15N Analysis of nitric oxide and nitrous oxide by cryotrap enrichment using a gas chromatograph quadrupole mass spectrometer and its application to (15)N-tracer investigations of NO/N(2)O formation in soil

Nitric oxide (NO) and nitrous oxide (N(2)O) are two important trace gases in the atmosphere. Determining the concentration and (15)N abundance of NO and N(2)O in air is difficult owing to their very low concentration in the atmosphere (NO < 1 ppb(v); N(2)O approximately 0.32 ppm(v)). Although (15)N analysis of N(2)O in ambient concentrations can be carried out using a gas chromatograph quadrupole mass spectrometer system (GC-QMS) and a dosage of 2 mL of air by means of a sample loop, this system is not sensitive enough to measure the ambient concentration of NO and its (15)N abundance. Therefore the concentration of NO must be enriched by cryotrapping (cooling with liquid nitrogen). The (15)N analytical method developed enables the sensitive and sufficiently precise measurement of (15)N-enriched NO in air. Furthermore, the analytical equipment developed greatly improves existing (15)N(2)O analysis using the GC-QMS technique. An application of the (15)N analysis method will be shown for an investigation on the NO and N(2)O formation in black earth soil after (15)NH(4)(+), (15)NO(3)(-) and (15)NO(2)(-) labelling. Copyright 1999 John Wiley & Sons, Ltd.     

基于FTIR光谱辐射测量分析大气透过率

提出了一种利用FTIR光谱仪进行大气透过率测量的方法。通过黑体对系统的光谱响应进行标定,由两点温度校准得到测量光谱的辐射亮度谱。在一定的距离内实测并分析计算出了CO2红外吸收波段的大气透过率谱。采用非线性最小二乘方法将测量的CO2透过率谱与HITRAN数据库中的光谱拟合得到了干洁大气中的CO2浓度值。实验结果表明,该方法是测量大气透过率和定量分析气体组分的可行性方法。     

Pulsed quantum cascade laser instrument with compact design for rapid, high sensitivity measurements of trace gases in air

We have developed a compact instrument for sensitive, rapid and continuous measurement of trace gases in air, with results presented here for methane (CH₄), nitric oxide (NO), nitrous oxide (N₂O) and ammonia (NH₃). This instrument takes advantage of recent technology in quantum cascade (QC) lasers and infrared detectors, which allows high sensitivity without cryogenic liquids, e.g., 0.2 ppb (0.2×10^-9) of NH₃ in air in 1 s. One may substitute a QC laser operating at a different wavelength to measure other gases. The instrument operates continuously, requiring little operator attention, and web-based remote access is provided for instrument control, calibration and data retrieval. The instrument design includes a thermoelectrically (TE) cooled pulsed distributed feedback (DFB) QC laser, a low volume (0.5 l) multipass cell offering 76 m absorption path length and a TE cooled detector. Integrated software for laser control and data analysis using direct absorption provides quantitative trace gas measurements without calibration gases. The instrument may be applied to field measurements of gases of environmental concern. PACS  07.57.Ty; 42.62.Fi; 92.70.Cp     

开放式长光程傅里叶变换红外光谱系统在环境气体分析中的应用

设计了一套用于环境气体分析的长开放光路傅里叶变换红外光谱系统。该系统具有往返250 m的开放式长距离采样光程,使用一台分辨率为1 cm-1的傅里叶变换红外光谱仪测量采样路径内的大气透过率光谱,然后进行非线性最小二乘光谱拟合,计算出待测组分浓度。实验部分通过选择特定波段分析了污染空气中CH₄,CO,N₂O和CO₂的浓度,拟合残差的均方根误差小于1％。结果表明,该系统的结构简单,光路易于校准,环境适应性良好,测量速度快,采样范围广,可用于探测大气中一些重要的痕量和微量组分,开展较大区域的环境气体的监测和研究。     

PreCon: A Fully Automated Interface for the Pre-Gc Concentration of Trace Gases on Air for Isotopic Analysis

Abstract

For the high precision isotope analysis of atmospheric trace gases a computer controlled concentration interface has been developed. From small air samples it collects either N₂O or CO₂ derived from CH₄ at their respective concentrations (0.3 ppm for N₂O, 1.7 ppm for CH₄) into a small diameter cold trap (?196°C) and interfaces via GC and open split to an isotope ratio mass spectrometer (Finnigan MAT 252) for on-line isotope evaluation. External reproducibilities for repeated measurements of 100 ml air samples from the same source of < 0.2° (δ-notation) have been achieved for ¹³C/¹²C from CH₄ and for ¹⁵N/¹⁴N and ¹⁸O/¹⁶O from N₂O. The precision is adequate to monitor the isotopic changes in these gases during a day's course.     

基于光谱波段优化选择的FTIR测量与分析

在主动式红外遥感测量中,大气中痕量气体的红外吸收与不同红外波段的透过率光谱有关。在很多情况下,透过率光谱在光谱定量分析中起到重要的作用,因此,对测量和仿真的透过率光谱的波段进行优化选择是定量分析的关键。文章对最佳透过率测量范围进行了理论分析, 得到了对应于待测气体浓度反演相对误差最小的理论最佳透过率值;基于谱线的洛伦兹线型通过计算得到了待测气体分子的吸收截面, 同时给出了透过率光谱的校准训练集;确定了单组分CO₂光谱测量分析的波段,优化了多组分CO, CO₂和N₂O光谱同时测量分析的波段并成功地应用于开放光路光谱仪系统。光谱拟合分析结果表明,测量光谱与参考光谱得到了很好的拟合,拟合均方根误差小于1%。     

高功率微波单一气体及混合气体击穿特性

综合考虑高功率微波对电子的加速过程以及电子与气体分子的碰撞过程,建立了单一气体与混合气体击穿过程的蒙特卡罗仿真模型,编写了三维蒙特卡罗仿真程序(3D-MCC)。针对单一气体Ar和N2以及混合气体N2/O2展开研究,仿真了气体雪崩击穿电子云形成过程,对比分析了不同气体电子能量分布函数随压强的变化规律。发现了Ar击穿特性受电子能量分布函数影响较大,而N2击穿特性受电子能量分布函数影响较小。通过分析平均电子能量以及电子密度随时间的变化过程,得到了Ar和N2击穿时间,并通过与流体模型计算得到的击穿时间比对分析验证了3D-MCC模型的正确性。在真空腔体内开展了S波段高功率微波大气击穿实验,测量得到了场强为6.38 kV/cm时不同压强下的大气击穿时间。通过在辐射源与真空腔体之间增加聚焦透镜,大大减小了壁效应的影响,并且采用模型仿真得到的大气击穿时间与实验结果吻合较好。     

Comparison of infrared sources for a differential photoacoustic gas detection system

A prototype of the differential photoacoustic measurement system with an optical cantilever microphone has been developed. The system is based on gas filter correlation method. The proposed system allows real-time measurement of various IR-absorbing gases from the flowing sample or in the open air. Three setups with different kind of infrared sources were carried out to study selectivity and sensitivity of the prototype and applicability of the source types with differential method. The sources were a mechanically chopped blackbody radiator, electrically chopped blackbody radiator and mechanically chopped CO₂-laser. A detection limit for C₂H₄ was estimated with all three infrared sources. Cross sensitivity and detection limits of gases CH₄, C₂H₄ and CO₂ were measured with the mechanically chopped blackbody radiator. This crossinterference matrix was also modeled using HITRAN database and completed with CO and H₂O. The measurements indicate that at least ppb-level detection of ethylene using CO₂-laser, sub-ppm level with mechanically chopped blackbody and ppm-level with electrically modulated blackbody is possible with a proposed differential system.     

Preliminary results of an aircraft system based on near-IR diode lasers for continuous measurements of the concentration of methane, carbon dioxide, water and its isotopes

The Federal Agency for Hydrometeorology of the Russian Federation created the flying laboratory on board the passenger airplane Yak-42D for geophysical monitoring of the environment, including aircraft measurements of vertical concentrations of greenhouse gases in the troposphere. Within the limits of this project, General Physics Institute of the Russian Academy of Science developed airborne tunable diode laser spectrometer (TDLS) on the basis of diode lasers of a near-IR range for measurement of the altitude profiles of CO₂, CH₄, H₂O and its isotopes. TDLS complex was integrated aboard in standard 19-in. rack. Air samples, taken over an aircraft on the pipeline, were injected into the optical cell. Using the system of inflow and heating, the air was set laminar with a flowrate of 0.2?l/s at a reduced pressure of 100?mbar for detecting narrow absorption lines of water vapor isotopes. For registration of the absorption spectra and for the measurement of greenhouse gas concentrations in online mode, modulation-correlation technique was used. Diode laser spectrometer output data were transferred to the airborne central computer. Sensitivity of TDLS measurements was 20?C30?ppm for water, 3?C4?ppm for CO₂ and 20?C25?ppb for CH₄. Time of one-unit measurement is about 30?ms.     

基于微型光纤光谱仪的DOAS系统对大气中NO2,SO2和O3的监测研究

提出了将基于微型光纤光谱仪的DOAS系统用于空气中NO2、O3和SO2的监测,并对系统的性能包括探测器的偏置、暗电流、噪声和线性以及光谱仪的的光谱分辨率和杂散光进行了测试.在2006年3月合肥郊区用该系统对NO2、O3和SO2进行了连续观测,测量结果与购买的商用仪器DOAS2000（美国热电公司）的测量结果具有很好的相关性.结果显示该系统灵敏、简单易操作、并具有高时间分辨率的优点,非常适用于NO2、O3和SO2的连续观测.     

空气中O2和N2摩尔分数的拉曼散射多通道测量

开发了一套基于激光拉曼散射的多通道气体光学检测系统,应用于空气中主要组分的摩尔分数定量测量.针对性的设计了532 nm激光脉冲展宽器,能有效地避免脉冲激光在高能量状态下造成气体裂解、石英玻璃损伤等现象的发生,提高了气体拉曼散射的信噪比.在实验室环境压力和温度下,对气体样池内空气进行了长66 mm×直径1 mm激发区域同步10通道(每通道长约6.6 mm)的拉曼散射实验.得到了各通道下氧气(O2)和氮气(N2)的拉曼光谱和摩尔分数,及O2相对于N2的相对响应因子RO2.完成了26次重复性实验,每次为200个激光脉冲激发自发拉曼光谱的累加.结果表明,各通道间计算的平均的氧摩尔分数x-O2和相对于氮气的相对响应因子-RO2的标准偏差分别为0.015和0.024,但它们的平均值与10通道合并方式下的实验结果完全相同,准确率达98%,完全满足实时地并具有时空分辨力的定量测量混合气体摩尔分数的要求.该系统可满足于各种动态燃烧过程的光谱检测与分析.     

A trace methane gas sensor using mid-infrared quantum cascaded laser at 7.5 μm

Presented is a compact instrument developed for in situ high-stable and sensitive continuous measurement of trace gases in air, with results shown for ambient methane (CH₄) concentration. This instrument takes advantage of recent technology in thermoelectrically cooled pulsed Fabry–Perot (FP) quantum cascaded (QC) laser driving in a pulse mode operating at 7.5 μm to monitor a well-isolated spectral line near the ν4 fundamental band of CH₄. A high-quality liquid nitrogen cooled mercury cadmium telluride mid-infrared detector with time discriminating electronics is used along with a total reflection coated gold ellipsoid mirror offering 20 cm single pass optical absorption in an open-path cell to achieve stability of 5.2 × 10^?3 under experimental condition of 200 ppm measured ambient CH₄. The instrument operates continuously, and integrated software for laser control using direct absorption provides quantitative trace gas measurements without calibration. One may substitute a QC laser operating at a different wavelength to measure other gases. The instrument can be applied to field measurements of gases of environmental concern.     

Effects of dissolved gases and an echo contrast agent on ultrasound mediated in vitro gene transfection

The effects of acoustic cavitation on in vitro transfection by ultrasound were investigated. HeLa cells were exposed to 1.0 MHz continuous ultrasound in culture media containing the luciferase gene. Transfection efficiency was elevated when an echo contrast agent, Levovist was added or air was dissolved in the medium. When cells were sonicated in medium saturated with Ar, N2 or N2O which have different gamma values (Cp/Cv), or were saturated with He, Ar or Ne with different thermal conductivities, the effectiveness for the dissolved gases in the ultrasound mediated transfection was Ar > N2 > N2O or Ar > Ne > He, respectively. When free radical formation in water by ultrasound was monitored as a measure of inertial cavitation, it was similarly affected by dissolved gases. These results indicate that the efficiency of ultrasound mediated transfection was significantly affected either by occurrence of or by modification of inertial cavitation due to various gases.     

Diagnostics of dielectric barrier discharges in noble gases: atmospheric pressure glow and pseudoglow discharges and spatio-temporal patterns

We present experimental results of atmospheric pressure glow discharges (APGD) in a dielectric barrier discharge reactor. These are examined in different noble gases and in the N/sub 2//O/sub 2/ system (air and pure N/sub 2/), under varying experimental conditions (frequency f; gap length d; and electric field intensity E). Discharge diagnostics have been carried out using ultrahigh speed imaging, and synchronous dual-detection of light emission and current-voltage measurements, the former using a photomultiplier . The time evolutions of the discharges and of columnar patterns in regular geometric arrangements at atmospheric pressure under different experimental conditions are reported for all of the noble gases studied here. We present evidence that columnar patterns and APGD are manifestations of the same discharge physics, which is discussed with reference to recent work reported by others.     

Absorption spectroscopy with quantum cascade lasers

Novel pulsed and cw quantum cascade distributed feedback (QC-DFB) lasers operating near lambda=8 micrometers were used for detection and quantification of trace gases in ambient air by means of sensitive absorption spectroscopy. N2O, 12CH4, 13CH4, and different isotopic species of H2O were detected. Also, a highly selective detection of ethanol vapor in air with a sensitivity of 125 parts per billion by volume (ppb) was demonstrated.     

空气中激光清洗过程的等离子体光谱分析

在空气环境下,激光诱导等离子体光谱用于激光清洗状态的在线分析快速而准确。该文利用中阶梯光栅光谱仪探测脉冲激光器作用于干净及表面污染的铜币样品产生的等离子体光谱谱线,这些谱线中不但包含了清晰的铜原子发射谱线,还包含空气中氧气和氮气与激光作用产生分解效应的原子谱线。为了消除单次测量的不确定性,分析了多次测量的分布恒定的氧原子和氮原子谱线的统计规律,表明强度分布规律一致,且相对标准差基本相同,可以采用单次测量的光谱图变化表示清洗过程中状态。表面污染的铜币光谱图中包含多元素原子谱线和连续谱线,清洗干净铜币的光谱图连续谱线消失且只有铜元素谱线,观察谱线变化就可以表明样品是否被清洗干净。     

ARL3520型ICP顺序扫描光谱仪的改造技术

在仔细研究了ＡＲＬ３５２０型ＩＣＰ顺序扫描光谱仪的整体结构及控制电路的基础上，根据被改造仪器的实际情况，保留其分光系统、驱动电路和执行部件，用一台新型通用替换原有的专用计算机系统；通过一块接口板，实现由微机直接实时控制ＩＣＰ光谱仪的顺序扫描，重新设计了光电测量电路；重新开发了基于Ｗｉｎｄｏｗｓ９５操作平台的ＩＣＰ实时分析软件。     

Thermal efficiency of the principal greenhouse gases

Atmospheric gases are ranked according to the efficiency with which they absorb and radiate longwave radiation.The open international HITRAN database of gaseous absorption lines of high resolution together with inverse Fourier transform were used.The autocorrelation functions of the total dipole moment of the basic greenhouse gases molecules such as H2O,CO2,O3,N2O,and CH4were obtained.Absorption coefficient spectra and emission power spectra of infrared radiation of these gases were calculated.Analysis of the emissive ability of all gases under consideration was carried out.Compared to CO2,all the gases under investigation have more effective emission except ozone.An efficiency criterion of IR absorption and emission is defined and is calculated for each studied gas,and the gases are ranked accordingly as follows(from strong to weak):H2O,CH4,CO2,N2O,and O3.     

Spectral properties of gaseous biomarkers and choice of the optimal analytical line at interference of the spectra of detected gases

A method for comparative investigation of the absorption line properties at interference of vibration-rotation bands of the detected and interfering gases is proposed. This method is intended for highly sensitive analysis of complex gas mixtures when measurement of absorption in a weak analytical line is hindered by a stronger, closely located interfering line. Disappearance of the analytical line extrema in the spectrum studied is proposed as an assessment criterion. The concentration ratio of the analytical and interfering gases under this condition could be used for quantitative analysis and comparison of the properties. This criterion can be applied to the first and second derivatives of the absorption spectra. To demonstrate the potential of the approach proposed, it was applied to the NO and NH₃ lines that are promising for monitoring the contents of these compounds in atmospheric and exhaled air. The interference of the absorption bands of H₂O, CO₂, and several gaseous biomarkers was analyzed in the near-IR spectral region using the HITRAN2000 database. It was demonstrated that the problem of the vibration-rotation band interference for detected and interfering gases is aggravated in this spectral region. This aggravation is caused not only by the decrease in the absolute band intensity for overtones and combination bands of the molecular vibrations but also by the relative increase in the absorption in H₂O lines and high density of CO₂ lines in the near-IR spectral region.     

熔融盐循环热载体无烟燃烧体系的选择

介绍了一种全新的燃烧系统-熔融盐循环热载体无烟燃烧技术。本技术将燃料与助燃空气的燃烧分为氧化剂的生成和燃料与氧化剂接触反应两个过程。并且这两个阶段通常在两个反应室中进行,在氧化剂生成室,空气中的氧全部被氧载体吸收,剩余的高纯度氮气则被回收利用;在燃烧室,氧载体把自身的一部分或全部氧传递给燃料,完成燃烧过程。在燃烧室中,若燃料完全反应,那么只有高纯度的CO2生成,也可以直接回收用作化工原料。因为N2从燃烧系统中分离出去,且硫和重金属元素被熔融盐吸收而不被烧掉,所以燃烧过程没有NOx、 CO2、和SO2等污染物的排放。本文对几个典型的无烟燃烧系统进行了分析,并与传统燃烧过程进行了比较,对熔融盐循环热载体无烟燃烧体系的选择具有指导意义。