Ammonia Generation Research Articles

Electrochemically Induced Conversion of Urea to Ammonia

A novel electrochemically induced method for ammonia synthesis (eU2A) on demand from urea in alkaline media was demonstrated. A Nickel based electrode was employed as the active catalyst. The effective rate of ammonia generation of the eU2A process at 70°C is ~28 times higher than the thermal hydrolysis (THU) of urea. The eU2A operates at lower temperature (55% lower) and pressure (6 times lower) than the THU; this could lead to significant energy savings. The process finds applications on selective catalytic reduction (SCR) for the removal of nitride oxide from combustion systems (e.g., diesel vehicles, power plants, etc.).

NBCe1 expression is required for normal renal ammonia metabolism.

The mechanisms regulating proximal tubule ammonia metabolism are incompletely understood. The present study addressed the role of the proximal tubule basolateral electrogenic Na(+)-coupled bicarbonate cotransporter (NBCe1; Slc4a4) in renal ammonia metabolism. We used mice with heterozygous and homozygous NBCe1 gene deletion and compared these mice with their wild-type littermates. Because homozygous NBCe1 gene deletion causes 100% mortality before day 25, we studied mice at day 8 (±1 day). Both heterozygous and homozygous gene deletion caused a gene dose-related decrease in serum bicarbonate. The ability to lower urinary pH was intact, and even accentuated, with NBCe1 deletion. However, in contrast to the well-known effect of metabolic acidosis to increase urinary ammonia excretion, NBCe1 deletion caused a gene dose-related decrease in ammonia excretion. There was no identifiable change in proximal tubule structure by light microscopy. Examination of proteins involved in renal ammonia metabolism showed decreased expression of phosphate-dependent glutaminase and phosphoenolpyruvate carboxykinase, key enzymes in proximal tubule ammonia generation, and increased expression of glutamine synthetase, which recycles intrarenal ammonia and regenerates glutamine. Expression of key proteins involved in ammonia transport outside of the proximal tubule (rhesus B glycoprotein and rhesus C glycoprotein) was not significantly changed by NBCe1 deletion. We conclude from these findings that NBCe1 expression is necessary for normal proximal tubule ammonia metabolism.

Instrumental Role of Helicobacter pylori γ-Glutamyl Transpeptidase in VacA-Dependent Vacuolation in Gastric Epithelial Cells.

Helicobacter pylori causes cellular vacuolation in host cells, a cytotoxic event attributed to vacuolating cytotoxin (VacA) and the presence of permeant weak bases such as ammonia. We report here the role of γ-glutamyl transpeptidase (GGT), a constitutively expressed secretory enzyme of H. pylori, in potentiating VacA-dependent vacuolation formation in H. pylori-infected AGS and primary gastric cells. The enhancement is brought about by GGT hydrolysing glutamine present in the extracellular medium, thereby releasing ammonia which accentuates the VacA-induced vacuolation. The events of vacuolation in H. pylori wild type (WT)- and Δggt-infected AGS cells were first captured and visualized by real-time phase-contrast microscopy where WT was observed to induce more vacuoles than Δggt. By using semi-quantitative neutral red uptake assay, we next showed that Δggt induced significantly less vacuolation in AGS and primary gastric epithelial cells as compared to the parental strain (P<0.05) indicating that GGT potentiates the vacuolating effect of VacA. Notably, vacuolation induced by WT was significantly reduced in the absence of GGT substrate, glutamine (P<0.05) or in the presence of a competitive GGT inhibitor, serine-borate complex. Furthermore, the vacuolating ability of Δggt was markedly restored when co-incubated with purified recombinant GGT (rGGT), although rGGT itself did not induce vacuolation independently. Similarly, the addition of exogenous ammonium chloride as a source of ammonia also rescued the ability of Δggt to induce vacuolation. Additionally, we also show that monoclonal antibodies against GGT effectively inhibited GGT activity and successfully suppressed H. pylori-induced vacuolation. Collectively, our results clearly demonstrate that generation of ammonia by GGT through glutamine hydrolysis is responsible for enhancing VacA-dependent vacuolation. Our findings provide a new perspective on GGT as an important virulence factor and a promising target in the management of H. pylori-associated gastric diseases.

Pathogen re-colonization of in-house composted and noncomposted broiler litter

In-house litter composting has been reintroduced to the industry and shown to reduce bacteria by as much as 2 orders of magnitude. Other industries have demonstrated that pathogens can recolonize a waste-residual when microbial competition has been reduced or inhibited following composting. Poultry growers, in the process of shifting to in-house composting for pathogen control, should be aware of this potential problem. A laboratory microcosm study investigated pathogenic bacteria recolonization into composted and noncomposted broiler litter over a simulated broiler grow-out cycle. Objectives were to: 1) determine colonization potential for zoonotic and poultry bacterial pathogens, 2) identify beneficial bacteria which reduce pathogen recolonization, and 3) identify the effects of ammonia on pathogen recolonization. Composted broiler litter allowedListeria andCampylobacter to colonize within the first 2 wk of the grow-out period while noncomposted litter resisted colonization. Colonization was nearly identical by the end of the grow-out period, and showed that bacterial pathogens had essentially been overtaken by commensal or normal bacteria. 16S rRNA libraries demonstrated reductions in Proteobacteria associated with composted litter (48 vs. 16%), which may indicate that this phylum occupies a niche which zoonotic pathogens prefer to occupy. Ammonia generation neither inhibited nor promoted bacterial colonization, as levels were high for both litter treatments. This study neither suggests nor condemns the continued use of this cost-effective, litter-treatment process; findings suggest that while the beneficial microbial population was initially reduced, it quickly recovered and pathogen colonization was neither enhanced nor inhibited because of this. This study demonstrates that the recently adopted in-house composting process may continue to be used, provided poultry health gains continue to be seen.

Kinetics of nitrate adsorption and reduction by nano-scale zero valent iron (NZVI): Effect of ionic strength and initial pH

Kinetic models for pollutants reduction by Nano-scale Zero Valent Iron (NZVI) were tested in this study to gain a better understanding and description of the reaction. Adsorption kinetic models and a heterogeneous catalytic reaction kinetic equation were proposed for nitrate removal and for ammonia generation, respectively. A widely used pseudo-first-order reaction model was a poor fit for nitrate removal in an iron-limiting condition and for ammonia generation in an excess iron condition. However, in this study, pseudo-first-order and pseudo-second-order adsorption kinetic equations were a good fit for nitrate removal; in addition, a Langmuir-Hinshelwood kinetic equation was able to successfully describe ammonia generation, regardless of the NZVI dose, the ionic strength, and the initial pH. These results strongly indicate that nitrate reduction by NZVI is a heterogeneous catalytic reaction, and that that the kinetic models can be used in diverse conditions. The kinetic parameters correlate well with the reaction condition, unless the NZVI dose was greatly increased or unless the NZVI surface was significantly changed at a very high initial pH.

Nitrate reduction to nitrite, nitric oxide and ammonia by gut bacteria under physiological conditions.

The biological nitrogen cycle involves step-wise reduction of nitrogen oxides to ammonium salts and oxidation of ammonia back to nitrites and nitrates by plants and bacteria. Neither process has been thought to have relevance to mammalian physiology; however in recent years the salivary bacterial reduction of nitrate to nitrite has been recognized as an important metabolic conversion in humans. Several enteric bacteria have also shown the ability of catalytic reduction of nitrate to ammonia via nitrite during dissimilatory respiration; however, the importance of this pathway in bacterial species colonizing the human intestine has been little studied. We measured nitrite, nitric oxide (NO) and ammonia formation in cultures of Escherichia coli, Lactobacillus and Bifidobacterium species grown at different sodium nitrate concentrations and oxygen levels. We found that the presence of 5 mM nitrate provided a growth benefit and induced both nitrite and ammonia generation in E.coli and L.plantarum bacteria grown at oxygen concentrations compatible with the content in the gastrointestinal tract. Nitrite and ammonia accumulated in the growth medium when at least 2.5 mM nitrate was present. Time-course curves suggest that nitrate is first converted to nitrite and subsequently to ammonia. Strains of L.rhamnosus, L.acidophilus and B.longum infantis grown with nitrate produced minor changes in nitrite or ammonia levels in the cultures. However, when supplied with exogenous nitrite, NO gas was readily produced independently of added nitrate. Bacterial production of lactic acid causes medium acidification that in turn generates NO by non-enzymatic nitrite reduction. In contrast, nitrite was converted to NO by E.coli cultures even at neutral pH. We suggest that the bacterial nitrate reduction to ammonia, as well as the related NO formation in the gut, could be an important aspect of the overall mammalian nitrate/nitrite/NO metabolism and is yet another way in which the microbiome links diet and health.

Removal of nitrate ion from water by electrochemical approaches

This study is focused on the mechanism of nitrate removal from aqueous solutions by electrochemical denitrification process (EDN) in an undivided electrolytic cell. The sacrificial (Fe and Al) electrodes and Inert (graphite (Gr)) electrode are employed for evaluation of operational parameters, namely current density, electrolysis time and sodium chloride concentration. The experimental results reveal that nitrate-N removal efficiency of 92% for Al–Fe (anode-cathode) and 80% for Fe–Fe are achieved at a current density of 25 mAcm−2 and 180min electrolysis time in 100ppm of NaCl when the initial nitrate-N concentration is 100ppm. However, during this process approximately 20ppm of ammonia-N is also formed. Ammonia-N generated is significantly lower compared to the amount of nitrate-N removal. It can be attributed to the fact that nitrate ion can be removed by both electrocoagulation (EC) and electrochemical reduction (ER) processes simultaneously. Experiments using Al, Fe and Gr as cathodes as well as anodes indicate that the contribution of EC increases when dissolving anodes are used. Further confirmation of nitrate-N removal by EC pathway is obtained by quantitative estimation of nitrate present in the sludge. During EDN, pH of the solution also increases with ammonia generation.

Operando XAFS study of carbon supported Ni, NiZn, and Co catalysts for hydrazine electrooxidation for use in anion exchange membrane fuel cells

Carbon supported Ni, Ni0.87Zn0.13, and Co hydrazine electrooxidation catalysts were synthesized by an impregnation/freeze-drying procedure followed by thermal annealing for use as anode catalyst of direct hydrazine hydrate fuel cells (DHFCs). The cell performance of DHFCs changed significantly when different catalysts were used as anode. Ammonia generation from anode outlet at open circuit voltage (OCV) condition was higher for Co/C than for Ni-based catalysts. To better understand the cause of different performance and selectivity of each anode catalyst, extensive ex-situ and operando characterization was carried out. Operando XAFS measurement of Ni–K and Co–K edge shows the potential dependence of atomic structure of Ni/C, Ni0.87Zn0.13/C, and Co/C during hydrazine electrooxidation reaction.

The contribution of biowaste disposal to odor emission from landfills

The biowaste fractions in municipal solid waste (MSW) are the main odor sources in landfill and cause widespread complaints from residents. The ammonia (NH3) and hydrogen sulfide (H2S) generation processes were simulated and compared between four typical biowaste fractions individually and combined in the mixed MSW. Food waste was found to be the main contributor to odor emission in mixed MSW, with H2S generation potential of 48.4 μg kg−1 and NH3 generation potential of 4742 μg kg−1. Fruit waste was another source for NH3 generation, with 3933 μg kg−1 NH3 generation potential. Meanwhile, nitrogen (N) was released in a faster way than sulfur (S) in waste, since 31% and 46% of total NH3 and H2S were generated in the first 90 days after disposal, with 1811 and 72 μg kg−1, and more emphasis should be placed in this initial period.Implications: Monitoring of odor generation from biowastes in MSW on a laboratory scale showed that food waste is the main source for NH3 and H2S generation, whereas waste fruit is another main contributor for NH3 released. Generally, N was released in a faster way than S from mixed-waste landfilling.

Generation of Ammonia during Wear Processes in Adhesive Wear of Titanium

We report a short note of preliminary and new experimental results that the generation of ammonia (i.e. nitrogen fixation) can occur on tribologically activated surfaces formed as a result of the frictional sliding of pure titanium when this is performed in a mixed gaseous environment of dinitrogen and dihydrogen at a total pressure of 6 × 10

Effect of Tannin and Species Variation on In vitro Digestibility, Gas, and Methane Production of Tropical Browse Plants.

Nineteen tanniferous browse plants were collected from South Africa to investigate their digestibility, gas production (GP) characteristics and methane production. Fresh samples were collected, dried in forced oven, and ground and analyzed for nutrient composition. In vitro GP and in vitro organic matter digestibility (IVOMD) were determined using rumen fluid collected, strained and anaerobically prepared. A semi- automated system was used to measure GP by incubating the sample in a shaking incubator at 39°C. There was significant (p<0.05) variation in chemical composition of studied browses. Crude protein (CP) content of the species ranged from 86.9 to 305.0 g/kg dry matter (DM). The neutral detergent fiber (NDF) ranged from 292.8 to 517.5 g/kg DM while acid detergent fiber (ADF) ranged from 273.3 to 495.1 g/kg DM. The ash, ether extract, non-fibrous carbohydrate, neutral detergent insoluble nitrogen, and acid detergent insoluble nitrogen and CP were negatively correlated with methane production. Methane production was positively correlated with NDF, ADF, cellulose and hemi-cellulose. Tannin decreased GP, IVOMD, total volatile fatty acid and methane production. The observed low methanogenic potential and substantial ammonia generation of some of the browses might be potentially useful as rumen manipulating agents. However, a systematic evaluation is needed to determine optimum levels of supplementation in a mixed diet in order to attain a maximal depressing effect on enteric CH4 production with a minimal detrimental effect on rumen fermentation of poor quality roughage based diet.

ChemInform Abstract: In situ Generation of Ammonia for the Copper‐Catalyzed Synthesis of Primary Aminoquinolines.

AbstractFormamide acts as ammonia source in the copper‐catalyzed synthesis of primary aminoquinolines.

Caries-free subjects have high levels of urease and arginine deiminase activity.

ObjectivesThis study investigated the relationship between urease and arginine deiminase system (ADS) activities and dental caries through a cross-sectional study.Material and MethodsUrease and ADS activities were measured in saliva and plaque samples from 10 caries-free subjects and 13 caries-active. Urease activity was obtained from the ammonia produced by incubation of plaque and saliva samples in urea. ADS activity was obtained from the ammonia generated by the arginine-HCl and Tris-maleate buffer. Specific activity was defined as micromoles of ammonia per minute per milligram of protein. Shapiro-Wilk statistical test was used to analyze the distribution of the data, and Mann-Whitney test was used to determine the significance of the data.ResultsThe specific urease activity in saliva and plaque was significantly higher in individuals with low DMFT scores. ADS activity in saliva (6.050 vs 1.350, p=0.0154) and plaque (8.830 vs 1.210, p=0.025) was also higher in individuals with low DMFT scores.ConclusionsCaries-free subjects had a higher ammonia generation activity by urease and arginine deiminase system for both saliva and plaque samples than low caries-active subjects. High levels of alkali production in oral environment were related to caries-free subjects.

Ammonia Generation over TWC for Passive SCR NOX Control for Lean Gasoline Engines

A commercial three-way catalyst (TWC) was evaluated for ammonia (NH3) generation on a 2.0-liter BMW lean burn gasoline direct injection engine as a component in a passive ammonia selective catalytic reduction (SCR) system. The passive NH3 SCR system is a potential low cost approach for controlling nitrogen oxides (NOX) emissions from lean burn gasoline engines. In this system, NH3 is generated over a close-coupled TWC during periodic slightly rich engine operation and subsequently stored on an underfloor SCR catalyst. Upon switching to lean, NOX passes through the TWC and is reduced by the stored NH3 on the SCR catalyst. NH3 generation was evaluated at different air-fuel equivalence ratios at multiple engine speed and load conditions. Near complete conversion of NOX to NH3 was achieved at =0.96 for nearly all conditions studied. At the =0.96 condition, HC emissions were relatively minimal, but CO emissions were significant. Operation at AFRs richer than =0.96 did not provide more NH3 yield and led to higher HC and CO emissions. Results of the reductant conversion and consumption processes were used to calculate a representative fuel consumption of the engine operating with an ideal passive SCR system. The results show a 1-7% fuel economy benefit at more » various steady-state engine speed and load points relative to a stoichiometric engine operation. « less

In situ generation of ammonia for the copper-catalyzed synthesis of primary aminoquinolines

Primary aminoquinolines were synthesized from iodoquinolines in the presence of a copper(i) iodide catalyst and formamide as both solvent and source of ammonia generated in situ.

Reaction pathways and mechanism for ammonia formation and removal over palladium-based three-way catalysts: Multiple roles of CO

In-situ ammonia generation over a three-way catalyst is an important part of the “passive ammonia SCR” technology being developed at GM Global R&D as a low-cost alternative to the current lean NOx emission control technologies. The purpose of this laboratory reactor study is to clarify the reaction pathways and to identify/quantify the key controlling factors for the formation and destruction of ammonia over Pd-based three-way catalysts under realistic feedstream conditions simulating the exhaust from a lean gasoline engine operating at fuel-rich air–fuel ratios. In addition to the “full-feed” experiments, we also conducted some “simple-feed” experiments to better understand the NH3 formation process (via the NO+H2 reaction with and without CO) as well as the possible removal process of the NH3 formed (via the NH3+O2 reaction or NH3 decomposition). Of particular interest in this study are the multiple roles that CO plays in both the formation and destruction of NH3. It is also found that the presence of Rh and/or Ce in a Pd-based three-way catalyst decreases the amount of NH3 formation significantly under fuel-rich (net-reducing) conditions of practical interest.

Biodegradation of Cyanide Complex Compounds in Aqueous Media by Pseudomonas resinovorans

Abstract Biodegradation of some complex cyanide compounds, including sodium hexacyanoferrate (II) trihydrate [Na4Fe(CN)6·3H2O], potassium hexacyanoferrate (II) decahydrate [K4Fe(CN)6·10H2O], and potassium cyano-argentate [KAg(CN)2] by free cells of Pseudomonas resinovorans strain, was investigated in aqueous suspension as a function of pH, cyanide concentration, and initial glucose concentration. The minimum inhibition concentration (MIC) for each cyanide compound was determined while bacterial growth, ammonia generation, and glucose utilization were monitored during the experiments. The results indicate that P. resinovorans is able to degrade both the potassium and sodium cyanide complexes by using these compounds as sources of nitrogen. However, KAg(CN)2 was observed to inhibit the growth of the bacteria. The MIC values were determined to be 25 mM (10.55 g/L) and 75 mM (36.3 g/L) for K4Fe(CN)6·3H2O and Na4Fe(CN)6·10H2O, respectively, for P. resinovorans, whereas the maximum ammonia generated during cyan...

Nitrate removal by Fe0/Pd/Cu nano-composite in groundwater

Nitrate pollution in groundwater shows a great threat to the safety of drinking water. Chemical reduction by zero-valent iron is being considered as a promising technique for nitrate removal from contaminated groundwater. In this paper, Fe0/Pd/Cu nano-composites were prepared by the liquid-phase reduction method, and batch experiments of nitrate reduction by the prepared Fe0/Pd/Cu nano-composites under various operating conditions were carried out. It has been found that nano-Fe0/Pd/Cu composites processed dual functions: catalytic reduction and chemical reduction. The introduction of Pd and Cu not only improved nitrate removal rate, but also reduced the generation of ammonia. Nitrate removal rate was affected by the amount of Fe0/Pd/Cu, initial nitrate concentration, solution pH, dissolved oxygen (DO), reaction temperature, the presence of anions, and organic pollutant. Moreover, nitrate reduction by Fe0/Pd/Cu composites followed the pseudo-first-order reaction kinetics. The removal rate of nitrate and total nitrogen were about 85% and 40.8%, respectively, under the reaction condition of Fe–6.0%Pd–3.0%Cu amount of 0.25 g/L, pH value of 7.1, DO of 0.42 mg/L, and initial nitrate concentration of 100 mg/L. Compared with the previous studies with Fe0 alone or Fe–Cu, nano-Fe–6%Pd–3%Cu composites showed a better selectivity to N2.

Symptomatic hyperammonemia after lung transplantation: Lessons learnt

Hyperammonemia, post-orthotopic lung transplantation, is a rare but mostly fatal complication. Various therapies, including those to decrease ammonia generation, increase nitrogen excretion, and several dialytic methods for removing ammonia have been tried. We describe three lung transplant recipients who developed acute hyperammonemia early after transplantation. Two of the three patients survived after a multidisciplinary approach including discontinuation of drugs, which impair urea cycle, aggressive ammonia reduction with prolonged daily intermittent hemodialysis (HD), and overnight slow low-efficiency dialysis in conjunction with early weaning of steroids and other therapeutic measures. Our experience suggests that early initiation of dialysis, high dialysis dose, increased frequency, and HD preferably to less efficient modalities increases survival in these patients.

Deactivation of nanoscale zero-valent iron by humic acid and by retention in water

The effects of the deactivation of nanoscale zero-valent iron (NZVI), induced by humic acid (HA) and by the retention of NZVI in water, on nitrate reduction were investigated using a kinetic study. Both the nitrate removal and generation of ammonia were significantly inhibited as the HA adsorption amount and retention time were increased. However, HA removal was greatly enhanced when the NZVI was used after 1 d or 25 d of retention in water. The results are caused by the formation of iron oxides/hydroxides, which increased the specific surface area and the degree of NZVI aggregation which was observed by transmission electron microscopy (TEM). However, the nitrate reduction was greater at the beginning of reaction in the presence of HA when fresh NZVI was used, because of the enhanced electron transfer by the HA in bulk phase and on NZVI surface as train sequences. The pseudo second order adsorption kinetic equation incorporating deactivation and a Langmuir-Hinshelwood (LH) type kinetic equation provided accurate descriptions of the nitrate removal and ammonia generation, respectively. The deactivation constant and the reaction rate constant of the LH type kinetic equation were strongly correlated with the HA amount accumulated on NZVI. These results suggest that the HA accumulation on the NZVI surface reactive sites plays the dominant role in the inhibition and the inhibition can be described successfully using the deactivation model. The HA accumulation on NZVI was verified using TEM.