Nitrogen-15 and Oxygen-18 Natural Abundance of Potassium Chloride Extractable Soil Nitrate Using the Denitrifier Method

In agroecosystems, most isotopic investigations of NO3- involve the use of tracers that are artificially enriched in 15N. Although the dual isotope composition of NO3-— d15N and d18O is especially beneficial for understanding the origin and fate of NO3-, its use for KCl-extractable soil NO3- has been hampered by the lack of a suitable analytical technique. Our objective was to test whether the denitrifier method, whereby NO3- is reduced to N2O before mass spectrometric analysis, can be used to determine the N and O isotopic composition of NO3- from 2 M KCl soil extracts. Several internationally accepted NO3- standards were dissolved in 2 M KCl, the conventional extractant for soil inorganic N, and inoculated with the bacterial strain Pseudomonas aureofaciens (ATCC no. 13985). The standard deviation of the NO3- standards analyzed did not exceed 0.2‰ for d15N and 0.3‰ for d18O values. After appropriate corrections, differences between our measured and consensus d15N and d18O values of standard NO3- generally were within the standard deviations given for the consensus values. Both d15N and d18O values were reproducible among separate analytical runs. The method was also tested on genuine 2 M KCl extracts from unfertilized and fertilized soils. Depending on N fertilization, the soils had distinct d15N and d18O values, which were attributed to amendment with NH4NO3 fertilizer. Hence, our data indicate that the denitrifier method provides a fast, reliable, precise, and accurate way of simultaneously analyzing the natural abundances of 15N and 18O in KCl-extractable soil NO3-.

Nitrile-Functionalized Pyridinium, Pyrrolidinium, and Piperidinium Ionic Liquids

Two series of 1-alkylpyridinium and N-alkyl-N-methylpiperidinium ionic liquids fiinctionalized with a nitrile group at the end of the alkyl chain have been synthesized. Structural modifications include a change of the alkyl spacer length between the nitrile group and the heterocycle of the cationic core, as well as adding methyl or ethyl substituents on different positions of the pyridinium ring. The anions are the bromide and the bis(trifluoromethylsulfonyl)imide ion. All the bis(trifluoromethylsulfonyl)imide salts as well as the bromide salts with a long alkyl spacer were obtained as viscous liquids at room temperature, but some turned out to be supercooled liquids. In addition, pyrrolidinium and piperidinium ionic liquids with two nitrile functions attached to the heterocyclic core have been prepared. The crystal structures of seven pyridinium bis(trifluoromethylsulfonyl)imide salts are reported. Quantum chemical calculations have been performed on model cations and ion pairs with the bis(trifluoromethylsulfonyl)imide anion. A continuum model has been used to take solvation effects into account. These calculations show that the natural partial charge on the nitrogen atom of the nitrile group becomes more negative when the length of the alkyl spacer between the nitrile functional group and the heterocyclic core of the cation is increased. Methyl or methoxy substituents on the pyridinium ring slightly increase the negative charge on the nitrile nitrogen atom due to their electron-donating abilities. The position of the substituent (ortho, meta, or para) has only a very minor effect on the charge of the nitrogen atom. The N-15 NMR spectra of the bis(trifluoromethylsulfonyl)imide ionic liquids were recorded with the nitrogen-15 nucleus at its natural abundance. The chemical shift of the N-15 nucleus of the nitrile nitrogen atom could be correlated with the calculated negative partial charge on the nitrogen atom.

Insight into the key aspects of the regeneration process in the NOx storage reduction (NSR) reaction probed using fast transient kinetics coupled with isotopically labelled (NO)-N-15 over Pt and Rh-containing Ba/Al2O3 catalysts

For the first time, the coupling of fast transient kinetic switching and the use of an isotopically labelled reactant (15NO) has allowed detailed analysis of the evolution of all the products and reactants involved in the regeneration of a NOx storage reduction (NSR) material. Using realistic regeneration times (ca. 1 s) for Pt, Rh and Pt/Rh-containing Ba/Al2O3 catalysts we have revealed an unexpected double peak in the evolution of nitrogen. The first peak occurred immediately on switching from lean to rich conditions, while the second peak started at the point at which the gases switched from rich to lean. The first evolution of nitrogen occurs as a result of the fast reaction between H2 and/or CO and NO on reduced Rh and/or Pt sites. The second N2 peak which occurs upon removal of the rich phase can be explained by reaction of stored ammonia with stored NOx, gas phase NOx or O2. The ammonia can be formed either by hydrolysis of isocyanates or by direct reaction of NO and H2.

The study highlights the importance of the relative rates of regeneration and storage in determining the overall performance of the catalysts. The performance of the monometallic 1.1%Rh/Ba/Al2O3 catalyst at 250 and 350 °C was found to be dependent on the rate of NOx storage, since the rate of regeneration was sufficient to remove the NOx stored in the lean phase. In contrast, for the monometallic 1.6%Pt/Ba/Al2O3 catalyst at 250 °C, the rate of regeneration was the determining factor with the result that the amount of NOx stored on the catalyst deteriorated from cycle to cycle until the amount of NOx stored in the lean phase matched the NOx reduced in the rich phase. On the basis of the ratio of exposed metal surface atoms to total Ba content, the monometallic 1.6%Pt/Ba/Al2O3 catalyst outperformed the Rh-containing catalysts at 250 and 350 °C even when CO was used as a reductant.

Electroreduction of oxygen in a series of room temperature ionic liquids composed of group 15-centered cations and anions

The electrochemical reduction of oxygen is reported in four room temperature ionic liquids (RTILs) based on quaternary alkyl -onium cations and heavily fluorinated anions in which the central atom is either nitrogen or phosphorus. Data were collected using cyclic voltammetry and potential step chronoamperometry at gold, platinum, and glassy carbon disk electrodes of micrometer dimension under water-free conditions at a controlled temperature. Analysis via fitting, to appropriate theoretical equations was then carried out to obtain kinetic and thermodynamic information pertaining to the electrochemical processes observed. In the quaternary ammonium electrolytes, reduction of oxygen was found to occur reversibly to give stable superoxide, in an analogous manner to that seen in conventional aprotic solvents such as dimethyl sufoxide and acetonitrile. The most significant difference is in the relative rate of diffusion; the diffusion coefficients of oxygen in the RTILs are an order of magnitude lower than in common organic solvents, and for superoxide these values are reduced by a further factor of 10. In the quaternary phosphonium ionic liquids, however, more complex voltammetry is observed, akin to that expected for the reduction of oxygen in acidified organic media. This is shown to be consistent with the occurrence of a proton abstraction reaction between the electrogenerated superoxide and quaternary alkyl phosphonium cations following the initial electron transfer.

Small genetic differences between ericoid mycorrhizal fungi affect nitrogen uptake by Vaccinium

Ericoid mycorrhizal fungi have been shown to differ in their pattern of nitrogen (N) use in pure culture. Here, we investigate whether this functional variation is maintained in symbiosis using three ascomycetes from a clade not previously shown to include ericoid mycorrhizal taxa. Vaccinium macrocarpon and Vaccinium vitis-idaea were inoculated with three fungal strains known to form coils in Vaccinium roots, which differed in their patterns of N use in liquid culture. (15)N was used to trace the uptake of -N, -N and glutamine-N into shoots. (15)N transfer differed among the three fungal strains, including two that had identical internal transcribed spacer (ITS) sequences, and was quantitatively related to fungal growth in liquid culture at low carbon availability. These results demonstrate that functional differences among closely related ericoid mycorrhizal fungi are maintained in symbiosis with their hosts, and suggest that N transfer to plant shoots in ericoid mycorrhizas is under fungal control.

Electron paramagnetic resonance studies of nitrogen interstitial defects in diamond

We report on electron paramagnetic resonance (EPR) studies of nitrogen doped diamond that has been N-15 enriched, electron irradiated and annealed. EPR spectra from two new nitrogen containing S = 1/2 defects are detected and labelled WAR9 and WAR10. We show that the properties of these defects are consistent with them being the < 001 >-nitrogen split interstitial and the < 001 >-nitrogen split interstitial-< 001 >-carbon split interstitial pair, respectively. We also provide an explanation for why these defects have previously eluded discovery.

Hyperfine interaction in the ground state of the negatively charged nitrogen vacancy center in diamond

The N-14, N-15, and C-13 hyperfine interactions in the ground state of the negatively charged nitrogen vacancy (NV-) center have been investigated using electron-paramagnetic-resonance spectroscopy. The previously published parameters for the N-14 hyperfine interaction do not produce a satisfactory fit to the experimental NV- electron-paramagnetic-resonance data. The small anisotropic component of the NV- hyperfine interaction can be explained from dipolar interaction between the nitrogen nucleus and the unpaired-electron probability density localized on the three carbon atoms neighboring the vacancy. Optical spin polarization of the NV- ground state was used to enhance the electron-paramagnetic-resonance sensitivity enabling detailed study of the hyperfine interaction with C-13 neighbors. The data confirmed the identification of three equivalent carbon nearest neighbors but indicated the next largest C-13 interaction is with six, rather than as previously assumed three, equivalent neighboring carbon atoms.

Electron paramagnetic resonance studies of the neutral nitrogen vacancy in diamond

Despite the numerous experimental and theoretical studies on the negatively charged nitrogen vacancy center (NV-) in diamond and the predictions that the neutral nitrogen vacancy center (NV0) should have an S=1/2 ground state, NV0 has not previously been detected by electron paramagnetic resonance (EPR). We report new EPR data on a trigonal nitrogen-containing defect in diamond with an S=3/2 excited state populated via optical excitation. Analysis of the spin Hamiltonian parameters and the wavelength dependence of the optical excitation leads to assignment of this S=3/2 state to the (4)A(2) excited state of NV0. This identification, together with an examination of the electronic structure of the NV centers in diamond, provides a plausible explanation for the lack of observation (to date) of an EPR signal from the NV0 ground state.

Reactions of nitrogen and oxygen surface groups in nanoporous carbons under inert and reducing atmospheres

The reactions of surface functional groups have an important role in controlling conversion of char nitrogen to NOx during coal combustion. This study involved an investigation of the thermal stability and reactions of nitrogen surface functional groups in nanoporous carbons. Four suites of carbons, which were used as models for coal chars, were prepared with a wide range of nitrogen and oxygen contents and types of functional groups. The porous structures of the carbons were characterized by gas adsorption methods while chemical analysis, X-ray photoelectron spectroscopy, and X-ray near edge structure spectroscopy were used to characterize the surface functional groups. Temperature programmed desorption and temperature programmed reduction methods were used to study the reactivity of the surface functional groups during heat treatment under inert and reducing conditions. Heat treatment studies show that the order of stability of the functional groups is quaternary nitrogen > pyridinic > pyrrolic > pyridine N-oxide. Pyridine N-oxide surface groups desorb NO and form N-2 via surface reactions at low temperature. Pyrrolic and pyridinic functional groups decompose and react with surface species to give NH3, HCN, and N-2 as desorption products, but most pyrrolic groups are preferentially converted to pyridinic and quaternary nitrogen. The main desorption product is N-2. Approximately 15-40 wt % of the original nitrogen was retained in the carbons mainly as quaternary nitrogen after heat treatment to 1673 K. The results are discussed in terms of decomposition ranges for surface functional groups and reaction mechanisms of surface species.

Adsorption of aqueous metal ions on oxygen and nitrogen functionalized nanoporous activated carbons

In this study, the adsorption characteristics of two series of oxygen and nitrogen functionalized activated carbons were investigated. These series were a low nitrogen content(similar to 1 wt % daf) carbon series derived from coconut shell and a high nitrogen content (similar to 8 wt % daf) carbon series derived from polyacrylonitrile. In both series, the oxygen contents were varied over the range similar to 2-22 wt % daf. The porous structures of the functionalized activated carbons were characterized using N-2 (77 K) and CO2 (273 K) adsorption. Only minor changes in the porous structure were observed in both series. This allowed the effect of changes in functional group concentrations on metal ion adsorption to be studied without major influences due to differences in porous structure characteristics. The surface group characteristics were examined by Fourier transform infrared (FTIR) spectroscopy, acid/base titrations, and measurement of the point of zero charge (pH(PZC)). The adsorption of aqueous metal ion species, M2+(aq), on acidic oxygen functional group sites mainly involves an ion exchange mechanism. The ratios of protons displaced to the amount of M2+(aq) metal species adsorbed have a linear relationship for the carbons with pH(PZC) <= 4.15. Hydrolysis of metal species in solution may affect the adsorption of metal ion species and displacement of protons. In the case of basic carbons, both protons and metal ions are adsorbed on the carbons. The complex nature of competitive adsorption between the proton and metal ion species and the amphoteric character of carbon surfaces are discussed in relation to the mechanism of adsorption.

A fast transient kinetic study of the effect of H-2 on the selective catalytic reduction of NOx with octane using isotopically labelled (NO)-N-15

The H-2-assisted hydrocarbon selective catalytic reduction (HC-SCR) of NO, was investigated using fast transient kinetic analysis coupled with isotopically labelled (NO)-N-15. This allowed monitoring of the evolution of products and reactants during switches of H-2 in and out of the SCR reaction mix. The results obtained with a time resolution of less than 1 s showed that the effect on the reaction of the removal or addition of H-2 was essentially instantaneous. This is consistent with the view that H-2 has a direct chemical effect on the reaction mechanism rather than a secondary one through the formation of "active" Ag clusters. The effect of H-2 partial pressure was investigated at 245 degrees C, it was found that increasing partial pressure of H-2 resulted in increasing conversion of NO and octane. It was also found that the addition of H-2 at 245 degrees C had different effects on the product distribution depending on its partial pressure. The change of the nitrogen balance over time during switches in and out of hydrogen showed that significant quantities of N-containing species were stored when hydrogen was introduced to the system. The positive nitrogen balance on removal of H-2 from the gas phase showed that these stored species continued to react after removal of hydrogen to form N-2. (c) 2006 Elsevier Inc. All rights reserved.

Lovastatin biosynthesis depends on the carbon-nitrogen proportion: model development and controller design

Lovastatin biosynthesis depends on the relative concentrations of dissolved oxygen and the carbon and nitrogen resources. An elucidation of the underlying relationship would facilitate the derivation of a controller for the improvement of lovastatin yield in bioprocesses. To achieve this goal, batch submerged cultivation experiments of lovastatin production by Aspergillus flavipus BICC 5174, using both lactose and glucose as carbon sources, were performed in a 7 liter bioreactor and the data used to determine how the relative concentrations of lactose, glucose, glutamine and oxygen affected lovastatin yield. A model was developed based on these results and its prediction was validated using an independent set of batch data obtained from a 15-liter bioreactor using five statistical measures, including the Willmott index of agreement. A nonlinear controller was designed considering that dissolved oxygen and lactose concentrations could be measured online, and using the lactose feed rate and airflow rate as process inputs. Simulation experiments were performed to demonstrate that a practical implementation of the nonlinear controller would result in satisfactory outcomes. This is the first model that correlates lovastatin biosynthesis to carbon-nitrogen proportion and possesses a structure suitable for implementing a strategy for controlling lovastatin production.

Oxygen reduction reaction mechanism on nitrogen-doped graphene:A density functional theory study

Nitrogen-doped graphene (N-graphene) was reported to exhibit a good activity experimentally as an electrocatalyst of oxygen reduction reaction (ORR) on the cathode of fuel cells under the condition of electropotential of similar to 0.04 V (vs. NNE) and pH of 14. This material is promising to replace or partially replace the conventionally used Pt. In order to understand the experimental results. ORR catalyzed by N-graphene is studied using density functional theory (DFT) calculations under experimental conditions taking the solvent, surface adsorbates, and coverages into consideration. Two mechanisms, i.e., dissociative and associative mechanisms, over different N-doping configurations are investigated. The results show that N-graphene surface is covered by O with 1/6 monolayer, which is used for reactions in this work. The transition state of each elementary step was identified using four different approaches, which give rise to a similar chemistry. A full energy profile including all the reaction barriers shows that the associative mechanism is more energetically favored than the dissociative one and the removal of O species from the surface is the rate-determining step. (C) 2011 Elsevier Inc. All rights reserved.

Organo-mineral complexation alters carbon and nitrogen cycling in stream microbial assemblages

Inland waters are of global biogeochemical importance receiving carbon inputs of ~ 4.8 Pg C y^-1. Of this 12 % is buried, 18 % transported to the oceans, and 70 % supports aquatic secondary production. However, the mechanisms that determine the fate of organic matter (OM) in these systems are poorly defined. One important aspect is the formation of organo-mineral complexes in aquatic systems and their potential as a route for OM transport and burial vs. their use potential as organic carbon (C) and nitrogen (N) sources. Organo-mineral particles form by sorption of dissolved OM to freshly eroded mineral surfaces and may contribute to ecosystem-scale particulate OM fluxes. We tested the availability of mineral-sorbed OM as a C & N source for streamwater microbial assemblages and streambed biofilms. Organo-mineral particles were constructed in vitro by sorption of ¹³C:¹⁵N-labelled amino acids to hydrated kaolin particles, and microbial degradation of these particles compared with equivalent doses of ¹³C:¹⁵N-labelled free amino acids. Experiments were conducted in 120 ml mesocosms over 7 days using biofilms and streamwater sampled from the Oberer Seebach stream (Austria), tracing assimilation and mineralization of ¹³C and ¹⁵N labels from mineral-sorbed and dissolved amino acids.Here we present data on the effects of organo-mineral sorption upon amino acid mineralization and its C:N stoichiometry. Organo-mineral sorption had a significant effect upon microbial activity, restricting C and N mineralization by both the biofilm and streamwater treatments. Distinct differences in community response were observed, with both dissolved and mineral-stabilized amino acids playing an enhanced role in the metabolism of the streamwater microbial community. Mineral-sorption of amino acids differentially affected C & N mineralization and reduced the C:N ratio of the dissolved amino acid pool. The present study demonstrates that organo-mineral complexes restrict microbial degradation of OM and may, consequently, alter the carbon and nitrogen cycling dynamics within aquatic ecosystems.