基于长光程的土壤氧化亚氮排放规律的FTIR光谱法研究

氧化亚氮（N₂O）的过量排放会对臭氧层造成破坏,合理施肥和采取减排措施对减缓温室效应具有重要的现实意义。本文利用FTIR光谱法研究了施肥和水分对白菜地土壤排放N₂O的影响。为了提高系统的灵敏度,我们利用多个反射镜加长了光程。通过比对施肥前后N₂O红外光谱和NIST谱库N₂O红外光谱,最终选取2 160～2 225 cm-1作为定量计算N₂O的特征波段。研究发现,施肥和水分能促进白菜地土壤N₂O气体排放,这为农田N₂O的减排和减缓温室效应提供了理论依据。最后,还研究了施肥后土壤N₂O的昼夜排放规律,结果表明,N₂O白天的排放量高于晚上,通过和前人研究结果对比,验证了此方法的可行性。本文研究证实,基于长光程的FTIR光谱法是一种测量土壤排放N₂O气体规律的快速有效方法,它可以对施肥后的白菜地土壤N₂O气体排放进行测量,相对其他传统测量方法具有高速、简便等优势。     

红外高光谱资料AIRS反演晴空条件下大气氧化亚氮廓线

N₂O是一种非常重要的温室气体和臭氧损耗物。由于观测资料有限,对于N₂O在这两方面所发挥的作用定量描述还存在很多的不确定性。利用热红外卫星数据AIRS可以反演监测甲烷和二氧化碳气体,但对氧化亚氮的反演还很少见到。因此该工作首次在国内针对高光谱红外卫星资料AIRS,开展利用最优估计法反演大气N₂O廓线的模拟研究。讨论了先验廓线的获取方法及反演通道的选取方法,并将反演结果和HIPPO飞机观测数据进行比较,发现AIRS观测数据可以很好的捕获N₂O的垂直分布,在300～900 hPa,与HIPPO数据趋势一致,且反演精度较高,相对误差仅为0.1%,与所选取反演通道的jacobian峰值区间一致。反演结果相比于特征向量统计法也有显著提高。     

基于便携式柱面镜多通池的二氧化碳高灵敏度探测研究

二氧化碳作为大气中重要的温室气体，与气候变化和人类活动密切相关，因此对其浓度的探测具有重要意义。利用近红外可调谐二极管激光器结合自主设计的便携式小型化柱面镜光学多通吸收池，实现了二氧化碳气体的高灵敏探测。通过Matlab编写光线传输矩阵，优化设计了基于柱面镜的光学多通吸收池，相比于传统Herriott型多通池，具有腔镜利用面积高、在相同体积内可实现有效光程长等特点，在物理基长为15 cm的情况下，实现了14 m的有效光程。实验中使用中心波长为1.57 μm的DFB二极管激光器，采用直接吸收光谱方法对CO₂气体进行了探测研究，并用Allan方差对系统性能进行了分析。结果表明，在平均时间为5 s时，系统的探测灵敏度为33.1 μL·L-1，平均时间为235 s时，系统的探测灵敏度可达到5.3 μL·L-1。此外，利用该系统实现了大气中CO₂的探测，得到大气中的CO₂浓度为383.4 μL·L-1。基于柱面镜多通池搭建的可调谐激光吸收光谱(TDLAS)系统，结合了柱面镜多通池可在小体积内实现长光程和可调谐激光吸收光谱技术高灵敏度、高分辨率、快速响应的优点，大大减小了系统体积，提高了系统探测灵敏度，在气体探测领域有广泛的应用。     

中红外二氧化碳传感器的研制及在农业中的应用

利用二氧化碳气体分子在4.25μm处的基频吸收带,研制了一种差分式中红外二氧化碳检测系统.系统的光路部分由热辐射红外光源、双通道热释电探测器和球面反射镜构成,电路部分主要包括信号处理、光源驱动及主控模块.采用Tracepro软件对气室结构进行仿真和优化设计,使气体吸收光程达到30cm,改善了系统的性能.实验研究了系统对不同浓度二氧化碳气体样品的传感特性.实验结果表明,由拟合曲线得到的浓度与实际浓度误差较小,在0~5 000ppm范围内,测得二氧化碳浓度的标准差小于45ppm,而在500ppm以下,测量浓度的标准差小于5ppm;对浓度为0ppm的二氧化碳气体样品连续测量2h,测量结果的标准差约为2.8ppm;根据Allan方差分析得到系统的1σ检测下限为2.5ppm.在每个二氧化碳传感器上增加无线模块nRF24L01,构成传感器节点,在选定的日光温室大棚中构建了无线传感器网络,采集了温室大棚中的二氧化碳浓度信息,验证了所研制的传感器性能.     

Cavity-enhanced optical frequency comb spectroscopy in the mid-infrared application to trace detection of hydrogen peroxide

We demonstrate the first cavity-enhanced optical frequency comb spectroscopy in the mid-infrared wavelength region and report the sensitive real-time trace detection of hydrogen peroxide in the presence of a large amount of water. The experimental apparatus is based on a mid-infrared optical parametric oscillator synchronously pumped by a high-power Yb:fiber laser, a high-finesse broadband cavity, and a fast-scanning Fourier transform spectrometer with autobalancing detection. The comb spectrum with a bandwidth of 200 nm centered around 3.76 μm is simultaneously coupled to the cavity and both degrees of freedom of the comb, i.e. the repetition rate and carrier envelope offset frequency, are locked to the cavity to ensure stable transmission. The autobalancing detection scheme reduces the intensity noise by a factor of 300, and a sensitivity of 5.4×10^?9 cm^?1?Hz^?1/2 with a resolution of 800 MHz is achieved (corresponding to 6.9×10^?11 cm^?1?Hz^?1/2 per spectral element for 6000 resolved elements). This yields a noise equivalent detection limit for hydrogen peroxide of 8 parts-per-billion (ppb); in the presence of 2.8 % of water the detection limit is 130 ppb. Spectra of acetylene, methane, and nitrous oxide at atmospheric pressure are also presented, and a line-shape model is developed to simulate the experimental data.     

On-line monitoring of cyclotron target-gas output by means of tunable lead salt diode laser absorption spectroscopy

We demonstrate what is, to our knowledge, the first use of mid-infrared laser absorption spectroscopy for trace-gas measurements of cyclotron target outputs used for the generation of radioactive carbon-11 in positron emission tomography (PET). The spectrometer was based upon a liquid-nitrogen-cooled lead salt diode laser generating single-mode radiation in the wavenumber range of 2230–2240 cm^?1. The sample flowed to a multiple-pass optical cell with a total path length of 15.23 m and the laser radiation was detected by two liquid-nitrogen-cooled InSb photodetectors. We present the results of CO, N₂O and CO₂ measurements on PET trace cyclotron output and discuss future work on ¹¹CO and ¹¹CO₂ detection.     

Quantum-noise-limited cavity ring-down spectroscopy

We demonstrate a heterodyne-detected cavity ring-down spectroscopy (CRDS) method that allows for a noise-equivalent absorption coefficient of 6 × 10^?14 cm^?1 Hz^?1/2, the lowest which has been reported in a CRDS measurement. It is shown that heterodyne-detected CRDS also reaches the quantum noise limit at reasonable optical powers. In addition to offering ultra-high sensitivity, this technique provides high frequency agility over a range of 2 THz in the near-infrared, which allows entire absorption bands to be recorded in minutes. As a demonstration experiment, high resolution spectra of a near-infrared carbon dioxide band have been recorded.     

Correlation of plume dynamics and oxygen pressure with VO2 stoichiometry during pulsed laser deposition

Vanadium dioxide thin films have been deposited on Corning glass substrates by a KrF laser ablation of V₂O₅ target at the laser fluence of 2 J?cm^?2. The substrate temperature and the target-substrate distance were set to 500 ^°C and 4 cm, respectively. X-ray diffraction analysis showed that pure VO₂ is only obtained at an oxygen pressure range of 4×10^?3–2×10^?2 mbar. A higher optical switching contrast was obtained for the VO₂ films deposited at 4×10^?3–10^?2 mbar. The films properties were correlated to the plume-oxygen gas interaction monitored by fast imaging of the plume.     

高温二氧化碳气体红外辐射实验研究

主要介绍了依托高频等离子体风洞建立的高温气体辐射测量平台,并在此平台上开展了高温二氧化碳气体红外辐射实验测量。介绍了高频等离子体风洞的运行原理、流场特性及工作介质;介绍了实验测量的条件、装置、标定、数据处理方法和结果分析;通过自建的高温气体发射光谱测量平台实验测量了二氧化碳气体在1 500～3 000 K范围内4个温度点的红外发射光谱;介绍了Abel变换在测量二氧化碳气体红外辐射空间分布中的应用,通过Abel变换获得了高温下二氧化碳气体红外辐射的空间分布结果; 分析了高温二氧化碳气体在4.3 μm附近的红外辐射的强度及其中心波长随温度变化的分布,得到了发射峰中心波长随温度的升高向长波方向展开的结果,并与文献结果进行了对比分析。     

Diagnostic and characterization of the VCSEL diodes based on GaSb

Vertical-Cavity Surface-Emitting Laser (VCSEL) diodes are among the youngest members of the semiconductor laser diode family. The main aim of our work focuses on the measurement of the basic properties (the spectral range of the laser emission, temperature and current tunability) of experimental VCSEL diode lasers based on GaSb operating in the infrared region around 4250 cm^?1. A high-resolution FTIR Bruker IFS 120 HR spectrometer with a maximum resolution of 0.0035 cm^?1 was used in the emission setup for the laser diagnostic research. The absorption spectra of atmospheric pollutants like methane, carbon monoxide and ammonia have been measured using these VCSELs for the first time.     

The reaction of nitrous oxide with rhodium

A clean rhodium filament at room temperature is highly reactive towards nitrous oxide. The oxygen atom of the N₂O molecule is adsorbed with a sticking probability of 0.45 whilst the nitrogen atoms appear in the gas phase as molecular nitrogen. The room temperature uptake of oxygen is about 5 × 10¹⁴ atom cm^?2 and is independent of nitrous oxide pressure in the range 3.5 × 10^?8 to 1.1 × 10^?6 torr. The adsorption curve is of typical form with an initial region of essentially constant sticking probability. For the first 80% of adsorption at room temperature the shape is satisfactorily accounted for if molecules are able to visit 4–5 adsorption sites whilst held in a weakly-bonded precursor state.     

Broadly tunable quantum cascade laser in cantilever-enhanced photoacoustic infrared spectroscopy of solids

An external cavity quantum cascade laser (EC-QCL) is applied in the photoacoustic detection of solid samples. The EC-QCL used has a broad tuning range of 676 cm^?1 (970–1,646 cm^?1) in the mid-infrared region, which enables accurate broadband spectroscopy of large molecules. The high spectral power density of the EC-QCL is combined with an extremely sensitive optical cantilever microphone of the photoacoustic detector to achieve an ultimate sensitivity. The carbon black, polyethylene, and hair fiber samples were measured with the EC-QCL photoacoustic detection using electrical amplitude modulation to demonstrate the possibilities of the setup. The same measurements were repeated with a Fourier transform infrared (FTIR) spectrometer combined with a photoacoustic detector for a comparison. The EC-QCL photoacoustic setup yielded roughly a decade better signal-to-noise ratios than the FTIR setup with the same measurement time.     

Quantitative Analysis of Added Ammonium and Nitrate in Silica Sand and Soil Using Diffuse Reflectance Infrared Spectroscopy

Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) in both near infrared (NIR) and mid infrared (MIR) has been previously shown to be effective in quantifying soil nitrogen concentrations when calibrated using numerous field soil samples. However, such an approach incorporates samples that may contain substantial correlations between physical and chemical properties. To address these concerns, the performance of DRIFTS coupled with PLS regression in NIR regions, 5000–4000 cm^? 1 (2000–2500 nm) and 6500–5500 cm^? 1 (1540–1820 nm), and the MIR region, 3400–2400 cm^? 1 (2940–4170 nm), was assessed through analysis of the concentration of ammonium (NH₄ ⁺) (0–50 ppm) and nitrate (NO₃ ^?) (0–200 ppm) artificially incorporated into a series of silica sand samples with a consistent particle size. The influence of different particle sizes of sand was also analyzed quantitatively. The Pima clay loam soil was then evaluated with concentration ranges of 0–200 ppm NH₄ ⁺ and 180–1000 ppm NO₃ ^? added to the soil samples. With sand samples, accurate NH₄ ⁺ measurements could be performed using all three ranges. The MIR region was significantly more useful for NO₃ ^? measurement than those of NIR regions. The MIR region also performed reasonably well with soil samples but both NIR regions provided poor results. The detection limits for NH₄ ⁺ and NO₃ ^? measurements in sand were 9 ppm NH₄ ⁺ and 39 ppm NO₃ ^? with the correlation coefficients (R²) of roughly 97% and 96%, respectively, and in soil were 100 ppm NH₄ ⁺ and 330 ppm NO₃ ^? with the correlation coefficients (R²) of roughly 80% and 90%, respectively.     

Remote Measurement of Motorcycle Exhaust Using Fourier Transform Infrared System

Abstract

We have explored the basic theory and quantitative methods for the measurement of motorcycle exhaust using a Fourier transform infrared interferometer system. Remote sensing direct measurements were made and the species carbon monoxide, carbon dioxide, nonmethane paraffinic carbon(CH^x) and unburned additional harmful species in motorcycle exhaust were determined. Typical concentrations observed in absorption for carbon monoxide, carbon dioxide and nonmethane paraffinic carbon were about 1.11%, 1.91%, 0.54% respectively. Furthemore, this paper describes the remote sensing Fourier transform infrared spectrometer system. The system covers the infrared spectral region from 700 to 6000 cin^?1 at a maxim resolution of 0.06 cm^?1 for beamsplitter of gerrniuiirun coated zinc selenide and receiver telescope with zinc selriide leis. For air multipollutant monitoring the analytica1 methods have the potential and become important. The remote measurements usirig the Fourier transform inf raid spectroscopy could become niore practical.     

Vibration-rotation bands of 14N216O: 1.2 micron-3.3 iicron region

The infrared spectrum of nitrous oxide has been measured and analyzed from 3000 cm^?1 to 8200 cm^?1. The spectra have been recorded with the Fourier transform interferometer of Laboratoire Aimé Cotton. Rotational constants for 51 vibrational states have been calculated. Local perturbations are present for the levels 10⁰1, 33^1c,dO, 07^1c,d1, 12⁰1.     

Enhanced Upconversion Luminescence of Erbium–Nitrogen-Doped Zinc Oxide Nano-Wires by Implantation of Ytterbium Ions

Erbium–nitrogen codoped zinc oxide nanowires of ytterbium-doped are prepared by thermal evaporation and ion implantation methods. Ytterbium ions are doped into nanowires at a fluence of (0, 1, 3, 5, and 9) × 10¹⁵ cm^?2. Microstructural and optical properties of specimen are investigated by X-ray diffractometer, absorption spectra, Raman, and upconversion photoluminescence examinations. Upconversion photoluminescence emissions at 550 nm and 660 nm are obtained under 980-nm light excitation. Both intensities of green and red peaks are enhanced by the introduction of ytterbium ions. When ytterbium ion fluence is 5 × 10¹⁵ cm^?2, light emission intensity reaches maximum value. The energy transfer and cross-relaxation processes are responsible for the change of emission intensity.     

Vibrational Spectroscopic Characterization of the Arsenate Mineral Barahonaite: Implications for the Molecular Structure

The mineral barahonaite is in all probability a member of the smolianinovite group. The mineral is an arsenate mineral formed as a secondary mineral in the oxidized zone of sulphide deposits. We have studied the barahonaite mineral using a combination of Raman and infrared spectroscopy. The mineral is characterized by a series of Raman bands at 863 cm^?1 with low wavenumber shoulders at 802 and 828 cm^?1. These bands are assigned to the arsenate and hydrogen arsenate stretching vibrations. The infrared spectrum shows a broad spectral profile. Two Raman bands at 506 and 529 cm^?1 are assigned to the triply degenerate arsenate bending vibration (F ₂, ν₄), and the Raman bands at 325, 360, and 399 cm^?1 are attributed to the arsenate ν₂ bending vibration. Raman and infrared bands in the 2500–3800 cm^?1 spectral range are assigned to water and hydroxyl stretching vibrations. The application of Raman spectroscopy to study the structure of barahonaite is better than infrared spectroscopy, probably because of the much higher spatial resolution.     

Simultaneous detection of trace gases using multiplexed tunable diode lasers and a photoacoustic cell containing a cantilever microphone

We report what we believe to be a novel demonstration of simultaneous detection of multiple trace gases by near-IR tunable diode laser photoacoustic spectroscopy using a cell containing a cantilever microphone. Simultaneous detection of carbon monoxide (CO), ethyne (C₂H₂), methane (CH₄) and combined carbon monoxide/carbon dioxide (CO+CO₂) in nitrogen-based gas mixtures was achieved by modulation frequency division multiplexing the outputs of four near-IR tunable diode lasers. Normalized noise-equivalent absorption coefficients of 3.4×10^?9, 3.6×10^?9 and 1.4×10^?9 cm^?1?W?Hz^?1/2 were obtained for the simultaneous detection of CO, C₂H₂ and CH₄ at atmospheric pressure. These corresponded to noise-equivalent detection limits of 249.6 ppmv (CO), 1.5 ppmv (C₂H₂) and 293.7 ppmv (CH₄) respectively over a measurement period of 2.6 s at the relevant laser power. The performance of the system was not influenced by the number of lasers deployed, the main source of noise arising from ambient acoustic effects. The results confirm that small-volume photoacoustic cells can be used with low optical power tunable diode lasers for rapid simultaneous detection of trace gases with high sensitivity and specificity.     

Photoacoustic spectrometer for accurate,continuous measurements of atmospheric carbon dioxide concentration

We have developed a portable photoacoustic spectrometer that offers routine, precise and accurate measurements of the molar concentration of atmospheric carbon. The temperature-controlled spectrometer continuously samples dried atmospheric air and employs an intensity-modulated distributed feedback laser and fiber amplifier operating near 1.57 µm. For measurements of carbon dioxide in air, we demonstrate a measurement precision (60-s averaging time) of 0.15 µmol mol^?1 and achieve a standard uncertainty of 0.8 µmol mol^?1 by calibrating the analyzer response in terms of certified gas mixtures. We also investigate how water vapor affects the photoacoustic signal by promoting collisional relaxation of the carbon dioxide.     

Thin yttrium and rare earth oxide films produced by plasma enhanced CVD of novel organometallic π-complexes

Novel volatile cyclooctatetraenyl-pentamethylcyclopentadienyl sandwich complexes have been used as precursors to deposit thin yttrium and rare earth oxide films by means of PECVD. These compounds form pure oxide films in plasmas of argon/oxygen or argon/water-vapour, in nitrous oxide, and carbon dioxide at substrate temperatures of 350–400° C and power densities of 1.0–1.5 W/cm².The films were characterized by metal analysis, carbon analysis, XPS, CTEM electron diffraction, SEM micrographs, and FTIR spectra.