Showing papers on "Ammonia published in 2007"

Secondary aerosol formation from atmospheric reactions of aliphatic amines

Abstract: Although aliphatic amines have been detected in both urban and rural atmospheric aerosols, little is known about the chemistry leading to particle formation or the potential aerosol yields from reactions of gas-phase amines. We present here the first systematic study of aerosol formation from the atmospheric reactions of amines. Based on laboratory chamber experiments and theoretical calculations, we evaluate aerosol formation from reaction of OH, ozone, and nitric acid with trimethylamine, methylamine, triethylamine, diethylamine, ethylamine, and ethanolamine. Entropies of formation for alkylammonium nitrate salts are estimated by molecular dynamics calculations enabling us to estimate equilibrium constants for the reactions of amines with nitric acid. Though subject to significant uncertainty, the calculated dissociation equilibrium constant for diethylammonium nitrate is found to be sufficiently small to allow for its atmospheric formation, even in the presence of ammonia which competes for available nitric acid. Experimental chamber studies indicate that the dissociation equilibrium constant for triethylammonium nitrate is of the same order of magnitude as that for ammonium nitrate. All amines studied form aerosol when photooxidized in the presence of NOx with the majority of the aerosol mass present at the peak of aerosol growth consisting of aminium (R3NH+) nitrate salts, which repartition back to the gas phase as the parent amine is consumed. Only the two tertiary amines studied, trimethylamine and triethylamine, are found to form significant non-salt organic aerosol when oxidized by OH or ozone; calculated organic mass yields for the experiments conducted are similar for ozonolysis (15% and 5% respectively) and photooxidation (23% and 8% respectively). The non-salt organic aerosol formed appears to be more stable than the nitrate salts and does not quickly repartition back to the gas phase.

Influence of temperature and pH on the kinetics of the Sharon nitritation process

Abstract: The SHARON (Single reactor High activity Ammonia Removal Over Nitrite) process is an innovative process that improves the sustainability of wastewater treatment, especially when combined with an Anammox process. It aims at ammonium oxidation to nitrite only, while preventing further nitrate formation. In order to optimize this process by means of modelling and simulation, parameters of the biological processes have to be assessed. Batch tests with SHARON sludge clearly showed that ammonia rather than ammonium is the actual substrate and nitrous acid rather than nitrite is the actual inhibitor of the ammonium oxidation in the SHARON process. From these batch tests the ammonia affinity constant, the nitrous acid inhibition constant and the oxygen affinity constant were determined to be 0.75mgNH3-N L −1 ,2 .04mgHNO2-N L −1 and 0.94mgO2 L −1 . The influence of pH and temperature on the oxygen uptake rate of SHARON biomass was determined, indicating the existence of a pH interval between 6.5 and 8 and a temperature interval from 35 to 45 ◦ C where the biomass activity is maximal. The kinetic parameters of the SHARON process were determined based on batch experiments. These parameters can now be implemented in a simulation model for further optimization of the SHARON process.  2007 Society of Chemical Industry

Ammonia volatilisation from urease inhibitor-treated urea applied to sugarcane trash blankets.

Abstract: Legal restrictions from burning sugarcane prior to harvest are causing a sharp increase in acreage which is harvested as green cane. The presence of a thick sugarcane trash mulch left after harvest makes it difficult to incorporate fertilisers in the soil. Since large losses of ammonia may occur when urea is surface applied to trash, it is important to find ways to improve urea-N use efficiency. The urease inhibitor NBPT slows down urea hydrolysis and thus may help decrease ammonia losses. Ammonia traps were set up in seven sugarcane fields covered with trash and fertilised with ammonium sulfate or ammonium nitrate, urea, and NBPT-treated urea. All N fertilisers were surface-applied at rates of 80 or 100 kg N ha-1. Very little N was lost when ammonium nitrate or ammonium sulfate were used. However, volatilisation losses as ammonia from the urea treatments varied from 1% (rainy days after fertilisation) to 25% of the applied N. The percentage of reduction in volatilisation due to NBPT application ranged from 15% to 78% depending on the weather conditions during the days following application of N. Addition of NBPT to urea helped to control ammonia losses, but the inhibitor was less effective when rain sufficient to incorporate urea into the soil occurred only 10 to 15 days or latter after fertiliser application.

Redirection of Metabolism for Biological Hydrogen Production

Abstract: A major route for hydrogen production by purple photosynthetic bacteria is biological nitrogen fixation. Nitrogenases reduce atmospheric nitrogen to ammonia with the concomitant obligate production of molecular hydrogen. However, hydrogen production in the context of nitrogen fixation is a rather inefficient process because about 75% of the reductant consumed by the nitrogenase is used to generate ammonia. In this study we describe a selection strategy to isolate strains of purple photosynthetic bacteria in which hydrogen production is necessary for growth and independent of nitrogen fixation. We obtained four mutant strains of the photosynthetic bacterium Rhodopseudomonas palustris that produce hydrogen constitutively, even in the presence of ammonium, a condition where wild-type cells do not accumulate detectable amounts of hydrogen. Some of these strains produced up to five times more hydrogen than did wild-type cells growing under nitrogen-fixing conditions. Transcriptome analyses of the hydrogen-producing mutant strains revealed that in addition to the nitrogenase genes, 18 other genes are potentially required to produce hydrogen. The mutations that caused constitutive hydrogen production mapped to four different sites in the NifA transcriptional regulator in the four different strains. The strategy presented here can be applied to the large number of diverse species of anoxygenic photosynthetic bacteria that are known to exist in nature to identify strains for which there are fitness incentives to produce hydrogen.

Effect of Ammonia on Secondary Organic Aerosol Formation from α-Pinene Ozonolysis in Dry and Humid Conditions

Abstract: This study examines the influence of ammonia (NH3) on secondary organic aerosol (SOA) formation from the alpha-pinene/ozone oxidation system for dry and humid conditions. Aerosol yield differed depending on which OH scavenger was used, with the highest yield noted for CO, followed by cyclohexane and 2-butanol. Number and volume concentrations were quickly increased within the reactor by 15 and 8%, respectively, when NH3 was added after the reaction ceased. The increase in number concentration indicated the formation of new particles resulting from gas-to-particle conversion. Moreover, average particle size increased from 242 to 248 nm. The resulting aerosol growth was attributed to ammonium salts formed by the reaction between organic acids and NH3. When NH3 was added to aerosolized cis-pinonic acid in the environmental reactor, a dramatic increase in both number and volume concentrations of cis-pinonic acid was observed. This provides further evidence that NH3 can interact with gas-phase organic acids forming condensable salts and thereby enhancing SOA formation. Initially present NH3 significantly enhanced aerosol yield in alpha-pinene-ozone reactions, regardless of the presence of water vapor. The role of NH3 on SOA formation in the dry and humid conditions is discussed in terms of a theoretical modeling study.

Ammonia scr catalyst and method of using the catalyst

Abstract: A DPF with an SCR catalyst and a method for selectively reducing nitrogen oxides with ammonia, filtering particulates, and reducing the ignition temperature of soot on a DPF are provided. The catalyst includes a first component of copper, chromium, cobalt, nickel, manganese, iron, niobium, or mixtures thereof, a second component of cerium, a lanthanide, a mixture of lanthanides, or mixtures thereof, and a component characterized by increased surface acidity. The catalyst may also include strontium as an additional second component. The catalyst selectively reduces nitrogen oxides to nitrogen with ammonia and oxidizes soot at low temperatures. The catalyst has high hydrothermal stability.

Interactions of ammonia with the surface of microporous carbon impregnated with transition metal chlorides

Abstract: The BPL carbon samples impregnated with chlorides of copper, nickel, and zinc were used as ammonia adsorbents in dynamic conditions with various amounts of water present in the systems. The initial and exhausted samples were characterized using adsorption of nitrogen, XRF, XRD, FTIR, SEM, and thermal analysis. The results indicate that metal chlorides are active centers for ammonia adsorption via formation of complexes. Water enhances the amount of ammonia adsorbed, promoting its dissolving into the film of water adsorbed in micropores and formation of NH4+ ions. Even though the pore system of activated carbon provides spaces for dispersion of metals, it still contributes significantly to the amount of ammonia adsorbed (about 80%) via dispersive forces. The most efficient adsorbent for ammonia removal is the carbon impregnated with copper. In this material the efficiency is governed by the amount of copper introduced to the carbon and its dispersion on the surface.

Metabolic and immune responses in Chinese mitten-handed crab (Eriocheir sinensis) juveniles exposed to elevated ambient ammonia.

Abstract: The toxicity of ammonia to Eriocheir sinensis juveniles was determined. The 24 h-, 48 h-, 72 h-, 96 h-LC(50) values of total ammonia (TAN) were 251.68, 217.61, 156.05, and 119.67 mg L(-1), respectively. Following these results, crabs were then exposed for a 2-day period to 20, 40, 60 and 80 mg L(-1) TAN and sampled at 3, 6, 24 and 48 h for changes in metabolic parameters (including haemolymph ammonia concentration, glucose, lactate, urea, triacylglycerol, glutamine, and glutamate levels) and immunity indicators (the total of haemocyte count and superoxide dismutase activity). Results showed a distinct linear relationship between ambient ammonia and haemolymph ammonia and a notable increase in haemolymph ammonia content after ammonia exposure. Compared with the control group, lower concentration of triglycerides and significantly higher glucose, urea, and lactate level in haemolymph were observed when ambient ammonia increased. This suggested a reduced use of carbohydrates through anaerobic metabolism and an increase in the use of lipids to satisfy the metabolic demand. A significant surge of the ammonia metabolic product, glutamate, was observed after 3 h ammonia exposure, and the compensatory response to reduced glutamate was manifested by increased glutamine synthesis. During the same period, total haemocyte count decreased while ambient ammonia increased. Superoxide dismutase (SOD) activity in haemolymph was stimulated by lower ambient ammonia concentration after short time exposure and depressed by higher ammonia concentration. Therefore, haemolymph ammonia accumulation resulted in an increase in energy demand and a depression in immune capacity. The mechanism to detoxification of ammonia may be to transform ammonia to urea and glutamine.

Catalytic Effects of Metal-loaded Membrane-like Alumina Tubes on Ammonia Synthesis in Atmospheric Pressure Plasma by Dielectric Barrier Discharge

Abstract: Plasma synthesis of ammonia was studied at atmospheric pressure using a dielectric-barrier-discharge-plasma reactor equipped with a metal-loaded membrane-like alumina tube as a catalyst between the electrodes. Introducing the pure alumina into N2–H2 plasma resulted in an increase in the ammonia yield and the further improvement was achieved by loading the alumina with Ru, Pt, Ni, and Fe. These results clearly demonstrate the catalytic effects of the alumina and the metals in the plasma reaction. Temperature-programmed desorption and isotope exchange reaction of nitrogen revealed that plasma-excited N2 molecules were subjected to dissociative adsorptions mainly on the alumina to form atomic N(a) (The suffix “(a)” denotes adsorbed species) species, which were converted into ammonia by H2 plasma. A role of the metals is considered to be acceleration of ammonia formation by the reaction of the alumina-adsorbed N(a) atoms with plasma-activated hydrogen species.

Electrochemical treatment of ammonia in wastewater by RuO2–IrO2–TiO2/Ti electrodes

Abstract: This study investigated the removal of ammonia in wastewater by an electrochemical method using titanium electrodes coated with ruthenium and iridium (RuO2–IrO2–TiO2/Ti) with low chlorine evolution over-voltage. The effects of operating parameters, including chloride ion concentration, current density and initial pH, were also investigated. The results were evaluated primarily by considering the efficiency of the elimination of NH 4 + -N. The removal of ammonia by electrochemical oxidation mainly resulted from the indirect oxidation effect of chlorine/hypochlorite produced during electrolysis. The direct anodic oxidation efficiency of ammonia was less than 5%, and the current efficiency was less than 10%. The ammonia removal followed pseudo-first-order kinetics. The electrochemical process can be applied successfully as a final polishing step, or as an alternative method to biological nitrification. The process seems to be most beneficial for small coastal cities

Unraveling the Source of Nitric Oxide Emission during Nitrification

Abstract: Nitric oxide production was measured during nitrification in a laboratory-scale bioreactor, operated at conditions relevant to municipal nitrifying wastewater treatment plants. This study aims to determine which type of microorganism and which metabolic pathway is responsible for nitric oxide emission during nitrification. Simulation studies were used to identify which pathway is the main source of nitric oxide emission, based on the following three hypothetical pathways for nitric oxide emission: (a) nitrification, (b) denitrification by ammonia-oxidizing bacteria with ammonium as electron donor, and (c) heterotrophic denitrification. The results of the study suggest that, in a nitrifying reactor treating wastewater containing solely ammonium and nutrients, denitrification by ammonia- oxidizing bacteria is the main nitric-oxide-producing pathway. During the experiments, 0.025% of the treated ammonium is emitted as nitric oxide, independent of the aeration rate imposed. Nitrite presence and oxygen limitation were found to increase the nitric oxide emission. Water Environ. Res., 79, 2499 (2007).

Vapor−Liquid Equilibrium of Ammonia + Lithium Nitrate + Water and Ammonia + Lithium Nitrate Solutions from (293.15 to 353.15) K

Abstract: The vapor pressure of ammonia + lithium nitrate + water and ammonia + lithium nitrate mixtures was measured by a static method from (293.15 to 353.15) K in ammonia mass fractions ranging from 0.2 to 0.6. The experimental vapor pressure data were correlated with the temperature and the liquid-phase composition using an analytical polynomial equation. The capability of the electrolyte nonrandom two liquid (E-NRTL) model to predict the vapor−liquid equilibrium (VLE) of the ternary mixture was evaluated by comparing predicted and experimental data of the ammonia + lithium nitrate + water solutions. The binary interaction parameters of ammonia + lithium nitrate needed for the prediction of ternary VLE were determined from binary experimental data.

Identification of adsorbed species on Cu-ZSM-5 under NH3 SCR conditions

Abstract: The selective catalytic reduction of nitrogen oxides with ammonia as the reducing agent was studied using Fourier transform infrared (FTIR) spectroscopy. The adsorbed species found on a Cu-ZSM-5 powder during exposure to NO, NO2 or NH3 was compared to the adsorbed species identified during SCR conditions. A blocking effect caused by ammonia at 175 °C was investigated by a stepwise increase of the ammonia concentration, and the spectra indicated that the formation of nitrites or nitrates decreased as surface coverage of ammonia increased. No such effect was observed at 350 °C, since the oxidation of ammonia results in very low ammonia coverage. The effect of changes in the NO to NO2 ratio was also studied at 350 °C, and the species identified during SCR reaction indicated that the enhanced activity at equimolecular amounts of NO and NO2 possibly involves gas phase components as well as adsorbed species.

Detailed study of the plasma-activated catalytic generation of ammonia in N2-H2 plasmas

Abstract: We investigated the efficiency and formation mechanism of ammonia generation in recombining plasmas generated from mixtures of N2 and H2 under various plasma conditions. In contrast to the Haber-Bosch process, in which the molecules are dissociated on a catalytic surface, under these plasma conditions the precursor molecules, N2 and H2, are already dissociated in the gas phase. Surfaces are thus exposed to large fluxes of atomic N and H radicals. The ammonia production turns out to be strongly dependent on the fluxes of atomic N and H radicals to the surface. By optimizing the atomic N and H fluxes to the surface using an atomic nitrogen and hydrogen source ammonia can be formed efficiently, i.e., more than 10% of the total background pressure is measured to be ammonia. The results obtained show a strong similarity with results reported in literature, which were explained by the production of ammonia at the surface by stepwise addition reactions between adsorbed nitrogen and hydrogen containing radicals at the surface and incoming N and H containing radicals. Furthermore, our results indicate that the ammonia production is independent of wall material. The high fluxes of N and H radicals in our experiments result in a passivated surface, and the actual chemistry, leading to the formation of ammonia, takes place in an additional layer on top of this passivated surface.

Significance of ammonia in growth of atmospheric nanoclusters.

Abstract: We apply accurate quantum chemistry methods to study the thermochemistry of molecular clusters containing ammonia, water, and sulfuric acid and investigate initial reaction steps in atmospheric nucleation by calculating free energies for the related reactions. The results indicate that ammonia is a key reactant enhancing the growth of small water-sulfuric acid clusters in atmospheric conditions. The role of ammonia becomes significant when the nanoclusters contain more than one or two sulfuric acid molecules. This implies a lower limit of 1:3 for the NH3/H2SO4 mole ratio of atmospheric sulfuric acid-water-ammonia clusters.

Acid strengths and catalytic activities of sulfonic acid on polymeric and silica supports

Abstract: The acidic and catalytic properties of sulfonic acids supported on polystyrene, on silica (via propyl and phenyl tethers) and on a fluorinated hydrocarbon polymer (Nafion) are compared. Surface acidities are characterised using ammonia adsorption calorimetry under flow conditions in which pulses of ammonia are introduced to the sample from a flowing carrier stream. The extent of adsorption and molar enthalpies of ammonia adsorption (ΔHads°) are interpreted in terms of the abundance, accessibility and strength of surface acid sites. Catalytic activities are measured for the isomerisation of α-pinene. The Nafion catalysts show the highest ΔHads°(NH3) and the highest catalytic activities. Although both silica-supported and polystyrene-supported sulfonic acids show lower specific activities and lower ΔHads°(NH3) values, the correlation between activity and ΔHads°(NH3) is relatively poor for these supported forms of the acid. It appears that while ΔHads°(NH3) is certainly sensitive to the strength of acid groups on which ammonia is adsorbed, it can only be used to compare acid strengths in a meaningful way for structurally similar catalysts.

Estimating the NH 3 :H 2 SO 4 ratio of nucleating clusters in atmospheric conditions using quantum chemical methods

Abstract: We study the ammonia addition reactions of H 2 SO 4 ·NH 3 molecular clusters containing up to four ammonia and two sulfuric acid molecules using the ab initio method RI-MP2 (Resolution of Identity 2nd order Moller-Plesset perturbation theory). Together with results from previous studies, we use the computed values to estimate an upper limit for the ammonia content of small atmospheric clusters, without having to explicitly include water molecules in the quantum chemical simulations. Our results indicate that the NH 3 :H 2 SO 4 mole ratio of small molecular clusters in typical atmospheric conditions is probably around 1:2. High ammonia concentrations or low temperatures may lead to the formation of ammonium bisulfate (1:1) clusters, but our results rule out the formation of ammonium sulfate clusters (2:1) anywhere in the atmosphere. A sensitivity analysis indicates that the qualitative conclusions of this study are not affected even by relatively large errors in the calculation of electronic energies or vibrational frequencies.