Nitrogen-15 Fractionation in the Thermal Decomposition of Nitrous Oxide of Natural Isotopic Composition

Abstract

The ¹⁵N fractionation in the thermal decompostion of nitrous oxide (N₂O) of natural isotopic composition has been investigated in quartz reaction vessel in the temperature interval 888–1073K. The formulas relating the observed experimentally ¹⁵N fractionations with the primary ¹⁵N kinetic isotope effect, (k ¹⁴/k ¹⁵)_p for ¹⁴N¹⁵N¹⁶O, and secondary ¹⁵N kinetic isotope effect, (k ¹⁴/k ¹⁵)_s for ¹⁵N¹⁴N¹⁶O, have been derived. The experimentally estimated ¹⁵N kinetic isotope effects have been compared with the primary and secondary ¹⁵N kinetic isotope effects calculated with the absolute rate theory formulations applied to linear three atom molecules. A good agreement was found for the primary ¹⁵N kinetic isotope effect, (k ¹⁴/k ¹⁵)_p, in the temperature interval 888–1007K. But at 1073K the decompositions of N₂O, accompanied by NO (nitric oxide) formation proceed with a twice times smaller primary kinetic isotope effect, (k ¹⁴/k ¹⁵)_p of 1.0251 ± 0.0009, only, suggesting the nonlinear transition state structures with participation of the fourth external atom at high temperature decompositions of nitrous oxide. The nitrogen isotope effects determined in this study correlate well with nitrogen isotope fractionations observed in the natural biological, earth and atmospheric processes.     

15N Isotopic Effects on the Raman Spectra of Tribromoacetamide

Abstract

¹⁵N-Tribromoacetamide has been synthesized with an isotopic content of 99, 4%, its Raman spectra have been recorded in the range 4.000–50 cm^?1. The isotopic shifts arising from ¹⁵N have been determined and interpreted. We have assigned the vibrational spectra of Br₃CCONH₂ and some overtones, combinations and difference bands. The molecular structure of tribromoacetamide has been studied employing the Ab Initio teoretical calculations and the Teller - Redlich isotopic product rule has been applied by assuming these geometrical parameters:

rCN = 1.4623 Å, rCC = 1.6014 Å, rBrC = 1.9468 Å, rCO = 1.2144 Å, rNH = 1.0292 Å, C-C-Br = 108.83320, C-C-0:118.2440, C-C-N:120.4137, C-N-H:110.45930     

15N Distribution in Wheat and Chemical Fractionation of Root-Borne 15N in the Soil

Abstract

Spring wheat plants were grown in split-root containers and labelled with ¹⁵N by fertilizing one compartment of the container with ¹⁵NH₄ ¹⁵NO₃ (95 at.-% ¹⁵N exc.). After the harvest, approx. 90% of the ¹⁵N incorporated by the plants were found in the shoots and 3% in the roots; approx. 7% had been released into the soil of the unlabelled compartment. The ¹⁵N in the soil of the unlabelled compartment was extracted with KCl and hydrolysed with HCl. Approx. 60% of the ¹⁵N was found in the hydrolysable organic N pool of the soil and 9% in the fraction of the soluble and exchangeable inorganic nitrogen.     

Nitrous oxide conversion in laminar premixed flames of CH4 + O2 + Ar

Experimental measurements of the adiabatic burning velocity in neat and NO formation in CH₄ + O₂ + Ar flames doped with small amounts of N₂O are presented. The oxygen content in the oxidizer was varied from 15 to 17%. Non-stretched flames were stabilized on a perforated plate burner at 1 atm. The Heat Flux method was used to determine burning velocities under conditions when the net heat loss of the flame is zero. Adiabatic burning velocities of methane + oxygen + argon mixtures were found in satisfactory agreement with the modeling. The NO concentrations in the flames doped with N₂O (100 ppm in the argon stream before mixing) were measured in the burnt gases at a fixed distance from the burner using probe sampling. Axial profiles of [NO] were found insensitive to the downstream heat losses. Experimental dependencies of [NO] versus equivalence ratio had a maximum between φ = 1.1 and 1.2. Calculated concentrations of NO were in good agreement with the measurements. In lean flames calculated concentrations of NO strongly depends on the rate constant of reaction N₂O + O=NO + NO if too high values proposed in the literature are employed. These new experimental data thus allowed for validation of the key reactions of the nitrous oxide mechanism of NO formation in flames.     

Fourier-transform spectroscopy of NNO in the 3500-9000 cm region

The Fourier-transform absorption spectrum of ¹⁵N¹⁴N¹⁶O-enriched nitrous oxide has been recorded at the Doppler limited resolution in the spectral range 3500-9000 cm⁻¹. More than 15 000 transitions of ¹⁵N¹⁴N¹⁶O were observed and assigned based on the global effective Hamiltonian model. The band-by-band analysis led to the determination of the ro-vibrational parameters of a total of 133 bands. Among these bands, 103 were newly observed, and the rotational analysis of 30 others were significantly extended and improved.     

Enrichment of the nitrogen atomic component with the <Superscript>15</Superscript>N isotope in a post-discharge zone

Isotope atomic composition in the post-discharge zone of a pulsed discharge in a nitrogen flow was studied by electron paramagnetic resonance. It is shown that, while the atomic concentration in the post-discharge zone decreases, the relative content of the ¹⁵N isotope increases more than 30 times compared to its natural abundance. Such a high isotope enrichment exceeds more than fourfold the corresponding maximal value that is predicted for the nitrogen atoms by the existing theoretical model. Analysis of the experimental results shows that the isotope-selective dissociation of nitrogen molecules proceeds in the post-discharge zone after the most part of atoms created in the discharge zone had recombined at the tube surface. A mechanism that explains that a nitrogen isotope enrichment as high as that is quite possible is proposed.     

High-resolution infrared spectroscopy of NNO and NNO in the 1200–3500 cm region

We present a continuation of our investigation of the second most abundant isotopic species of nitrous oxide, ¹⁴N¹⁵N¹⁶O and ¹⁵N¹⁴N¹⁶O, in the infrared (IR). Our two previous contributions looked at the 3500–9000 cm⁻¹ region for ¹⁴N¹⁵N¹⁶O and ¹⁵N¹⁴N¹⁶O, respectively, in the 3500–9000 cm⁻¹ region. The use of highly enriched isotopologue samples in this study allowed us to go further into the IR, down to 1200 cm⁻¹. A total of 2 2742 transitions have been assigned based on the effective Hamiltonian model, with 108 of them being reported here for the first time. Rovibrational analyses of 98, 101, 8, 3, 6, 1 and 1 bands for the ¹⁴N¹⁵N¹⁶O, ¹⁵N¹⁴N¹⁶O, ¹⁵N¹⁵N¹⁶O, ¹⁴N¹⁵N¹⁸O, ¹⁵N¹⁴N¹⁸O, ¹⁴N¹⁵N¹⁷O and ¹⁵N¹⁴N¹⁷O isotopologues, respectively, were also performed.     

The position dependent 15N enrichment of nitrous oxide in the stratosphere.

The position dependent 15N fractionation of nitrous oxide (N2O), which cannot be obtained from mass spectrometric analysis on molecular N2O itself, can be determined with high precision using isotope ratio mass spectrometry on the NO+ fragment that is formed on electron impact in the source of an isotope ratio mass spectrometer. Laboratory UV photolysis experiments show that strong position dependent 15N fractionations occur in the photolysis of N2O in the stratosphere, its major atmospheric sink. Measurements on the isotopic composition of stratospheric N2O indeed confirm the presence of strong isotope enrichments, in particular the difference in the fractionation constants for 15N14NO and 14N15NO. The absolute magnitudes of the fractionation constants found in the stratosphere are much smaller, however, than those found in the lab experiments, demonstrating the importance of dynamical and also additional chemical processes like the reaction of N2O with O(1D).     

Fourier transform spectroscopy of N2O weak overtone transitions in the 1-2 μm region

The absorption spectrum of the natural sample of nitrous oxide has been recorded at Doppler limited resolution with a Fourier-transform spectrometer in the spectral range 5000-10 000 cm⁻¹. Ten cold bands (8Σ − Σ and 2Σ − Π), thirteen hot bands (11Π − Π, Σ − Σ, and Δ − Δ) of ¹⁴N₂¹⁶O and the 3ν₃ band of ¹⁴N¹⁵N¹⁶O have been newly detected. The uncertainty of the line position determination is estimated to be about 0.005 cm⁻¹ for unblended lines. The assignment of the spectrum has been done with the help of the prediction performed within the framework of the polyad model of effective Hamiltonian. The spectroscopic parameters G_v, B_v, D_v, H_v, and q_v have been determined for all newly detected bands. The line intensities of 13 weak bands have been measured. The uncertainty of the obtained line intensity values varies from 7 to 13%.     

The Effect of Zinc Oxide and Calcium Carbonate Nanoparticles on the Thermal Conductivity of Polypropylene

The thermal conductivity (TC) of compression-moulded polypropylene (PP) and PP filled with 5–15% zinc oxide (ZnO) or calcium carbonate (CaCO₃) nanoparticles, prepared by extrusion, was studied using a thermal conductivity analyzer (TCA). The effect of nanoparticle content and crystallinity on the thermal conductivity was investigated using conventional methods, including SEM, XRD, and DSC. The incorporation of nanoparticles improved the crystallinity and thermal conductivity simultaneously. The experimental TC values of the PP nanocomposites with different level of nanoparticles concentration showed a linear increase with an increase in crystallinity. The TC improvement in PP/ZnO nanocomposite was greater than that of PP/calcium carbonate nanocomposites. This fact can be attributed to the intrinsic, better thermal conductivity of the ZnO nanoparticles. Several models were used for prediction of the TC in the nanocomposites. In the PP/ZnO nanocomposites the TC values correlated well with the values predicted by the Series, Maxwell, Lewis and Nielson, Bruggeman, and De Loor models up to 10 wt%.     

Fourier-transform spectroscopy of NNO in the 3800-9000 cm region and global modeling of its absorption spectrum

The absorption spectrum of ¹⁴N¹⁵N¹⁶O-enriched sample of nitrous oxide has been recorded at Doppler limited resolution with a Fourier-transform spectrometer in the spectral range 3500-9000 cm⁻¹. More than 12 000 transitions of ¹⁴N¹⁵N¹⁶O were observed and ro-vibrationally assigned on the basis of the global effective Hamiltonian model. The band-by-band analysis led to the determination of the ro-vibrational parameters of a total of 107 bands. Among the 107 bands, 80 are newly observed, for 27 others the rotational analysis is significantly extended and improved. The effective Hamiltonian parameters are determined from global fitting to the observed line positions presented in this paper and collected from the literature. As a result, a set of 117 obtained effective Hamiltonian parameters reproduces 16 134 observed line positions of 148 bands with RMS of 0.0014 cm⁻¹.     

氧化物分子束外延技术及其在关联材料电子态研究中的应用

氧化物分子束外延薄膜和异质结生长技术近年来迅速发展,人们已实现以单原子层的精度来精确生长多种复杂量子材料,有力地推动了铜氧化物高温超导电性、二维电子气、氧化物电子学和自旋电子学器件等领域的研究.文章介绍了氧化物分子束外延的技术关键,并以La1-xSrxMnO3薄膜为例,介绍了钙钛矿结构的氧化物薄膜生长和刻画.特别是文章作者通过建立超高真空下的原位样品传送系统,可把薄膜样品直接传送到角分辨光电子能谱仪中,实现了薄膜的原位电子结构测量.所测得的La1-xSrxMnO3的电子结构与能带计算结果较为相符.而此类立方结构的、不可解理材料的电子结构,过去往往是无法直接测量的.     

Long-term evolution in the tropospheric concentration of chlorofluorocarbon 12 (CCl2F2) derived from high-spectral resolution infrared solar absorption spectra: retrieval and comparison with in situ surface measurements

The average tropospheric volume mixing ratios of chlorofluorocarbon 12 (CCl₂F₂) have been retrieved from high-spectral resolution ground-based infrared solar-absorption spectra recorded from March 1982 to October 2003 with the McMath Fourier transform spectrometer at the US National Solar Observatory facility on Kitt Peak in southern Arizona (31.9°N, 111.6°W, 2.09 km altitude). The retrievals are based on fits to the unresolved ν₈ band Q-branches near using the SFIT2 retrieval algorithm. The annual increase rate was equal to (16.88±1.37) parts per trillion (10^-12) by volume at the beginning of the time series, March 1982, or (4.77±0.04)%, 1 sigma, declining progressively to (2.49±1.24) parts per trillion, by volume at the end, October 2003, or (0.46±0.24)%, 1 sigma. Average tropospheric mixing ratios from the solar spectra have been compared with average surface flask and in situ sampling measurements from the Climate Monitoring and Diagnostics Laboratory (CMDL) station at Niwot Ridge, CO, (USA) (40.0°N, 105.5°W, 3013 m altitude). The average ratio and standard deviation of the monthly means of the retrieved tropospheric mixing ratios relative to the CMDL surface mixing ratios is (1.01±0.03) for the overlapping time period. Both datasets demonstrate the progressive impact of the Montreal protocol and its strengthening amendments on the trend of CCl₂F₂, though a tropospheric decrease has yet to be observed.     

The Fate of [15N]Ammonium and [15N]Nitrate in the Soil of a 140-Year-Old Spruce Stand (Picea Abies) in the Fichtelgebirge (NE-Bavaria)

Abstract

A ¹⁵N tracer-experiment was carried out in a 140-year-old spruce stand (Picea abies (L.) Karst.) in the Fichtelgebirge (NE-Bavaria, Germany). Highly enriched (98 at%) [¹⁵N]ammonium and [¹⁵N]nitrate were applied as tracers by simulation of a deposition of 41.3 mol N ha^?1 with 11 water m^?2. To examine seasonal variations of uptake by spruce and understorey vegetation, different plots were labelled in spring, summer and autumn 1994.

One aim of the present study was to perfect a method of preparation of soil extracts for isotope ratio mass spectrometry (IRMS) measurements. Ammonium and nitrate from soil extracts were prepared for IRMS measurements by steam distillation and subsequent freeze drying. Additionally, tracer distribution and transformations in the soil nitrogen pools were examined. Ammonium, nitrate and total nitrogen were examined in the organic layer and the upper 10 cm of the mineral soil during 3 months after the first tracer application in spring 1994.

In July 1994, three months after tracer application, 40% of the [¹⁵N]ammonium label and 29% of the [¹⁵N]nitrate label, respectively, were recovered in the total N pool of the investigated soil horizons. In the organic layer the L/Of horizon retained most of the recovered tracers. Nitrification, immobilisation and mineralisation occurred even under the conditions of high soil acidity at the study site.     

FIA—ICP—AES法测定土壤提取液中游离氧化铁的研究

研究了土壤提取液中游离氧化铁含量的ＦＩＡ－ＩＣＰ－ＡＥＳ测定法。考察了采术量以及提取剂（盐酸羟胺和草酯）的浓度对的影响。试验表明：如果选择５０μＬ采样环进样,并将盐酸羟爱和草酸的浓度控制在１０ｍｇ．ｍＬ＾－１以下,则进样顺畅,不出现喷雾嘴堵塞的现象,分析线的背景干扰也得到有效抑制。此法的回收率为９７．６％～１００％,ＲＳＤ≤３．５％。     

Evaluation of 15N Methods for the measurement of Denitrification in Soils

The precision of the ¹⁵N-emission and that of the ¹⁵N-balance methods was evaluated and both methods were compared in a denitrification experiment. ¹⁵N-analysis was performed with an isotope ratio mass spectrometer which was coupled to an elemental analyzer. The measuring sensitivity in soil and gas analysis was tested by analyzing ¹⁵N-standards. The detection limit for gas samples with two different procedures of ¹⁵N-gas analysis was δ¹⁵N = (4.5 ± 1.0)‰ and (0.5 ± 0.05)‰, respectively. The error in measurement was 19% and 12% respectively. ¹⁵N-analysis of a ¹⁵N-labelled soil (4.15 ppm ¹⁵N) resulted in a CV of 1.32%. The measurements had to be calibrated with soil standards because the ¹⁵N-values showed a continuous downward fluctuation in a range of 10–20% within several days, when only acetanilid was used for calibration. Mean ¹⁵N-losses which were determined with both methods during the denitrification experiment were in good agreement. The precision of the ¹⁵N-emission method was adequate in all variants of the experiment. The precision of the ¹⁵N-balance method however was unsatisfactory at low ¹⁵N-losses (0.2–2% of added ¹⁵N).     

Development of Oxidation Sources in Preparation of High-Tc Oxide Superconductor Thin Films Using the Molecular Beam Epitaxy Method

Film preparation of oxide superconductors, mainly of the 1-2-3 (RBa₂Cu₃O_x) and Bi-containing (Bi-Sr-Ca-Cu-O) systems, by evaporation of either metals or metal compounds by low pressure is summarized, with a particular focus on the development of oxidation sources essential to the technique. Oxidizing reagents that enable the oxidation of metal evaporates to take place in high (0·1 to 10_?3 Pa) or even ultra-high (<10_?5 Pa) vacuum are summarized using the experiments of those who tried to apply the molecular beam epitaxy method to atomically controlled fabrication of thin films of the material, especially for device processing. The evaporation in various kinds of oxidizing atmosphere, including the simple method of in situ annealing of the metal layers in oxygen to the more advanced in situ preparation of the films with strong oxidizing reagents such as atomic oxygen, ozone, nitric oxide, etc. along with the thermochemistry of the oxidation of metals by low pressure with these reagents is reviewed.     

聚环氧乙烷在水和叔丁醇溶液中分子构型变化的研究

在聚合物溶液中,聚合物单体和溶剂分子之间的相互作用会影响聚合物高分子的尺寸和结构。本文使用动态光散射实验系统研究了聚环氧乙烷在水+TBA二元混合溶液中的分子尺寸变化,实验结果表明聚环氧乙烷分子会呈现出收缩-膨胀的奇异性构型变化。本文也系统分析了产生该现象的原因,依次分析了在二元混合溶液中可能对聚合物分子尺寸产生影响三个原因:溶剂非理想性影响(Shultz-Flory理论)、临界涨落影响以及水+醇溶液所呈现出来的奇异性性质。结合这三个因素,本文较好地解释了实验所观测到的奇异现象。     

大气对激光传输的影响

本文分析了激光传输过程中大气这一传输介质对其的影响,由大气的成分出发,采用辐射传输理论描述了大气介质的吸收和散射特性,着重分析了其中对辐射影响最大的两种因素,即大气消光和大气湍流。并建立了大气传输系统的传递函数模型。最后通过LOWTRAN模拟软件包对本文所得的模型进行评估。     

The Fate of [(15)N]Ammonium and [(15)N]Nitrate in the Soil of a 140-Year-Old Spruce Stand (Picea Abies) in the Fichtelgebirge (NE-Bavaria)

Abstract A (15)N tracer-experiment was carried out in a 140-year-old spruce stand (Picea abies (L.) Karst.) in the Fichtelgebirge (NE-Bavaria, Germany). Highly enriched (98 at%) [(15)N]ammonium and [(15)N]nitrate were applied as tracers by simulation of a deposition of 41.3 mol N ha(-1) with 11 water m(-2). To examine seasonal variations of uptake by spruce and understorey vegetation, different plots were labelled in spring, summer and autumn 1994. One aim of the present study was to perfect a method of preparation of soil extracts for isotope ratio mass spectrometry (IRMS) measurements. Ammonium and nitrate from soil extracts were prepared for IRMS measurements by steam distillation and subsequent freeze drying. Additionally, tracer distribution and transformations in the soil nitrogen pools were examined. Ammonium, nitrate and total nitrogen were examined in the organic layer and the upper 10 cm of the mineral soil during 3 months after the first tracer application in spring 1994. In July 1994, three months after tracer application, 40% of the [(15)N]ammonium label and 29% of the [(15)N]nitrate label, respectively, were recovered in the total N pool of the investigated soil horizons. In the organic layer the L/Of horizon retained most of the recovered tracers. Nitrification, immobilisation and mineralisation occurred even under the conditions of high soil acidity at the study site.