Removal of nitrogen from wastewater for reusing to boiler feed-water by an anaerobic/aerobic/membrane bioreactor

The innovative process anaerobic/aerobic/membrane bioreactor (A/O/MBR) was developed to enhance pre-denitrification without the energy consumption of the recirculation pump for reusing wastewater to boiler feed-water. The performance of this bioreactor was investigated. Firstly, the septic tank wastewater with low ratio of COD/TN was disposed by a dynamic membrane bioreactor (DMBR). It was found that, although the high concentration of NO₂⁻–N in the effluent implied the potential ability of DMBR to realize shortcut nitrification and denitrification, the effluent of single DMBR was difficult to reach the criteria of reusing to boiler feed-water. Then, the process A/O/DMBR in disposing the septic tank wastewater was studied. The results indicated that this process not only accomplished the removal of 91.5% COD, 90.3% NH₄⁺–N and 60.2% TN, but also successfully realized pre-denitrification without additional recirculation pump. At last, based on the A/O/DMBR, a pilot plant A/O/MBR was built to dispose the municipal raw sewage. In the stable operation period, the average removal efficiencies for COD, NH₄⁺–N, TP and turbidity reached 90%, 95%, 70% and 99%, respectively. During the tested HRT run of 9.0 h, the effluent of COD, NH₄⁺–N, TP and turbidity was about 10 mg/L, 3 mg/L, below 1 mg/L and 1.2 NTU, respectively, which reached the criteria of the boiler feed-water in China.     

Effect of Co and Rh promoter on NOx storage and reduction over Pt/BaO/Al2O3 catalyst

Effect of cobalt and rhodium promoter on NO_x storage and reduction (NSR) kinetics was investigated over Pt/BaO/Al₂O₃. Kinetics of 2% cobalt loading over Pt/BaO/Al₂O₃ demonstrated highest NO_x uptake during lean cycle, while reduction efficiency during rich cycle appeared most poor. In contrast to this, rhodium showed suppressing effect of NO_x uptake during lean cycle and demonstrated an enhanced effect for the higher efficiency of NO_x reduction during rich cycle. DRIFT study for NO_x uptake and regeneration confirmed formation of surface BaNO_x from the band at 1300 cm⁻¹ and formation of bulk BaNO_x from the band at 1330 cm⁻¹.     

Nitrogen uptake efficiency in maize production using irrigation water high in nitrate

In order to achieve efficient use of nitrogen (N) and minimize pollution potentials, producers of irrigated maize (Zea mays L.) must make the best use of N from all sources. This study was conducted to evaluate crop utilization of nitrate in irrigation water and the effect N fertilizer has on N use efficiencies of this nitrate under irrigated maize production. The study site is representative of a large portion of the Central Platte Valley of Nebraska where ground water nitrate-N (NO₃-N) concentrations over 10 mg L^–1 are common. Microplots were established to accommodate four fertilizer N rates (0, 50, 100, and 150 kg ha^–1) receiving irrigation water containing three levels of NO₃-N (0, 10, 20 mg L^–1). Stable isotope¹⁵N was applied as a tracer in the irrigation water for treatments containing 10 and 20 mg L^–1 NO₃-N. Plots that did not receive nitrate in the irrigation water where tagged with¹⁵N fertilizer as a sidedress treatment. Sidedressed N fertilizer significantly reduced irrigation-N uptake efficiencies. When residual N uptake is added to first year plant usage, total irrigation NO₃-N uptake efficiencies are similar to total sidedress N fertilizer uptake efficiencies for our cropping system over the two year period. Efficiency of irrigation-N use depends on crop needs and availability of N from other sources during the irrigation season.     

甲醇为碳源时C/N对反硝化过程中亚硝酸盐积累的影响

如何获得稳定的NO2--N作为厌氧氨氧化细菌的电子受体是城镇污水通过厌氧氨氧化途径脱氮的瓶颈问题。为此考虑利用反硝化途径获取稳定的NO2--N。以甲醇为碳源,采用小试装置的SBR反应器,通过控制进水C/N(COD与NO3--N质量浓度比)的策略,研究了反硝化过程中的NO2--N积累的状况。试验结果表明以甲醇为碳源且投加量不足时(C/N3.2),反硝化过程中和反硝化结束后会产生稳定的NO2--N积累;在C/N不足的前提下,NO2--N积累量随甲醇投加量的增加而增加;进水C/N为2.4～3.2时,可获得约25%的NO2--N积累率;进水C/N为0.8时,NO2--N积累率仅为5.6%;C/N1时,NO2--N与NO3--N的还原速率随着COD浓度的增加而增加;C/N≥1时,COD浓度不再影响NO2--N与NO3--N的还原速率。     

Nitrogen fertigation of trickle-irrigated potato

This three-year field study, on Pellic Vertisol, was designed to investigate the response of trickle-irrigated potato (Solanum tuberosum L.) to four nitrogen levels continually applied with the irrigation stream. Waters containing 70, 130, 190, and 250 mg Nl^–1 and uniformly supplied with 50 and 120 mgl^–1 of P and K, respectively, were applied when the soil water potential was between 0.03 and 0.04 MPa. The amount of water applied at each irrigation was equivalent to 0.8 of pan evaporation from a screened USWB Class A pan. The resulting N application totals ranged from 205 to 735 kg ha^–1. Significant buildup of soil NO₃-N occurred below 45 cm depth with the two higher amounts of N but not with the 70 or 130 mg Nl^–1. A concentration of 130 mg Nl^–1 was adequate for maintaining petiole NO₃-N above the critical value throughout the growing period. The highest yield of good quality (58130 kg ha^–1; specific gravity 1.071) was obtained with 130 mg Nl^–1. It was concluded that fertigation (combined irrigation with fertilization) is a promising means for maintaining N concentration in the soil throughout the growing period at desirable levels, without undue losses by leaching.     

Nitrogen fertilization and nitrate pollution in groundwater in Japan: Present status and measures for sustainable agriculture

During the last two decades, nitrate nitrogen (NO₃-N) concentrations in groundwater in Japan have increased steadily due to the development of intensive agriculture. In some areas, they have reached or even exceeded the unacceptable level for drinking water, 10 mg l^–1. In 2000, the Environment Agency showed that 5.6% (173 of 3,374) tested wells and 4.7% (64 of 1,362) wells used for drinking water exceeded the standard level in 1999. The highest value of NO₃-N in the wells was 100 mg l^–1. Many researches have shown that NO₃-N pollution of groundwater was widely observed in Japan, except the paddy field regions. Farming practices in Kagamigahara city of Gifu prefecture have been typical ones for reducing NO₃-N pollution in groundwater. In the east district of the city, NO₃-N concentration was low in 1966, but reached 27.5 mg l^–1 in June, 1974. The farmers in this district began to reduce the nitrogen fertilizers in carrot cultivation, going from 256 kg N ha^–1 in 1970 to 153 kg N ha^–1 in 1991. The use of controlled release fertilizer increased fertilizer-nitrogen efficiency compared with common compound fertilizer and NO₃-N concentration in the groundwater began to decrease steadily. It was discussed that in order to decrease the NO₃-N pollution of groundwater, it is necessary to refocus not only agricultural technology but also agricultural policy, toward sustainable agriculture and rural development.     

Adsorption of MCPA pesticide by MgAl-layered double hydroxides

In the present study, the adsorption characteristics of the herbicide MCPA (4-chloro-2-methylphenoxyacetic acid) on layered double hydroxides (LDHs) were evaluated under laboratory conditions with particular attention to the effect of layer charge, original interlayer anion and morphology. The final objective is the use of LDHs and modified LDH materials as recyclable adsorbents and heterogeneous catalysts for the treatment of contaminated waste waters.The anionic clays tested were [Mg_1−xAl_x(OH)₂]^x+[X_x/m^m−·nH₂O] materials. The MCPA adsorption capacity was determined from adsorption isotherms and a kinetic study. We looked at the influence of the pH, the Mg²⁺/Al³⁺ ratio, i.e. the anion exchange capacity, the nature of the intercalated anion X (CO₃²⁻, NO₃⁻, Cl⁻) and the morphology of the adsorbent on the extent of adsorption. The adsorption isotherms, described by Freundlich model, are of S-type with tendency to L-type for high MCPA equilibrium concentration. Furthermore, the adsorption capacity increases with the layer charge density. Hence, MCPA adsorption on LDHs occurs by anion exchange in two steps, an external exchange followed by an interlayer exchange, which explain these changes of type within the same isotherm. Besides, the adsorption capacity depends on the nature of the starting anions, following the affinity order (NO₃⁻<Cl⁻<CO₃²⁻) proposed by Miyata and increases with the specific surface area.     

Effect of supplying a carbon extracting solution on denitrification in horizontal subsurface flow constructed wetlands

Denitrification strongly depends on the availability of carbon source in constructed wetlands (CWs). In this study, several relevant carbon source extracting solutions made from hydrolyzate of selected wetland litters were added to CWs for nitrogen removal enhancement. The feasibility of supplying a carbon extracting solution to improve potential denitrification rate in horizontal subsurface flow constructed wetland was deeply investigated. Combinations of different hydraulic retention time (HRT, especially for 2-day and 4-day) with different influent COD/N ratios were designed to prove the enhancement on denitrification by carbon source supplement. In addition, specific denitrification rate (SDNR) was calculated for the comparison of the nitrogen removal at different COD/N ratios. The sequential operation results on total nitrogen (TN) and nitrate (NO ₃ ^? -N) removal efficiencies were obtained in CW system with an influent COD/N ratio of 4.0. The accumulation of nitrite (NO ₂ ^? -N) was found to be closely related to the removal of NO ₃ ^? -N. Meanwhile, no obvious accumulation of NO ₂ ^? -N was found when the removal of NO ₃ ^? -N was relatively high.     

Nitrogen fertigation of greenhouse-grown strawberries

Two greenhouse experiments were conducted with strawberries (Fragaria ananassa) grown in plastic pots filled with 12 kg of soil, and irrigated by drip to evaluate the effect of 3 N levels and 3 N sources. The N levels were 3.6, 7.2 or 10.8 mmol Nl^–1 and the N sources were urea, ammonium nitrate and potassium nitrate for supplying NH₄/NO₃ in mmol Nl^–1 ratios of 7/0, 3.5/3.5 or 0/7, respectively. Both experiments were uniformly supplied with micronutrients and 1.7 and 5.0 mmoll^–1 of P and K, respectively. The fertilizers were supplied through the irrigation stream with every irrigation. The highest yield was obtained with the 7.2 mmol Nl^–1 due to increase in both weight and number of fruits per plant. With this N concentration soil ECe and NO₃-N concentration were kept at low levels. Total N and NO₃-N in laminae and petioles increased with increasing N level. With the N sources the highest yield was obtained with urea due to better fruit setting. The N source had no effect on soil salinity and residual soil NO₃-N; residual NH₄-N in the soils receiving urea and ammonium nitrate were at low levels.     

Catalytic wet air oxidation of dye pollutants by polyoxomolybdate nanotubes under room condition

In order to develop a catalyst with high activity and stability for catalytic wet air oxidation of pollutant dyes at room condition, a new polyoxometalate Zn_1.5PMo₁₂O₄₀ with nanotube structure was prepared using biological template. The structure and morphology were characterized using infrared (IR) spectra, UV–vis diffuse reflectance spectra (DR-UV–vis), elemental analyses, X-ray powder diffraction (XRD), and transmission electron microscopy (TEM). And the degradation of Safranin-T (ST), a hazardous textile dye, under air at room temperature and atmospheric pressure was studied as a model experiment to evaluate the catalytic activity of this polyoxomolybdate catalyst. The results show that the catalyst has an excellent catalytic activity in treatment of wastewater containing 10 mg/L ST, and 98% of color and 95% of chemical oxygen demand (COD) can be removed within 40 min. And the organic pollutant of ST was totally mineralized to simple inorganic species such as HCO₃⁻, Cl⁻ and NO₃⁻ during this time (total organic carbon (TOC) decreased 92%). The structure and morphology of the catalyst under different cycling runs show that the catalyst are stable under such operating conditions and the leaching tests show negligible leaching effect owning to the lesser dissolution. So this polyoxomolybdate nanotube is proved to be a heterogeneous catalyst in catalytic wet air oxidation of organic dye.     

Biological COD reduction and inorganic suspended solids accumulation in a pilot-scale membrane bioreactor for traditional Chinese medicine wastewater treatment

A pilot-scale test was conducted in a membrane bioreactor (MBR) for 452 days to treat high-strength traditional Chinese medicine (TCM) wastewater from two-phase anaerobic digest effluent. This study focuses on the chemical oxygen demand (COD) reduction and inorganic suspended solid (ISS) accumulation. The wastewater was high in COD, varying daily between 259 and 12,776 mg L⁻¹. Almost all the COD was removed by the MBR system, leaving a COD of <50 mg L⁻¹ in the MBR effluent. This indicated a great potential of the MBR in TCM wastewater reuse. ISS produced in the bioreactor by metabolism of microorganism increased from 265 to 4912 g h⁻¹, which showed that there were large numbers of ISS accumulation in the bioreactor. Two models, built on the material balances of COD and ISS, were developed for the simulation of MBR system performance in the biodegradation of TCM wastewater. Consequently, the kinetic constants including the maximum substrate specific biodegradation rate (V_max), the half-saturation coefficient (K_s) and the inorganic suspended solids growth rate (k) were calculated as V_max, 3.64, 3.82, 4.39 d⁻¹, K_s, 56.4, 225, 394 mg L⁻¹ and k, 265, 888, 4912 mg L⁻¹ d⁻¹ using the operational data at different hydraulic retention times (HRTs). The models well fitted the pilot-scale experimental data, and were able to simulate the COD reduction and ISS accumulation.     

Catalytic reduction of NH4NO3 by NO: Effects of solid acids and implications for low temperature DeNOx processes

Ammonium nitrate is thermally stable below 250 °C and could potentially deactivate low temperature NO_x reduction catalysts by blocking active sites. It is shown that NO reduces neat NH₄NO₃ above its 170 °C melting point, while acidic solids catalyze this reaction even at temperatures below 100 °C. NO₂, a product of the reduction, can dimerize and then dissociate in molten NH₄NO₃ to NO⁺ + NO₃⁻, and may be stabilized within the melt as either an adduct or as HNO₂ formed from the hydrolysis of NO⁺ or N₂O₄. The other product of reduction, NH₄NO₂, readily decomposes at ≤100 °C to N₂ and H₂O, the desired end products of DeNO_x catalysis. A mechanism for the acid catalyzed reduction of NH₄NO₃ by NO is proposed, with HNO₃ as an intermediate. These findings indicate that the use of acidic catalysts or promoters in DeNO_x systems could help mitigate catalyst deactivation at low operating temperatures (<150 °C).     

Highly oriented diamond growth on SixGe1−x (100) thin films

Highly oriented (100) diamond films have been successfully grown on Si_xGe_1−x (100) thin films by bias enhanced nucleation (BEN) in microwave plasma chemical vapor deposition (MPCVD) system. Raman spectra show the 1332 cm⁻¹ peak which proves the formation of diamond. Diamond nucleation density on Si_xGe_1−x substrate estimated by scanning electron microscopy is higher than 10⁹ cm⁻². The interface between diamond and Si_xGe_1−x substrate was characterized by transmission electron microscopy (TEM). About 20 nm decrease in thickness of the Si_xGe_1−x film was observed after bias enhanced nucleation step. TEM shows the existence of silicon carbide and heteroepitaxial diamond grains grown on Si_xGe_1−x substrate. Characterization from high-resolution TEM on the specimen of short time deposition reveals that a number of epitaxial diamond grains were directly nucleated on Si_xGe_1−x with {111} interplanar spacing ratio of diamond and Si_xGe_1−x of 2:3. The diamond nucleation is found to be preferred on the ridge position of the rough substrate surface. Diamond {100} facets were quickly developed in the early stage of growth.     

The Fate of <Emphasis Type="Italic">Lyngbya majuscula</Emphasis> Toxins in Three Potential Consumers

Blooms of Lyngbya majuscula have been reported with increasing frequency and severity in the last decade in Moreton Bay, Australia. A number of grazers have been observed feeding upon this toxic cyanobacterium. Differences in sequestration of toxic compounds from L. majuscula were investigated in two anaspideans, Stylocheilus striatus, Bursatella leachii, and the cephalaspidean Diniatys dentifer. Species fed a monospecific diet of L. majuscula had different toxin distribution in their tissues and excretions. A high concentration of lyngbyatoxin-a was observed in the body of S. striatus (3.94 mg/kg⁻¹) compared to bodily secretions (ink 0.12 mg/kg⁻¹; fecal matter 0.56 mg/kg⁻¹; eggs 0.05 mg/kg⁻¹). In contrast, B. leachii secreted greaterconcentrations of lyngbyatoxin-a (ink 5.41 mg/kg⁻¹; fecal matter 6.71 mg/kg⁻¹) than that stored in the body (2.24 mg/kg⁻¹). The major internal repository of lyngbyatoxin-a and debromoaplysiatoxin was the digestive gland for both S. striatus (6.31 ± 0.31 mg/kg⁻¹) and B. leachii (156.39 ± 46.92 mg/kg⁻¹). D. dentifer showed high variability in the distribution of sequestered compounds. Lyngbyatoxin-a was detected in the digestive gland (3.56 ± 3.56 mg/kg⁻¹) but not in the head and foot, while debromoaplysiatoxin was detected in the head and foot (133.73 ± 129.82 mg/kg⁻¹) but not in the digestive gland. The concentrations of sequestered secondary metabolites in these animals did not correspond to the concentrations found in L. majuscula used as food for these experiments, suggesting it may have been from previous dietary exposure. Trophic transfer of debromoaplysiatoxin from L.majuscula into S. striatus is well established; however, a lack of knowledge exists for other grazers. The high levels of secondary metabolites observed in both the anaspidean and the cephalapsidean species suggest that these toxins may bioaccumulate through marine food chains.     

Sorption–Desorption of NOx from a Lean Gas Mixture on H3PW12O40·6H2O Supported on Carbon Nanotubes

NO _x sorption capacities and efficiencies were measured on a new type of sorbent formed by 12-tungstophosphoric acid (HPW) supported on carbon nanotubes. On such a system, the sorption of both NO and NO₂ was observed but compared with HPW alone, a complementary sorption of NO _x is possible leading to a capacity of 25 mg/g_HPW at 300 °C with an efficiency of 50%. The sorption results from the formation of a [H⁺(NO₂ ^–,NO⁺)] complex on HPW and an additional mode of adsorption by a free-nitrate which was identified by the bands at 2261, 1384 and 1295 cm^–1 using infrared spectroscopy.     

Bimetallic nickel complexes of trimethyl phenyl linked salicylaldimine ligands: Synthesis, structure and their ethylene polymerization behaviors

Bimetallic salicylaldimine-nickel complexes, 2,4,6-Me₃-1,3-{[NCH–(3′-R-5′-Y-2′-O–C₆H₃)-κ²-N,O]Ni(Ph) (PPh₃)}₂ [R = tert-Bu, Y = Me, 1b; R = Ph, Y = H, 2b] were prepared and their catalytic behaviors of ethylene polymerization were investigated. The bimetallic complex 2b shows higher activities (2.9 × 10⁵ g PE mol⁻¹ Ni h⁻¹) for ethylene polymerization and affords polymer with high molecular weight (M_w = 1.41 × 10⁵) and broad molecular weight distribution (M_w/M_n = 6.1) than its mononuclear matrix, {[(2,6-Me₂C₆H₃)–NCH–(3′-Ph-2′-O–C₆H₃)-κ²-N,O]Ni(Ph)(PPh₃)} (3) (Activity = 5.5 × 10⁴ g PE mol⁻¹ Ni h⁻¹; M_w = 1.86 × 10⁴; M_w/M_n = 2.8).     

Potential for nitrate—N loss in central Alberta soils

Incubation experiments were conducted to determine the influence of soil type, soil depth and tillage-straw treatment on the capacity for NO₃-N loss under anaerobic incubation. In Experiment 1 with 14 cultivated surface soil samples, there were substantial NO₃-N losses in all soils regardless of the total organic carbon content. The total organic carbon content of these soils ranged from 21 to 55 g C kg^–1. Experiment 2 showed that the rate of NO₃-N loss decreased with depth of soil, but when glucose was added the rate of NO₃-N loss increased markedly and all of the added NO₃-N disappeared within less than a week. In Experiment 3, the soil under zero tillage where straw was retained gave slightly higher rate of NO₃-N loss than the soil from conventional tillage treatment. (Scientific Paper No. 628)     

Biological nutrient removal with volatile fatty acids from food wastes in sequencing batch reactor

Volatile fatty acids (VFAs) derived from food waste were used as an alternative carbon source in biological nutrient removal. The pH Profiles were monitored during the nutrient removal in an Na-acetate fed sequencing batch reactor (SBR) (C source). Effluent N, P and SCOD concentrations of 0.5 and 0.1 mg/L were achieved with 5.5 hour of HRT (hydraulic retention time) when influent concentrations of NH₄⁺-N, PO₄³⁻ and SCOD were 42.5, 5.92 and 180 mg/L. Then the SBR was fed with four solutions of VFAs produced under different acidogenesis conditions of food wastes. VFAs-added SBR showed similar specific nitrification rates (3.0 to 3.9 mg-N/g MLSS · h) to that of acetate, but specific denitrification rates (3.2 to 4.2 mg NO₃⁻N/g MLSS·h) were slightly lower than with acetate of 4.67 mg NO₃⁻-N/g MLSS·h. VFAs-introduced SBR efficiently removed phosphorus except when the SBR was fed with a VFA-solution containing high amounts of valerate and caproate.     

Application of real-time feedback control strategies based on effluent NH4-N and NO X -N concentrations in an A2/O process

This paper proposes two real-time feedback control strategies based on hourly measurements of effluent NH₄-N and NO _X -N concentrations. Using modified sigmoid functions to decide the DO setpoint, a control structure similar to the cascade-type control loop was selected as the real-time feedback NH₄-N control strategy. For the realtime feedback NO _X -N control strategy, a proper external carbon dose flow rate could be calculated based on the estimated NO _X -N concentration in anoxic reactor by using the empirical equation. A control system, which included two proposed control strategies, was developed and applied in the pilot-scale A²/O process. As a result, the effluent NH₄-N and NO _X -N concentrations were maintained stably lower than the target values of 3 and 5 mg/L, respectively. Moreover, because the manipulated variables for removing the NH₄-N and NO _X -N concentrations were divided in the control strategies, the two different control strategies could be successfully applied together in the A₂/O process.     

Core-shell microbioreactor microencapsulated denitrifying bacteria for nitrate-nitrogen treatment

Summary Droplets of water-in-oil-in-water (w/o/w) emulsion were prepared using sodium alginate solution with denitrifying bacteria (Paracoccus denitrificans IFO13301) and dichloromethane (DCM) with polymethylmethacrylate (PMMA). By phase-separation and solvent-evaporation these droplets could be formed into core-shell PMMA microencapsulated denitrifying bacteria (PMMA-MC) possessing a large single core and a highly porous wall. The average thickness of the PMMA shell was 30 μm and the denitrifying bacteria were incorporated in the inner core at a high density. The PMMA-MC completely reduced 20 mg/L nitrate-nitrogen (NO₃-N) and the intermediate product, nitrite-nitrogen (NO₂-N), to N₂ in the presence of H₂ using a batchwise method. Thus, incorporated denitrifying bacteria can be used to treat water polluted with NO₃-N. The PMMA-MC can be used repeatedly, and the third denitrification experiment directly denitrified (NO₃-N → N₂) without the intermediate step (NO₃-N → NO₂-N). In addition, the PMMA-MC with decreased activity could be reactivated by incubating in a culture medium.