Photonic sensing of the atmosphere by absorption spectroscopy

Chemically reactive atmospheric species play a crucial role in tropospheric processes which affect regional air quality and global climate change. Contrary to long-lived species such as greenhouse gases, interference-free accurate and precise concentration assessments of strongly reactive short-lived species represent a real challenge. In this paper, we report on the recent progress in spectroscopic instrumental developments for monitoring of OH, NO₃, HONO and NO₂ by using modern photonic sources (Quantum Cascade Laser, distributed feedback diode laser, light emitting diode) in conjunction with high-sensitivity spectroscopic measurement techniques such as multi-pass cell based long optical path length absorption spectroscopy, wavelength-modulation enhanced off-axis integrated cavity output spectroscopy, Faraday rotation spectroscopy, incoherent broadband cavity enhanced absorption spectroscopy. The main techniques available for routine atmospheric measurements of OH, NO₃ and HONO are overviewed, in comparison with the emerging modern photonic spectroscopy techniques.     

Sub-ppb NO2 detection by optical feedback cavity-enhanced absorption spectroscopy with a blue diode laser

We report preliminary results on the first application of optical feedback cavity-enhanced absorption spectroscopy with a blue (411 nm) extended cavity diode laser (ECDL) for NO₂ detection. While this technique was originally developed to operate with distributed feedback diode lasers in the near infrared, it is here extended to ECDLs and applied to the blue spectral region. With a simple and compact optical setup, we demonstrate from the baseline noise a minimum detectable NO₂ concentration of 6×10⁹ molecules/cm³ for a single laser scan (70 ms), which extrapolated under atmospheric conditions corresponds to 200 pptv. Signal averaging should allow further lowering of this limit. Observed absorption spectra display more structure than previous spectra obtained at lower resolution by Fourier-transform spectroscopy at the same wavelength. PACS 07.88.+y; 42.55.Px; 42.62.Fi     

Signal processing system in cavity enhanced spectroscopy

The paper presents a signal processing system used for nitrogen dioxide detection employing cavity enhanced absorption spectroscopy. In this system, the absorbing gas concentration is determined by the measurement of a decay time of a light pulse trapped in a cavity. The setup includes a resonance optical cavity, which was equipped with spherical and high reflectance mirrors, the pulsed diode laser (414 nm) and electronic signal processing system. In order to ensure registration of low-level signals and accurate decay time measurements, special preamplifier and digital signal processing circuit were developed. Theoretical analyses of main parameters of optical cavity and signal processing system were presented and especially signal-to-noise ratio was taken into consideration. Furthermore, investigation of S/N signal processing system and influence of preamplifier feedback resistance on the useful signal distortion were described. The aim of the experiment was to study potential application of cavity enhanced absorption spectroscopy for construction of fully optoelectronic NO₂ sensor which could replace, e.g., commonly used chemical detectors. Thanks to the developed signal processing system, detection limit of NO₂ sensor reaches the value of 0.2 ppb (absorption coefficient equivalent = 2.8 × 10⁻⁹ cm⁻¹).     

Development of an open-path incoherent broadband cavity-enhanced spectroscopy based instrument for simultaneous measurement of HONO and NO2 in ambient air

We report on the development of an optical instrument based on incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) for simultaneous open-path measurements of nitrous acid (HONO) and nitrogen dioxide (NO₂) in ambient air using a UV light emitting diode operating at ∼366 nm. Detection limits of ∼430 pptv for HONO and ∼1 ppbv for NO₂ were achieved with an optimum acquisition time of 90 s, determined by an Allan variance analysis. Based on a 1.85 m long high optical finesse open-path cavity, the effective optical path length of 2.8 km was realized in aerosol-free samples or in an urban environment at modest aerosol levels. Such a kilometer long optical absorption is comparable to that achieved in the well established differential optical absorption spectroscopy (DOAS) technology while keeping the instrument very compact. Open-path detection configuration allows one to avoid absorption cell wall losses and sampling induced artifacts. The demonstrated sensitivity and specificity shows high potential of this cost-effective and compact infrastructure for future field applications with high spatial resolution.     

Low-limit detection of NO2 by longitudinal mode selection in a photoacoustic resonant system

The paper reports the pulsed laser-based photoacoustic (PA) spectroscopy of NO₂ in a resonant PA cavity with special filters made of stainless steel. The PA cell along with special types of sound filters are designed and fabricated to excite only the second-order longitudinal mode inside the cavity. The second harmonic, i.e. λ?= 532 nm pulse width, of 7 ns obtained from Q-switched Nd:YAG laser at 10 Hz repetition rate has been used to study the saturation behaviour of the PA signal and absorption coefficient with respect to the input laser energy. Generally, the Q-factor of longitudinal modes in the acoustic cavities is quite low. However, by modifying the design of the cell and the filter, we can achieve high value of Q = 30. The combination of special filter along with the experimental data acquisition technique helped us to achieve the minimum detection concentration of NO₂ of the order of 9 ppbV which is much better than the previous value of the same PA cell without filter [Yehya and Chaudhary, Appl. Phys. B 106, 953 (2012)].     

利用差分吸收光谱法测量亚硝酸和反演气溶胶参数

利用差分光学吸收光谱仪(DOAS)进行亚硝酸(HONO)气体的测量并同时在固定的波长范围内(3 07—380 nm)反演气溶胶参数包括气溶胶的平均直径、总个数和总比表面积等. 实验结果表 明利用自测的NO₂标准吸收截面可以更加准确地拟合HONO的浓度，同时在较短的 波长范围内能准确反演气溶胶参数. 关键词： 差分光学吸收光谱(DOAS) 亚硝酸 气溶胶参数     

Magnetic resonance absorption in isolated metal/insulator/metal nanodot arrays with transmission geometry

In this study, we have systematically investigated a magnetic resonance absorption and tunability of absorption wavelength in isolated metal-insulator-metal (MIM) nanodot arrays with transmission geometry. The elemental electromagnetic resonances and their hybridizations are studied using 3-dimensional finite-difference time-domain (FDTD) calculation and resonance properties including the resonance peak tunability, magnetic permeability and quality (Q) factor are characterized with respect to the coupling strength. We have found the existence of electric and magnetic resonance mode in the MIM (Au/MgF₂/Au) structure and the magnetic resonance has larger wavelength tunability than the electric resonance. The absorption cross section calculation revealed that absorption is the dominant extinction process at the magnetic resonance only. Magnetic permeability (μ) calculations for the various MIM parameters showed the maximum value of the imaginary part of μ is 16.1 with Q factor of 9.2 when the size of nanodot is 200 nm and the inter-dot distance is 300 nm. The presented calculations can be used to tune the response of the magnetic resonance absorption with a variable resonance wavelength and Q factor by using the simple MIM structures with transmission geometry.     

Cavity ring down spectroscopy: detection of trace amounts of substance

We describe several applications of cavity ring-down spectroscopy (CRDS) for trace matter detection. NO₂ sensor was constructed in our team using this technique and blue-violet lasers (395–440 nm). Its sensitivity is better than single ppb. CRDS at 627 nm was used for detection of NO₃. Successful monitoring of N₂O in air requires high precision mid-infrared spectroscopy. These sensors might be used for atmospheric purity monitoring as well as for explosives detection. Here, the spectroscopy on sharp vibronic molecular resonances is performed. Therefore the single mode lasers which can be tuned to selected molecular lines are used. Similarly, the spectroscopy at 936 nm was used for sensitive water vapour detection. The opportunity of construction of H₂O sensor reaching the sensitivity about 10 ppb is also discussed.     

Experimental study using optoacoustic spectroscopy (OAS) on spherical gold nanoparticles

In this paper a spectroscopic characterisation method based on the optoacoustic technique has been used to investigate the optical properties of two separate spherical gold nanoparticle (SGNP) solutions where an absorption peak located at 520 nm has been observed. This analysis has been carried out over the visible wavelength range from 410 to 650 nm using a Q-switched Nd:YAG pumped optical parametric oscillator (OPO). To verify the reliability of optoacoustic spectroscopy (OAS), the results obtained have been compared to those from more standard and limited spectrophotometer and reference collimated optical transmission schemes, where good agreement is shown. The experimental procedure presented here demonstrates the potential of this technique for integration along with optoacoustic imaging methods to identify physiological information for non-destructive in-vivo applications.     

多轴差分吸收光谱技术测量近地面NO2体积混合比浓度方法研究

多轴差分吸收光谱技术(MAX-DOAS)通过测量不同角度的太阳散射光, 获取痕量气体的柱浓度信息, 广泛应用于整层NO₂柱浓度的监测. 由于缺少有效观测距离的信息, MAX-DOAS无法获取近地面NO₂的体积混合比浓度. 本文分析了消光系数和有效观测距离的关系, 提出了利用能见度信息获取有效观测距离, 进而将MAX-DOAS测量的水平方向NO₂斜柱浓度转换为体积混合比浓度的方法. 并在合肥开展了相应的观测实验, 成功实现了基于MAX-DOAS的NO₂体积混合比浓度测量. 通过与主动式长程差分吸收光谱仪测量的NO₂浓度进行对比, 结果呈现出较好的一致性, 说明了方法的可行性.研究为MAX-DOAS监测近地面NO₂体积混合比浓度提供了一种简单有效的方法, 拓展了MAX-DOAS的应用领域. 关键词： 多轴差分吸收光谱技术 大气消光系数 能见度 2体积混合比浓度')" href="#">NO₂体积混合比浓度     

Mid-infrared dual-comb spectroscopy with 2.4 μm Cr2+:ZnSe femtosecond lasers

The mid-infrared part of the electromagnetic spectrum is the so-called molecular fingerprint region because gases have tell-tale absorption features associated with molecular rovibrations. This region can be for instance exploited to detect small traces of environmental and toxic vapors in atmospheric and industrial applications. Novel Fourier-transform spectroscopy without moving parts, based on time-domain interferences between two comb sources, can in particular benefit optical diagnostics and precision spectroscopy. To date, high-resolution and -sensitivity proof-of-principle experiments have only been reported in the near-infrared region where frequency-comb oscillators are conveniently available. However, as most of the molecular transitions in this region are due to weak overtone bands, this spectral domain is not ideal for sensitive and rapid detection. Here we present a proof-of-principle experiment of frequency-comb Fourier-transform spectroscopy with two Cr²⁺:ZnSe femtosecond oscillators directly emitting in the 2.4 μm mid-infrared region. The acetylene absorption spectrum in the region of the n₁+n₅¹\nu_{1}+\nu_{5}^{1} band, extending from 2370 to 2525 nm, could be recorded within a 10 μs acquisition time without averaging with 12 GHz resolution.     

Time-resolved time-dependent photo-acoustic spectroscopy of NO2 in a high frequency multi-resonant cavity

The paper reports the pulsed laser-based time-resolved time-dependent Photo-acoustic (PA) spectroscopy of NO₂ gas in a specially designed multi mode-Resonant PA Cell which is made of Stainless Steel and has a “Q” value of the order of 79. Furthermore the designed cell allows us to excite some of the longitudinal, radial and azimuthal resonance modes of the photo-acoustic signals simultaneously in a very efficient manner. The presence of many newly excited modes occur at 7050 Hz, 10350 Hz and 14650 Hz frequencies is observed for the first time in NO₂ at room temperature. These results are obtained by employing second harmonics i.e. λ=532 nm pulses from Q-switched Nd:YAG laser having 7 ns pulse duration. Some of the new acoustic spectrum lines at higher frequencies are recorded between 0.5–10 ms data acquisition time, which also extends the frequency monitoring range of our system. The study also highlights some of the important aspects such as the decaying behavior of some of these resonant acoustic spectrum lines occur on the expense of others as well as the saturation behavior of some other modes in the NO₂ gas sample. The estimated low level detection limit of NO₂ buffered in air is of the order of 17.9 ppbV.     

Effective Mode Volume of Nanoscale Plasmon Cavities

The controlled squeezing of electromagnetic energy into nanometric volumes via surface plasmon-polariton excitations in plasmonic nanoresonators is analyzed using the concept of an effective electromagnetic mode volume V _eff, while taking careful account of the plasmon-polariton dispersion and the electromagnetic energy stored in the metal. Together with the quality factor Q of the cavity resonance, this enables a comparison with dielectric optical cavities, where V _eff is limited by diffraction. For a Fabry–Perot type planar metallic cavity, a one-dimensional analytic model as well as a three-dimensional finite-difference time-domain simulation reveal that V _eff is not bounded by diffraction, and that Q/V _eff increases for decreasing cavity size. In this picture, matter–plasmon interactions can be quantified in terms of Q and V _eff, and a resonant cavity model for the enhancement of spontaneous Raman scattering is presented.     

Pulsed cavity ring-down spectroscopy of NO and NO2 in the exhaust of a diesel engine

The application of pulsed cavity ring-down spectroscopy has been demonstrated for the in situ quantitative determination of NO and NO₂ in the exhaust of a diesel engine. NO absorption has been monitored at the transition from the Χ²Π ground state to the A²Σ⁺ state at 226 nm. For NO₂, absorption bands in the spectral region from 438 nm to 450 nm were used. At the selected engine conditions, concentrations of 212±22 ppm and 29±4 ppm have been measured for NO and NO₂, respectively, in good agreement with separate chemical exhaust gas analysis. The method is sensitive enough to meet the European Euro V standard directive on NO_x emissions. This communication discusses the relatively simple setup needed for this type of measurement, the problems encountered, as well as the prospects for single-stroke, simultaneous measurements of both NO and NO₂ at the sub-ppm level. Received: 30 November 2001 / Revised version: 18 February 2002 / Published online: 14 March 2002     

Optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS) in a ring cavity

Optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS) has been demonstrated by coupling a distributed feedback diode laser to a ring cavity. Frequency-selected light decaying from the ring cavity is retro-reflected, inducing a counter-propagating intra-cavity beam, and providing optical feedback to the laser. At specific laser-to-cavity distances, all cavity mode frequencies return to the diode laser with the same phase, allowing spectra to be accumulated across the range of frequencies of the current-tuned laser. OF-CEAS has been used to measure very weak oxygen isotopologue (¹⁶O¹⁸O and ¹⁶O¹⁷O) absorptions in ambient air at wavelengths near 762 nm using the electric-dipole forbidden O₂ A-band. A bandwidth reduced minimum detectable absorption coefficient of 2.2×10⁻⁹ cm⁻¹ Hz^−1/2 is demonstrated.     

Noise-immune cavity-enhanced optical heterodyne molecular spectroscopy: Current status and future potential

As a result of a combination of an external cavity and modulation techniques, noise-immune cavity-enhanced optical heterodyne molecular spectroscopy (NICE-OHMS) is one of the most sensitive absorption techniques, capable of reaching close-to-shot-noise sensitivities, down to 5×10^-13 fractional absorption at 1 s averaging. Due to its ability to provide sub-Doppler signals from weak molecular overtone transitions, the technique was first developed for frequency standard applications. It has since then also found use in fields of molecular spectroscopy of weak overtone transitions and trace gas detection. This paper describes the principles and the unique properties of NICE-OHMS. The historical background, the contributions of various groups, as well as the performance and present status of the technique are reviewed. Recent progress is highlighted and the future potential of the technique for trace species detection is discussed. PACS  33.80.-b; 07.57.-c; 42.62.Fi     

差分吸收光谱技术在工业污染源烟气排放监测中的应用

研究了差分吸收光谱技术在工业污染源烟气排放监测中的应用及实现.借助于独立的采样和前处理系统去除烟尘和水汽对光谱拟合的影响.为避免高浓度的SO2在常温下发生光解.将经前处理后的烟气加热至150℃进行测量.采用Voigt线型对SO2,NO,NO2在185-235 nm波段的吸收截面进行了展宽,获得了高温气体的标准吸收截面,并与归一化的光谱仪仪器函数进行卷积得到了光谱拟合所需的有效吸收截面.将反演结果与非分散红外分析仪的测量结果进行了实时对比,获得了较好的一致性,验证了差分吸收光谱方法高准确度测量工业污染源烟气排放的可行性.     

Gain versus tuning issues to Q-switch with Yb<Superscript>3+</Superscript>:LSO and amplify broad-bandwidth pulses

We report on the development of Incoherent Broadband Cavity Enhanced Absorption Spectroscopy (IBBCEAS) using a blue light emitting diode (LED) for the detection of NO₂ in laboratory ambient air. Absorption of the oxygen collisional pair in the atmosphere was also detected in the same spectral range. The mirror reflectivity was determined using a standard gas sample mixture of NO₂, and calibrated with the help of the absorption spectrum of the oxygen collisional pair in pure oxygen at atmospheric pressure. Optimization of the experimental parameters was investigated and is discussed in detail. For the first time in IBBCEAS involving broadband absorption spectra, averaging time for signal-to-noise ratio enhancement has been optimized using Allan variance plot. 18.1 ppbv NO₂ in laboratory ambient air has been retrieved from the absorption spectra using differential fitting method over a 40 nm spectral region centered at 470 nm. A minimum detection sensitivity of about 2.2 ppbv (1σ) for NO₂ at atmospheric pressure has been achieved using the optimal averaging time of 100 s by means of a high finesse optical cavity formed with two moderate reflectivity (∼99.55%) mirrors. No purging of the cavity mirrors by high purity He or N₂ gas streams was necessary to prevent contamination of the mirror faces for the in situ measurements.     

Broadband surface electromagnetic wave spectroscopy

Broadband generation and spectroscopic detection of infrared surface electromagnetic waves (SEW's) are reported from 600 to 1800 cm^?1. For KReO₄ coated metal samples a sharp absorption line near 1000 cm^?1 is used to compare the SEW and surface reflection spectroscopy (SRS) techniques. The integrated optical density of the absorption line is an order of magnitude larger with SEW spectroscopy than with SRS.     

用太阳光谱测量空气中NO2浓度的方法研究

根据Noxon方法,利用NO₂在430—450nm范围内的吸收特性,测量空气中NO ₂的浓度.介绍了一种利用光学差分吸收原理,以太阳光为光源,二极管阵列为探测器 ,黄山光明顶上的太阳光谱为参考光谱测量大气中NO₂浓度的新光学方法. 关键词： 太阳光谱 2垂直柱体密度')" href="#">NO₂垂直柱体密度 定日镜 环境空气质量监测