is regenerated with a recycled solution. The quality of the cycles decreases with the number of reuse of the regenerant as shown in Fig. 11. Nevertheless, it is interesting to note that after 3 reuses, the performance decrease is only 25% and the leakage, although it increases is smaller than 0.5 mg l^?1.Pilot results allowed us to propose a treatment of 30,000 m³ day^?1; the cost per cubic meter water treated, relative to NH₄⁺-removal, is about 0.165 FF (0.033 US $) for a plant and 0.77 FF (0.014 US $) for the same plant at the seaside. Using two serial columns decreased the cost by about 40–50%.     

Evaluating the influence of process parameters on soluble microbial products formation using response surface methodology coupled with grey relational analysis

Soluble microbial products (SMPs) present a major part of residual chemical oxygen demand (COD) in the effluents from biological wastewater treatment systems, and the SMP formation is greatly influenced by a variety of process parameters. In this study, response surface methodology (RSM) coupled with grey relational analysis (GRA) method was used to evaluate the effects of substrate concentration, temperature, NH₄⁺-N concentration and aeration rate on the SMP production in batch activated sludge reactors. Carbohydrates were found to be the major component of SMP, and the influential priorities of these factors were: temperature > substrate concentration > aeration rate > NH₄⁺-N concentration. On the basis of the RSM results, the interactive effects of these factors on the SMP formation were evaluated, and the optimal operating conditions for a minimum SMP production in such a batch activated sludge system also were identified. These results provide useful information about how to control the SMP formation of activated sludge and ensure the bioreactor high-quality effluent.     

The synthesis of the dissimilatory nitrate reductase under aerobic conditions in a number of denitrifying bacteria, isolated from activated sludge and drinking water

A number of denitrifying bacteria were isolated from activated sludge and drinking water. These bacteria were tested for the synthesis of the dissimilatory nitrate reductase under aerobic conditions (dissolved oxygen concentration above 4 mg · l⁻¹). The synthesis of this enzyme varied from total repression by oxygen in some bacteria, especially those isolated from drinking water, until a nearly non oxygen-repressed synthesis in other bacteria (strains 15 and N4). The effect of the dissolved oxygen concentration during growth of the bacteria on the synthesis of the dissimilatory nitrate reductase in cells of strain 15 was studied more extensively. A considerable repression of the enzyme synthesis was obtained when the dissolved oxygen concentration was relatively high (approx 15 mg·l⁻¹). Addition of chlorate to the growth medium of strain 15 (using NH⁺₄-N as nitrogen source) also resulted in a serious repression of the nitrate reductase synthesis during aerobic growth (dissolved oxygen above 4 mg·l⁻¹). The dissimilatory nitrate reductase of aerobically grown cells of strains 15 and N4 was found to be mainly localized in the membrane fraction.     

Nitrification process in activated sludge with suspended marble particles

The process of nitrification in activated sludge was investigated. As the solid support for nitrifiers' growth a suspension of marble particles has been used. The results proved the possibility of successful nitrification of 100 mg l^?1 NH₄-N simultaneously with the removal of 600 mg l^?1 COD.     

Thickening of waste activated sludge by biological flotation

Waste activated sludge was thickened by biological flotation without polymer flocculant dosage. The BIOFLOT® process utilizes the denitrifying ability of activated sludge bacteria. Gaseous products of anaerobic nitrate reduction cause spontaneous flotation of the sludge suspended solids. Laboratory tests confirmed the dependence of sludge thickening efficiency on available nitrate concentration, flotation time and temperature. Full-scale experiments were performed in a fully automatized unit for discontinuous sludge thickening from wastewater treatment plants with a capacity of up to 5000 I.E. Waste activated sludge from wastewater treatment plants at Pisek. Milevsko and Björnlunda was thickened from 6.2, 10.7 and 3.5 g/l MLSS to 59.4, 59.7 and 66.7 g/t MLSS, respectively. Concentrations of COD, ammonium and phosphate ions were decreased in sludge water. The average nitrate consumption for bioflotation was 21.2 mg NO₁⁻ per 1 g of MLSS of activated sludge. Flotation time ranged from 4 to 48 h.     

Treating landfill leachate using passive aeration trickling filters; effects of leachate characteristics and temperature on rates and process dynamics

Biological ammoniacal-nitrogen (NH₄⁺-N) and organic carbon (TOC) treatment was investigated in replicated mesoscale attached microbial film trickling filters, treating strong and weak strength landfill leachates in batch mode at temperatures of 3, 10, 15 and 30 °C. Comparing leachates, rates of NH₄⁺-N reduction (0.126-0.159 g m^− 2 d^− 1) were predominantly unaffected by leachate characteristics; there were significant differences in TOC rates (0.072-0.194 g m^− 2 d^− 1) but no trend relating to leachate strength. Rates of total oxidised nitrogen (TON) accumulation (0.012-0.144 g m^− 2 d^− 1) were slower for strong leachates. Comparing temperatures, treatment rates varied between 0.029-0.319 g NH₄⁺-N m^− 2 d^− 1 and 0.033-0.251 g C m^− 2 d^− 1 generally increasing with rising temperatures; rates at 3 °C were 9 and 13% of those at 30 °C for NH₄⁺-N and TOC respectively. For the weak leachates (NH₄⁺-N < 140 mg l^− 1) complete oxidation of NH₄⁺-N was achieved. For the strong leachates (NH₄⁺-N 883-1150 mg l^− 1) a biphasic treatment response resulted in NH₄⁺-N removal efficiencies of between 68 and 88% and for one leachate no direct transformation of NH₄⁺-N to TON in bulk leachate. The temporal decoupling of NH₄⁺-N oxidation and TON accumulation in this leachate could not be fully explained by denitrification, volatilisation or anammox, suggesting temporary storage of N within the treatment system. This study demonstrates that passive aeration trickling filters can treat well-buffered high NH₄⁺-N strength landfill leachates under a range of temperatures and that leachate strength has no effect on initial NH₄⁺-N treatment rates. Whether this approach is a practicable option depends on a range of site specific factors.     

Utilisation de la clinoptilolite en potabilisation des eaux—elimination de l'ion NH4

The objective of this study is to develop a technique to remove ammonium ion from water intended for potable purposes. An ion exchange method is used with a selective ion exchanger, a natural cation zeolite, clinoptilolite. Glass columns (Fig. 1) are used for laboratory experiments. These experiments show that the NH₄⁺ exchange capacity is very small compared to its total capacity 2.17 meq g⁻¹; its value depends essentially on the NH₄⁺ initial concentration and less on the Ca²⁺ concentration in the influent water. Figure 3 illustrates the practical exchange capacity relative to the initial concentration of ammonium ion for a soft water (Ca²⁺ = 35–50 mg l⁻¹). We were particularly interested in waters weak in ammonium ion concentration (NH₄⁺ = 1–3 mg l⁻¹). In this case and for 1 and 2 mg l⁻¹ NH₄⁺ concentration in water, the practical capacity is only 0.06 and 0.108 meq g⁻¹ respectively. The leakage is smaller than the ECC limit (European Community Council) for drinking waters (NH₄⁺ 0.5 mg l⁻¹) and the treated volume of water to breakthrough, defined at 0.5 mg l⁻¹ of NH₄⁺, is 720 BV (BV = bed volume) in both cases.In another way Fig. 6 shows that hard waters (due to Ca²⁺ ions) are more difficult to treat than soft waters. The practical capacity is smaller than before and the NH₄⁺-leakage is greater. To lessen NH₄⁺-leakage to less than 0.5 mg l⁻¹ for soft waters down-flow and up-flow, regeneration is used. Figure 7 shows that up-flow regeneration is more attractive than down-flow regeneration.Cycle reproducibility (Figs 4 and 5) shows that the regeneration conditions satisfied our requirements: in this case, the salt consumption is 180 eq of salt per eq of NH₄⁺ eliminated. This prompted us to try to reuse the regenerant (with NH₄⁺ ion). An increase of NH₄⁺-leakage is noticed in the presence of an NH₄⁺-residual in the regenerant. This increase is more significant with down-flow regeneration.After these laboratory experiments, we carried out a semi-industrial pilot-plant. Our objective was first to verify the laboratory results and secondly to study clinoptilolite behaviour relative to the time it was used. Two plexiglass columns comprise the pilot-plant shown in Fig. 9; soft water is used for these experiments. The first column is regenerated with fresh salt solution. The cycles obtained, considering their initial NH₄⁺-concentration, are reproduced in Fig. 10. For 2 mg l⁻¹ NH₄⁺ in the influent water, the leakage is about 0.2 mg l⁻¹ and the treated volume to breakthrough (0.5 mg l⁻¹ of NH₄⁺) is about 750 BV. The second column is regenerated with a recycled solution. The quality of the cycles decreases with the number of reuse of the regenerant as shown in Fig. 11. Nevertheless, it is interesting to note that after 3 reuses, the performance decrease is only 25% and the leakage, although it increases is smaller than 0.5 mg l⁻¹.Pilot results allowed us to propose a treatment of 30,000 m³ day⁻¹; the cost per cubic meter water treated, relative to NH₄⁺-removal, is about 0.165 FF (0.033 US $) for a plant and 0.77 FF (0.014 US $) for the same plant at the seaside. Using two serial columns decreased the cost by about 40–50%.     

Leachate treatment with nitrification of ammonia

Results are presented on the treatment of leachate to remove ammonia by biological nitrification. Outdoor activated sludge and trickling filter pilot plants were operated for 2 years at a major co-disposal landfill. Leachate ammonia nitrogen concentrations ranged from 150 to 550 mg l^?1 while TOC concentrations ranged from 200 to 500 mg l^?1. Very little of the TOC was degradable and BOD: NH₃-N ratios were typically 1:3.Nitrification was successfully established in both plants, and curves were established for the response of the kinetics to different temperatures. Maximum ammonia removal rate in the activated sludge plant was at least 131 g N kg VSS^?1 day^?1 achieved at an average temperature of 13°C. Maximum removal rate in the trickling filter was 309 mg N m^?2 day^?1, at 16°C.Operating problems and strategies for full-scale treatment are discussed.     

Batch monoethylamine degradation via nitrate respiration

Monoethylamine (MEA) degradation via nitrate respiration was evaluated in batch experiments using suspended growth bacterial cultures grown under low growth rate conditions. It was found that, under the conditions tested, MEA was highly degradable when the initial TOC/MLVSS ratio used in a batch experiment was < 0.35, beyond which, however, MEA inhibition was evident. The composition of the medium solution used to cultivate the bacterial cultures was critical in MEA degradation via nitrate respiration. In this study, the best MEA degradation was attained when cobalt (0.45 mg/l), copper (0.5 mg/l), molybdenum (0.5 mg/l), and yeast extract (1.0 mg/l) were all present in the medium solution. Ammonia was formed as an end product from MEA degradation via nitrate respiration. The MEA-N initially added in a batch experiment could be accounted for as NH⁺₄-N when the assimilatory requirements for nitrogen were negligible during the sampling period.     

Simultaneous nitrification and denitrification process in a new Tubificidae-reactor for minimizing nutrient release during sludge reduction

Nutrient release is reported as one of the main disadvantage of sludge reduction induced by aquatic worm. In this study, a Static Sequencing Batch Worm Reactor (SSBWR) was proposed with novel structure of perforated panels, combined aeration system and cycle operation. Effective simultaneous nitrification and denitrification were obtained owing to the stratified sludge layer containing aerobic and anoxic microzone formed on each carrier during most of the operation time in the SSBWR, which created suitable conditions for remarkable sludge reduction and nutrient removal. The results showed that the total nitrogen (TN) concentration, NO₃^?–N + NO₂^?–N concentration and NH₄⁺–N release could be reduced by 67.5%, 98.5% and 63.0%, respectively. And the soluble chemical oxygen demand (sCOD) released by sludge predation was also proved to provide a carbon source for denitrification leading to carbon release control and substantial cost savings. A schematic diagram of the stratified sludge layer and the mass balance of the nitrification–denitrification cycle were given, providing further insight into the nutrient (sCOD and nitrogen compounds) transformation during the worm predation in the SSBWR. For the mixed sludge liquid of 3000 mg TSS/L, 30 mg/L sCOD and 40 mg/L NO₃^?–N, the NO₃^?–N and NO₂^?–N came close to zero, and the sludge concentration, NH₄⁺–N release and sCOD release was reduced by 33.6%, 63.0% and 72.5%, respectively, during 48 h’ predation.     

Improving the efficiencies of simultaneous organic substance and nitrogen removal in a multi-stage loop membrane bioreactor-based PWWTP using an on-line Knowledge-Based Expert System

The results of the use of an expert system (ES) to control a novel multi-stage loop membrane bioreactor (MLMBR) for the simultaneous removal of organic substances and nutrients are reported. The study was conducted at a bench-scale plant for the purpose of meeting new discharge standards (GB21904-2008) for the treatment of chemical synthesis-based pharmaceutical wastewater (1200-9600 mg/L COD, 500-2500 mg/L BOD₅, 50-200 mg/L NH₄⁺-N and 105-400 mg/L TN in the influent water) by developing a distributed control system. The system allows various expert operational approaches to be deployed with the goal of minimizing organic substances and nitrogen levels in the outlet while using the minimum amount of energy. The proposed distributed control system, which is supervised by a Knowledge-Based Expert System (KBES) constructed with G2 (a tool for expert system development) and a back propagation BP artificial neural network, permits the on-line implementation of every operating strategy of the experimental system. A support vector machine (SVM) is applied to achieve pattern recognition. A set of experiments involving variable sludge retention time (SRT), hydraulic retention time (HRT) and dissolved oxygen (DO) was carried out. Using the proposed system, the amounts of COD, TN and NH₄⁺-N in the effluent decreased by 55%, 62% and 38%, respectively, compared to the usual operating conditions. These improvements were achieved with little energy cost because the performance of the treatment plant was optimized using operating rules implemented in real time.     

Integration of anammox into the aerobic granular sludge process for main stream wastewater treatment at ambient temperatures

Anaerobic ammonium oxidation, nitrification and removal of COD was studied at ambient temperature (18 °C ± 3) in an anoxic/aerobic granular sludge reactor during 390 days. The reactor was operated in a sequencing fed batch mode and was fed with acetate and ammonium containing medium with a COD/N ratio of 0.5 [g COD/gN]. During influent addition, the medium was mixed with recycled effluent which contained nitrate in order to allow acetate oxidation and nitrate reduction by anammox bacteria. In the remainder of the operational cycle the reactor was aerated and controlled at a dissolved oxygen concentration of 1.5 mg O₂/l in order to establish simultaneous nitritation and Anammox. Fluorescent in-situ hybridization (FISH) revealed that the dominant Anammox bacterial population shifted toward Candidatus “Brocadia fulgida” which is known to be capable of organotrophic nitrate reduction. The reactor achieved stable volumetric removal rates of 900 [g N₂-N/m³/day] and 600 [g COD/m³/day]. During the total experimental period Anammox bacteria remained dominant and the sludge production was 5 fold lower than what was expected by heterotrophic growth suggesting that consumed acetate was not used by heterotrophs. These observations show that Anammox bacteria can effectively compete for COD at ambient temperatures and can remove effectively nitrate with a limited amount of acetate. This study indicates a potential successful route toward application of Anammox in granular sludge reactors on municipal wastewater with a limited amount of COD.     

Kinetic constants of nitrification

A modified respirometric method for measuring the kinetic constants r_x,m and K_s, of the first stage of nitrification was developed and verified. The method has the following advantages; the duration of measurement is significantly decreased compared with the original method and r_x can be determined at relatively high concentrations of substrate. The effect of substrate and activated sludge composition (COD:NH₄⁺-N ratio, fraction of nitrifiers) on respirometric methods application is discussed.     

Performance analysis of a full-scale duckweed-covered sewage lagoon

A sewage lagoon for 2000–3000 capita (0.6 ha) has been operated successfully with a duckweed cover for over four years. The cover suppressed algal growth; the effluent turbidity was always below 12 Ntu. Because of inappropriate construction, one fifth of the inflow is lost by percolation and seepage during the dry season; during the wet season the loss is limited. During a detailed sampling period in the dry season actual hydraulic retention time was 20.4 d, and surface loading rate was 48–60 kgBOD₅/ha · d. Concentration reduction was 90–97% for COD, 95–99% for BOD₅, and 74–77% for Kjeldahl-N and total P. Effluent contained 2.7 mg Kjeldahl-N/l and 0.4 mg total P/l. The water column remained aerobic. At two-thirds of retention time the plants had absorbed virtually all NH⁺₄ and ortho-PO³⁻₄ from the water column. The duckweed harvest would remove in a watertight lagoon 60–80% of the N and P load, or 0.26 gN/m² · d and 0.05 gP/m² · d (in the first three-quarters of retention time). The results during this period were representative for the 4-year operation so far. Corrected for the leakage, plant productivity under these fertilised and managed conditions was sustained for several years at the level of 58–105 kg(dw)/ha · d, or 715–1200 kg/ha · d (over full lagoon surface) in the dry and wet season, respectively. We suggest that the microbial hydrolysis of the more complex organic N and P into NH⁺₄ and ortho-PO³⁻₄ is the limiting step for enhanced biomass production.     

Analyses and assessment of the spatial and temporal distribution of nitrogen compounds in surface waters

The temporal concentration variations and spatial distribution of nitrogen compounds (nitrate, nitrite, ammonium) in the natural surface waters of Stara Zagora Region, Bulgaria, over a period of 1 year were assessed in the present study. Nitrate‐nitrogen concentrations in all surface water samples, except for the December value – 21.8 mg/L in Zetyovo Reservoir, were within the permissible national quality standards. NO₂ ^–‐N could be classified as a priority pollutant of Chirpan and Zetyovo Reservoirs waters. The greatest extent of NH ₄ ⁺‐N pollution was registered in Chirpan Reservoir surface waters. The correlation study revealed appreciable mutual relationship only between NH₄ ⁺‐N and NO ₂ ^–‐N in the surface waters. The hierarchical cluster analysis (HCA) exhibited divergent apportionment of nitrogen compounds in the surface water bodies.     

Simultaneous nitrification and denitrification in a CEM (cation exchange membrane)-bounded two chamber system

A novel process was developed to induce a simultaneous oxidation of ammonia and denitrification in a single system consisting of two chambers separated by a cation exchange membrane. One was an anoxic chamber and the other was an aerobic chamber. The maximum mass flux via the membrane was calculated as 0.83 mg NH₄⁺-N/m² s in a batch test when the initial concentration of NH₄⁺ was 700 mg N/L. And it was observed that NO₃⁻ and NO₂⁻ moved via the membrane in a reverse direction when NH₄⁺ was transported. When the system was operated in a continuous mode by feeding a wastewater containing glucose and NH₄⁺, it was observed that soluble chemical oxygen demand and NH₄⁺ were simultaneously removed showing 99% and 71  86% of efficiency, respectively. Denitrification occurred in the anoxic chamber and nitrification was carried out in the aerobic chamber.     

Effect of ammonium on the hydraulic conductivity of geosynthetic clay liners

Hydraulic conductivity and swell index tests were conducted on a conventional geosynthetic clay liner (GCL) containing sodium-bentonite (Na-B) using 5, 50, 100, 500, and 1000 mM ammonium acetate (NH₄OAc) solutions to investigate how NH₄⁺ accumulation in leachates in bioreactor and recirculation landfills may affect GCLs. Control tests were conducted with deionized (DI) water. Swell index of the Na-B was 27.7 mL/2 g in 5 mM NH₄⁺ solution and decreased to 5.0 mL/2 g in 1000 mM NH₄⁺ solution, whereas the swell index of Na-B in DI water was 28.0 mL/2 g. Hydraulic conductivity of the Na-B GCL to 5, 50, and 100 mM NH₄⁺ was low, ranging from 1.6–5.9 × 10^?11 m/s, which is comparable to the hydraulic conductivity to DI water (2.1 × 10^?11 m/s). Hydraulic conductivities of the Na-B GCL permeated with 500 and 1000 mM NH₄⁺ solutions were much higher (e.g., 1.6–5.2 × 10^?6 m/s) due to suppression of osmotic swelling. NH₄⁺ replaced native Na⁺, K⁺, Ca²⁺, and Mg²⁺ in the exchange complex of the Na-B during permeation with all NH₄⁺ solutions, with the NH₄⁺ fraction in the exchange complex increasing from 0.24 to 0.83 as the NH₄⁺ concentration increased from 5 to 1000 mM. A Na-B GCL specimen permeated with 1000 mM NH₄⁺ solution to chemical equilibrium was subsequently permeated with DI water. Permeation with the NH₄⁺ converted the Na-B to “NH₄-bentonite” with more than 80% of the exchange complex occupied by NH₄⁺. Hydraulic conductivity of this GCL specimen decreased from 5.9 × 10^?6 m/s to 2.9 × 10^?11 m/s during permeation with DI water, indicating that “NH₄-bentonite” can swell and have low hydraulic conductivity, and that the impact of more concentrated NH₄⁺ solutions on swelling and hydraulic conductivity is reversible.     

The question of nitrification in the Passaic River, New Jersey: Analysis of historical data and experimental investigation

Historical NH₄⁺ and NO₃⁻ data from six stations on the Passaic River, New Jersey, were analyzed. The data for five of the stations span 1963 to 1976, and for the sixth station 1947 to 1976. Some of the conclusions reached are as follows:

1. (1) The concentration of NH₄⁺ fluctuated widely, but the trend was towards an increase with time.

2. (2) The concentration of NH₄⁺ was elevated during a period of extreme drought (1963 to 1966).

3. (3) The concentration of NO₃⁻ tended to increase smoothly with time.

4. (4) The concentration of NH₄⁺ increases longitudinally (with downstream travel).

5. (5) The loads (concentration × stream-flow) of both nitrogen species tended to increase with time.

6. (6) Substantial NO₃⁻ enters the stream from non-point sources.

7. (7) The potential for instream nitrification is not fully realized, as represented by elevated levels of NH₄⁺.

Item (7) was puzzling because conditions in the Passaic, especially in the summer, appear to be favorable for nitrification. The point was clarified, in part through an experimental investigation.River water samples, with and without added NH₄Cl, were incubated, and the course of the first step of nitrification was followed through the appearance of NO₂⁻. (The second step of nitrification was inactive during the experimental period.) The added NH₄Cl enhanced nitrification in samples from the uppermost stations (native NH₄⁺-N approximately 0.1 mg l⁻¹, but had little or no effect in samples from the middle and lower reaches (native NH₄⁺-N > 0.5 mg l⁻¹). Consequently, it was inferred that over most of the river's mainstem the growth of NH₄⁺-oxidizing bacteria was not substrate limited. There was also no indication of other nutrient limitations or of the presence of any inhibitors. This led to a projection of a 60-fold increase in the population density of planktonic NH₄⁺-oxidizers over a certain stretch of the river. However, no increase in the most-probable-number (MPN) of NH₄⁺-oxidizing bacteria was observed, which is consistent with item (7). In fact, at the end of a quiescent segment of the river the MPN's were anomalously low. This is attributed to the removal of cells from the water column through settling. This reasoning is extended to suggest that, throughout the river, settling may be the mechanism preventing a response of planktonic nitrifiers to the enrichment with NH₄⁺ from pollution sources. In turn, this could prevent a full expression of the potential for nitrification.The analyses are discussed from a regulatory perspective. It is concluded that the nitrification component of the Passaic's self-purification capacity is overburdened, and first became so in 1953.