Enzymatically-mediated uranium accumulation and uranium recovery using a Citrobacter sp. Immobilised as a biofilm within a plug-flow reactor

Biofilm-immobilised Citrobacter sp. removed uranyl ion from flows supplemented with glycerol 2-phosphate. The metal uptake mechanism was mediated by the activity of a cell-surface bound phosphatase that precipitated liberated inorganic phosphate with uranyl ion as HUO₂PO₄·4H₂O at the bacterial surface. A modified integrated form of the Michaelis–Menten equation is proposed to describe the removal of metal ion by a columnar bioreactor, where the efficiency of metal removal is semi-quantitatively related to the input flow rate, the total enzyme loading (E₀) and the bioreactor activity. With biofilm-immobilised bacteria, E₀ was further divisible (split) into subparameters of phosphatase titre per bacterium and total biomass surface area. Varying the split E₀ and the reaction temperature modified the bioreactor performance. The immobilised bacteria retained high metal loads without loss in steady-state activity. Accumulated metal was recovered as a concentrated solution.     

Application of the Stover–Kincannon kinetic model to nitrogen removal by Chlorella vulgaris in a continuously operated immobilized photobioreactor system

BACKGROUND: The aim of this study was to evaluate the ammonium nitrogen removal performance of algae culture Chlorella vulgaris in a novel immobilized photobioreactor system under different operating conditions and to determine the biokinetic coefficients using the Stover–Kincannon model. RESULTS: The photobioreactor was continuously operated at different initial ammonium nitrogen concentrations (NH₄‐N₀ = 10–48 mg L⁻¹), hydraulic retention times (HRT = 1.7–5.5 days) and nitrogen/phosphorus ratios (N/P = 4/1–13/1). Effluent NH₄‐N concentrations varied between 2.1 ± 0.5 mg L⁻¹ and 26 ± 1.2 mg L⁻¹ with increasing initial NH₄‐N concentrations from 10 ± 0.6 mg L⁻¹ to 48 ± 1.8 mg L⁻¹ at θ_H = 2.7 days. The maximum removal efficiency was obtained as 79 ± 4.5% at 10 mg L⁻¹ NH₄‐N concentration. Operating the system for longer HRT improved the effluent quality, and the percentage removal increased from 35 ± 2.4% to 93 ± 0.2% for 20 mg L⁻¹ initial NH₄‐N concentration. The N/P ratio had a substantial effect on removal and the optimum ratio was determined as N/P = 8/1. Saturation value constant, and maximum substrate utilization rate constant of the Stover–Kincannon model for ammonium nitrogen removal by C. vulgaris were determined as K_B = 10.3 mg L⁻¹ d⁻¹, U_max = 13.0 mg L⁻¹ day⁻¹, respectively. CONCLUSION: Results indicated that the algae‐immobilized photobioreactor system had an effective nitrogen removal capacity when the operating conditions were optimized. The optimal conditions for the immobilized photobioreactor system used in this study can be summarized as HRT = 5.5 days, N/P = 8 and NH₄‐N₀ = 20 mg L⁻¹ initial nitrogen concentration to obtain removal efficiency greater than 90%. Copyright © 2008 Society of Chemical Industry     

Production of SrCO3 and (NH4)2SO4 by the dry mechanochemical processing of celestite

A SrCO₃ formation starting from activated SrSO₄–(NH₄)₂CO₃ mixtures as a result of dry mechanochemical treatment for 180 min in a planetary ball mill of celestite together with (NH₄)₂CO₃ was studied. The phases that formed during milling were successfully characterized by X-ray diffraction measurement (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and chemical analysis. A novel hydrometallurgical process to convert both SrCO₃ (product) and (NH₄)₂SO₄ (by-product) from celestite via dry mechanochemical conversion with (NH₄)₂CO₃ was developed for the first time in this work. Under optimum conditions, the conversion of SrCO₃ was 98.1%. The (NH₄)₂SO₄ leach solution was crystallized.     

Simultaneous removal of SO2 and NO by low cost sorbent-catalysts prepared by lime, fly ash and industrial waste materials

The potential of the sorbent-catalysts prepared from three low cost materials, i.e., the lime, fly ash and some industrial waste material containing iron oxide, have been investigated for simultaneous removal of SO₂ and NO _x from flue gas in the temperature range 700–850 °C. NH₃ was chosen as the reducing agent for NO reduction in this study. Experimental results showed that SO₂ and NO could be simultaneously removed efficiently in the absence of O₂ at the temperature window of 700–800 °C. The effect of product layer generated from SO₂ removal on NO removal was not obvious. NO removal efficiency was strongly inhibited by O₂, which was attributed to the partial oxidation of NH₃ to NO over the sorbent-catalysts in the presence of oxygen. Neither NO₂ nor N₂O by-product was detected both in the absence and presence of O₂. Three routes were suggested to overcome the negative effect of O₂. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Structural and Thermal Characterization of A Novel High Nitrogen Energetic Material: (NH4)2DNMT

1,4‐Dihydro‐5H‐(dinitromethylene)‐tetrazole ammonium salt ((NH₄)₂DNMT), a high nitrogen energetic compound, was synthesized and structurally characterized by single‐crystal X‐ray diffraction. The thermal behavior of (NH₄)₂DNMT was studied with DSC and TG‐DTG methods. The kinetic equation of the thermal decomposition reaction is: dα/dT=10^13.17/3β(1−α)⁻² exp(−1.388×10⁵/RT). The critical temperature of thermal explosion is 182.7 °C. The specific heat capacity of (NH₄)₂DNMT was determined and the molar heat capacity is 301 J mol⁻¹ K⁻¹ at 298.15 K. The adiabatic time‐to‐explosion of (NH₄)₂DNMT was calculated to be 277 s. The detonation velocity and detonation pressure were also estimated. All results showed that (NH₄)₂DNMT presents good performance.     

One-Step Combustion Synthesis of Novel Nanocarbons via Magnesiothermic Reduction of Carbon-Containing Oxidants

The aim of this work was to transform carbon-containing ammonium oxalate, (NH₄)₂C₂O₄, and ammonium acetate, NH₄CH₃CO₂, into 3D graphene-like carbon nanomaterials via magnesiothermic reduction. Both raw and purified products were characterized by XRD, SEM, TGA, and Raman spectra. The conversion of the initial amount of carbon (in salts) into solid carbon (in purified product) varied between 8.5% (for oxalate) and 90.0% (for acetate). The XRD results confirmed the absence of starting salts in the raw products (MgO and C). The purified product was found to contain largely the turbostratic carbon forming a petal-like 3D graphene material. The application potential of synthesized materials was demonstrated on the example of the removal of 4-chlorophenol from its aqueous solution.     

Accumulation of zirconium and nickel by Citrobacter sp

Zirconium in aqueous flows was moderately biomineralized by immobilized Citrobacter N14 cells, in the form of gel‐like deposits, probably comprising a mixture of zirconium hydrogen phosphate (Zr(HPO₄)₂) and hydrated zirconia (ZrO₂). The simultaneous presence of uranyl ion (UO) did not facilitate zirconium deposition and the biomineralization of uranium itself as HUO₂PO₄ was repressed by zirconium in the presence of excess inorganic phosphate, liberated enzymatically. Nickel (Ni²⁺) was not significantly removed from aqueous flows by sorption into cell‐bound zirconium deposits, although cell‐bound hydrogen uranyl phosphate (HUP) facilitated nickel removal via intercalative ion exchange into its polycrystalline lattice. A preformed layer of HUP also promoted zirconium removal, at 100% efficiency at pH 2.6, maintained over 38 column fluid‐volumes before saturation. © 1999 Society of Chemical Industry     

An investigation of the phase transformations in a CaSO4/(NH4)2SO4/H2O system,directed at the preparation of a fine dispersed purified phosphogypsum

The process of recrystallization of apatite phosphogypsum (PHG) in a solution ammonium sulphate (AS) with the subsequent decomposition of the binary salt was investigated and the resulting highly dispersed products with a low P₂O₅ content have been discussed. The following effects were examined: (NH₄)₂SO₄ concentration, the quantity of ammonium sulphate, the reaction temperature of phosphogypsum with (NH₄)₂SO₄ solution, the time of treatment of phosphogypsum with (NH₄)₂SO₄ solution and the decomposition of the binary salt, as well as the liquid/solid ratio for the binary salts, Based on the results of the chemical and X-ray analysis, it was established that, depending on the technological conditions of the process of recrystallization, binary salts of (NH₄)₂SO₄·CaSO₄·H₂O and of (NH₄)₂SO₄·CaSO₄·H₂O and of (NH₄)₂SO₄·5 CaSO₄·H₂O were formed. As a result of the investigations carried out, a product with a low P₂O₅ content, suitable for direct processing to secondary products has been prepared.     

Application of magnetic polyaniline nanocomposite for separation of uranyl ions from aqueous solutions

Polyaniline (PANI) was synthesized chemically, and then modified with magnetic iron oxide nanoparticles (Fe₃O₄ NPs). PANI and PANI-Fe₃O₄ NPs were used for removal of uranyl ions (UO₂²⁺) from aqueous solutions using a batch system. The synthesized adsorbents were characterized using FT-IR, SEM, BET and XRD techniques. From isotherm investigation, the maximum adsorption capacities (q_m) were 150.0 and 108.0 mg g^?1 for PANI and PANI-Fe₃O₄NPs, respectively. The kinetics and equilibrium adsorptions were well-described by the pseudo-second-order kinetic and Langmuir model, respectively. Thermodynamic studies depicted that the adsorption of uranyl ions by PANI is a spontaneous exothermic process and in the case of PANI-Fe₃O₄ NPs, adsorption process is endothermic; therefore, the spontaneity is controlled by entropy.     

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).     

Hygroscopic Growth of an (NH 4 ) 2 SO 4 Aqueous Solution Droplet Measured Using an Environmental Scanning Electron Microscope (ESEM)

The contact angle, θ, and volume equivalent diameter of an (NH₄)₂SO₄ aqueous droplet was measured using an environmental scanning electric microscope (ESEM), showing the hygroscopic growth of the solution droplet as the relative humidity (RH) increased from 80% to 98%. (NH₄)₂SO₄ particles with diameters in the range 1–2 μ m were produced by an atomization technique, and collected onto a copper substrate that had been treated with polytetrafluoroethylene. To observe the hygroscope growth, the sample chamber of the ESEM was filled with water vapor at a pressure of 600 Pa, and the sample temperature was adjusted using a cooling stage to control the relative humidity inside the chamber. Before the observation of the hygroscopic growth, we determined the value of θ from overhead views of droplets on the stage at a tilted angle of 45°. The average value of θ was 96 ± 10°, and this value was used to estimate the droplet diameter. We measured the diameter of the (NH₄)₂SO₄ droplets at different RH, and observed that the growth factor, G, increased with increasing RH. The experimental value of G was consistent with the theoretically estimated value. This shows that our method for determining the value of θ was valid, and that the ESEM technique can be used to measure the diameters of droplets of aqueous solutions.     

Synthesis of nanocrystalline SnO2 powder from SnCl4 by mechanochemical processing

The rapid synthesis of nanocrystalline SnO₂ powder using a mechanochemical reaction of SnCl₄ (instead of the widely used tin (II) compounds) with (NH₄)₂CO₃ and the subsequent annealing of the product in air and under an H₂O/NH₃ atmosphere has been investigated using X-ray powder diffraction, TG and TEM. The reaction was complete within 5 min. Additional milling of the product at a higher milling intensity for 120 min led to the crystallisation of tetragonal SnO₂. The NH₄Cl salt matrix was removed by annealing at 300 °C. The average crystallite size of tetragonal SnO₂ was in the range of 2-48 nm and it can be controlled by variation heating temperatures and annealing atmospheres in the range of 300-700 °C.     

Simultaneous biofiltration of H<Subscript>2</Subscript>S,NH<Subscript>3</Subscript> and toluene using cork as a packing material

Simultaneous removal of ternary gases of NH₃, H₂S and toluene in a contaminated air stream was investigated over 185 days in a biofilter packed with cork as microbial support. Multi-microorganisms including Nitrosomonas and Nitrobactor for nitrogen removal, Thiobacillus thioparus (ATCC 23645) for H2S removal and Pseudomonas aeruginosa (ATCC 15692), Pseudomonas putida (ATCC 17484) and Pseudomonas putida (ATCC 23973) for toluene removal were used simultaneously. The empty bed residence time (EBRT) was 40–120 seconds and the inlet feed concentration was 50-180 ppmv for NH₃, 30–160 ppmv for H₂S and 40–130 ppmv for toluene, respectively. The observed removal efficiency was 45–100% for NH₃, 96–100% for H₂S, and 10–99% for toluene, respectively. Maximum elimination capacity was 5.5 g/m³/hr for NH₃, >20.4 g/m³/hr for H₂S and 4.5 g/m³/hr for toluene, respectively. During long-term operation, the removal efficiency of toluene gradually decreased, mainly due to depositions of elemental sulfur and ammonium sulfate on the cork surface. The results of microbial analysis showed that nearly the same population density was observed on the surfaces of cork chips collected at each sampling point. Kinetic model analyses showed that there were no particular evidences of interactions or inhibitions among the microorganisms.     

Ceramic membrane pretreatment of monosodium glutamate isoelectric supernatant to facilitate (NH4)2SO4 recovery by electrodialysis

BACKGROUND: The large output of monosodium glutamate in China has produced huge amounts of isoelectric supernatant containing 40–60 g L⁻¹ (NH₄)₂SO₄. With the increasing national emphasis on environmental protection and recycling, it is necessary to find a cost‐effective and environment‐friendly alternative to recover the (NH₄)₂SO₄. This paper reports on investigations of the electrodialysis process for (NH₄)₂SO₄ recovery from isoelectric supernatant pretreated by ceramic membrane. RESULTS: For ceramic membrane pretreatment, the optimal pore size chosen was 0.2 µm. After a 250 min run, permeate flux was still maintained at 90 L m⁻² h⁻¹ (v = 2.8 m s⁻¹, ΔTMP = 0.12 MPa, concentration factor = 7). Meanwhile, the total solids and proteins content in condensed supernatant were high, up to 78 g L⁻¹ and 24 g L⁻¹, respectively, which greatly favors future cell protein harvest. With the chosen current density of 17 mA cm⁻², the energy consumption and time for six consecutive batches for electrodialysis were 2.6–2.7 kW h kg⁻¹ sulfate and ∼100 min, based on ∼80% ammonium sulfate recovery from pretreated isoelectric supernatant. CONCLUSION: Ceramic membrane pretreatment was shown to be a promising pretreatment strategy, applicable to the electrodialysis process to recover ammonium sulfate from isoelectric supernatant produced during monosodium glutamate production. Copyright © 2008 Society of Chemical Industry     

Polyelectrolyte CASA hydrogels for uptake of uranyl ions from aqueous solutions

In this study, uranyl ion adsorption from aqueous solutions has been investigated by chemically crosslinked acrylamide/sodium acrylate (CASA) hydrogels. Adsorption studies were investigated by the spectroscopic method. CASA hydrogels with various compositions were prepared from ternary mixtures of acrylamide (A), sodium acrylate (SA), and water by free radical polymerization in aqueous solution, using multifunctional crosslinkers such as ethylene glycol dimethacrylate (EGDMA). Uranyl ion adsorption from aqueous solutions was studied by the batch sorption technique at 25°C. The effect of uranyl ion concentration and mass of adsorbent on the uranyl ion adsorption were examined. In experiments of sorption, L‐type sorption in the Giles classification system was found. Some binding parameters, such as initial binding constant (K_i), equilibrium constant (K), monolayer coverage (n), site‐size (u), and maximum fractional occupancy (Ô) for the CASA hydrogel–uranyl ion binding system, were calculated using the Langmuir linearization method. Finally, the amount of sorbed uranyl ion per gram of dry hydrogel (q) was calculated to be 4.44 × 10^?4–14.86 × 10^?4 mol uranyl ion per gram for CASA hydrogels. Adsorption of uranyl ion (percentage) was changed within a range of 12.86–46.71%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 200–204, 2007     

Ab initio calculation of the evolution of [SiN4-nOn] tetrahedron during β-Si3N4(0001) surface oxidation

The easy-going oxidation of silicon nitride (Si₃N₄) at high temperature greatly hampers its potential applications. Here, we explored the reaction mechanism between β-Si₃N₄ and O₂ via density functional theory (DFT) calculation, which discloses that O atoms are preferentially adsorbed on the top of Si atoms and N₂ starts to be generated as the dominant gas product at 2/3 monolayer (ML) O coverage. The vacancies formed by N₂ removal attract the O adatoms to transfer to the site of the N vacancy, which accelerates the adsorption of O and the formation of Si–O bonds toward the growth of SiO₂ product. The surface oxidation of β-Si₃N₄ (0001) has been clarified by the unambiguous evolution of [SiN_4-nO_n] (n = 0-4) tetrahedrons going through from [SiN₄] tetrahedron to [SiO₄] tetrahedron, providing a deep insight into intrinsic oxidation process of Si₃N₄ ceramic.     

Oxi-ammoniation of pine-bark particles

Pine-bark sawdust was oxidized with nitric acid (5-20% by weight) and further ammoniated with NH₃ or NH₄OH. Ammoniation with NH₃ was carried out in a fluidized bed reactor at 100 and 250°C and a NH, flow of 126 L/h (0°C; 101.3 kPa). Ammoniation with NH₄OH was carried out in a batch reactor by reacting the oxidized sample with NH₄OH (2 kmol/m³) at total reflux. Data on total nitrogen, ammonia nitrogen and KMnO₄ soluble nitrogen content are reported for the resulting product.     

Control of H2S waste gas emissions with a biological activated carbon filter

The removal of high concentrations of H₂S from waste gases containing mixtures of H₂S and NH₃ was studied using the pilot‐scale biofilter. Granular activated carbon (GAC), selected as support material in this study, demonstrated its high adsorption capacity for H₂S and good gas distribution. Extensive tests to determine removal characteristics, removal efficiency, and removal capacity of high H₂S levels and coexisting NH₃ in the system were performed. In seeking the appropriate operating conditions, the response surface methodology (RSM) was employed. H₂S removal capacities were evaluated by the inoculated bacteria (biological conversion) and BDST (Bed Depth Service Time) methods (physical adsorption). An average 98% removal efficiency for 0.083–0.167 mg dm^?3 of H₂S and 0.004–0.021 mg dm^?3 of NH₃ gases was achieved during the operational period because of rapid physical adsorption by GAC and subsequently an effective biological regeneration of GAC by inoculated Pseudomonas putida CH11 and Arthrobacter oxydans CH8. The results showed that H₂S removal efficiency for the system was not affected by inlet NH₃ concentrations. In addition, no acidification was observed in the BAC biofilter. High buffer capacity and low moisture demand were also advantages of this system. The maximal inlet loading and critical loading for the system were 18.9 and 7.7 g‐H₂S m^?3 h^?1, respectively. The results of this study could be used as a guide for the further design and operation of industrial‐scale systems. Copyright © 2004 Society of Chemical Industry     

Simultaneous removal of low concentrations of ammonium and humic acid from simulated groundwater by vermiculite/palygorskite columns

Vermiculite and palygorskite are common clay minerals having large surface area and high cation exchange capacities. They have different affinities for ammonium (NH₄⁺) and humic acid (HA), and hence were combined to remove NH₄⁺ and HA simultaneously from simulated groundwater in column tests. Three columns were assembled by filling the columns with the same amount of vermiculite and palygorskite but in different arrangements. The simulated groundwater containing NH₄⁺ and HA was pumped to the columns in an upward direction. The concentrations of N-NH₄⁺ and HA at different height of the columns were measured over time. No significant differences on HA removal among the three column settings were observed. However, the NH₄⁺ removal efficiencies were significantly different among the three column settings. For the column filled with separate vermiculite and palygorskite layers, NH₄⁺ was mainly adsorbed on the vermiculite layer. In contrast, when mixture of vermiculite and palygorskite was packed at the ratio of 1:1, NH₄⁺ was mainly accumulated at the bottom of the column.     

The role of sulfate as a competitive inhibitor of enzymatically‐mediated heavy metal uptake by Citrobacter sp: implications in the bioremediation of acid mine drainage water using biogenic phosphate precipitant

Heavy metals can be removed from solution via biocrystallization with enzymatically‐liberated inorganic phosphate, according to Michaelis–Menten kinetics, in free whole cells and cells immobilized within polyacrylamide gel in a flow‐through reactor. Sulfate is a competitive inhibitor of phosphate release and a predictive model was developed and shown to describe the effect of sulfate on the efficiency of phosphate release by flow‐through columns. The inhibitory effect was substantially less than anticipated in the case of metal removal by the columns. In the case of lanthanum removal metal removal efficiency was restored by increasing the substrate concentration in accordance with model predictions. In the case of uranyl ion its removal with an equivalent substrate supplement increased the activity by 20% over the initial value at a limiting flow rate. Since the initial loss in activity in the presence of 40 mmol dm⁻³ SO₄²⁻ (approximately twice the K_i value) was only approximately 20% with both metals this was considered to be a minor problem for bioprocess application. In confirmation, calculations made from a published ‘case history’ of application of the system to the bioremediation of acid mine drainage water (AMD) containing 0.22 mmol dm⁻³ of uranyl ion and 35 mmol dm⁻³ of SO showed that the benchscale model is a good representation of performance under actual load conditions. © 1999 Society of Chemical Industry