Isotope analysis of hydrocarbons: trapping, recovering and archiving hydrocarbons and halocarbons separated from ambient air

It is argued that isotope analysis of atmospheric non-methane hydrocarbons (NMHCs) and, in particular, the analysis of the deuterium/hydrogen (D/H) ratio is valuable because the dominant self-cleansing property of the troposphere is based on the OH radical which removes, e.g., CH4 and other alkanes by H-atom abstraction, which induces large kinetic isotope effects. The major obstacle in applying D/H isotope analysis to atmospheric NMHCs is not only the low abundance of D itself but, in particular, the low concentrations of NMHCs in the parts per trillion range. We show how a selection of NMHCs can be quantitatively separated from 300 L air samples together with CO2 as carrier gas matrix, by using high efficiency cryogenic traps. After diluting the extracted NMHC mixtures with hydrocarbon free air, and determining the mixing ratios, good agreement with original whole air sample analysis exists for alkanes and several halocarbons. For unsaturated hydrocarbons and some other halocarbons the extraction and recovery yield under the given conditions fell considerably, as a function of boiling point. Furthermore, the mixture of NMHCs in the CO2 matrix is proven to remain unchanged over several years when conveniently stored in glass ampoules. The 'extracts' or 'concentrates' of condensables extracted from larger air samples will enable the D/H isotope analysis of ultra trace gases in the atmosphere.     

A Study of Synthesis, Immobilization and Catalytic Capability of Metalloporphyrin

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网络上两类物资联合最大流问题的极流特征

当网络上(诸如交通网络、通讯网络)有多种不同物资或信息同时分别从相应的发点输送到相应的收点,要求每条线路上各类物资或信息的输送量总和不超过线路的容量时,寻求所有物资的最大输送量的问题,就是所谓网络多种物资的最大流问题,这个问题在生产实际和理论上都有着重要的意义,1963年T.C.Hu提出了求两类物资联合最大流的标号方法,但是为了保证有限步达到最大流,要求边的容量是偶数。 本文是文献[3]的继续,用图论的语言描述了两类物资最大流问题极流的特征,并对标号方法作了一点修改,使得有限步得到最大流,或者在某一步得到极流后,保证以后的迭代是从极流到极流.这样因极流的个数是有限的,并且最大流总可以在极流上达到,从而保证了有限步内得到所要求的最大流,无须对边的容量作任何限制, 本文所提的算法是使图形特征很强的标号算法和线性规划的极点迭代结合起来,这就使得有可能把这种方法,推广到更大的一类问题中,例如,研究容量的改变对最大流量的影响。     

分子束研究GaAs和InP与氯的激光化学反应动态学

本文采用CW超声分子束和时间分辨质谱技术,研究了在紫外和可见(355nm和560nm)脉冲激光辐照下GaAs(100)和InP(100)表面与氯的激光化学反应动态学。由质谱和飞行时间谱测得反应的主要产物为GaCl_x和InCl_x(x=1,2),研究了激光波长和能量密度对产物飞行时间谱的影响,首次发现提高入射Cl₂分子的平动能对上述激光诱导气-固相反应有明显的增强作用。     

Saturation Effects and the Colored Pump Noise in a Dye Laser

We investigate the statistical properties of two single-mode dye-laser models-the colored-loss-noise model and the colored-gain-noise model. Analytic expressions of the probability,the mean and the variance of the steady-state laser intensity are obtained through the unified expansion theory [Phys. Rev. A43 (1991) 700]. By comparison we find that when the cavity decay rate for the electric field is large and the pump parameter a₀ is small, the differences of the results of the two laser models are small. Otherwise, the differences are large. And the correlation time of the noise has very obvious influence on the results of the two models.     

Renormalization of the inverse square potential

The quantum-mechanical D-dimensional inverse square potential is analyzed using field-theoretic renormalization techniques. A solution is presented for both the bound-state and scattering sectors of the theory using cutoff and dimensional regularization. In the renormalized version of the theory, there is a strong-coupling regime where quantum-mechanical breaking of scale symmetry takes place through dimensional transmutation, with the creation of a single bound state and of an energy-dependent s-wave scattering matrix element.     

Reporting small Delta 17O values: existing definitions and concepts

The three-isotope tracer Delta(17)O is increasingly used in atmospheric chemistry and other research areas. Thanks to the development of isotope-ratio mass spectrometry (IRMS), delta(17)O and delta(18)O can be determined with a precision of a few 0.01 per thousand, and values for Delta(17)O may be calculated with similar precision. However, interpreting small and precisely determined Delta(17)O values as a deviation from an expected mass-dependent fractionation process is not straightforward. Several aspects are of high importance. In the present paper we review existing definitions, formulas and some other aspects of Delta(17)O reporting. One of the most confusing aspects is a variance of definitions and corresponding formulas. While Delta(17)O is traditionally defined to characterise a data point, i.e. Delta(17)O is considered as a deviation from an expected mass-fractionation line, the recently introduced definition (Miller MF. Geochim. Cosmochim. Acta 2002; 66: 188) characterises a fractionation line itself, in terms of its ordinate intercept. The formulas corresponding to this definition gives a characteristic for a specific process. When the 'traditionally defined' Delta(17)O is in use, an expected fractionation processes--the key point for Delta(17)O reporting--should be defined and parameterised with the same accuracy as intended for reporting Delta(17)O. When Delta(17)O is reported for a data point, not only a value for lambda but an ordinate intercept of a reference fractionation line should be given with high accuracy. We note that defining a single fractionation process is hardly possible for many natural compounds. For such compounds we propose to use a phenomenological reference line, namely an isotope composition range of natural sources. Next, aspects of Delta(17)O comparison and mass-balance calculations are considered. All the aspects considered for Delta(17)O may be relevant for others three-isotope tracers, e.g. Delta(33)S.     

Continuous-flow isotope analysis of the deuterium/hydrogen ratio in atmospheric hydrogen

A convenient method is described for analyzing the deuterium/hydrogen (D/H) ratio of atmospheric molecular hydrogen (H(2)) based on mass spectrometric isotope-ratio monitoring. The method requires small amounts of air ( approximately 300 mL STP), is operated on-line, and comprises four steps: (1). the condensation of the air matrix at approximately 40 K; (2). the collection of the non-condensed components of the air sample (H(2), Ne, He, and traces of N(2)) in a 5 A molecular sieves pre-concentration trap at approximately 63 K; (3). gas chromatographic purification of H(2) in a flow of He; and (4) quantification of the D/H ratio in an isotope-ratio mass spectrometer. The precision of the determination of the D/H ratio is better than 2 per thousand, which is comparable to, or better than, that obtained by conventional duel-inlet off-line analysis. There are, however, discrepancies relative to the D/H ratios determined by conventional duel-inlet analysis. This is due to differences in peak shape between reference and sample air, depending on the amount of H(2) injected. Consequently, calibration runs are required. After the calibration of the system, we obtained an accuracy of 1.5 per thousand, so that the accumulated uncertainty is estimated to be less than 4 per thousand. The method also allows determination of the H(2) concentration, with an uncertainty estimated to be 2%.     

非结构网格上一种新型的高分辨率高精度无波动的有限元格式

在非结构网格上构造出无波动无自由参数耗散性有限元格式 ,即NND有限元格式 .通过若干个典型二维跨音速和超音速可压缩无粘定常流动的算例证明这确是一个高精度的 ,对激波具有高分辨率的无波动的新型有限元格式 .特别与网格自适应相结合 ,可得到十分满意的结果