Pulsed differential optical absorption spectroscopy applied to air pollution measurement in urban troposphere

Differential optical absorption spectroscopy (DOAS) is useful for various types of trace gas measurements in the lower troposphere. In this paper, we report the DOAS measurement conducted in Chiba, Japan during 2009 and 2010. An optical path length of 5.5 km is employed to measure the average concentration of NO₂ using a xenon aviation obstruction light that flashes every 1.5 s. By virtue of the high stability of the light source intensity, the intensity measurement enables the retrieval of aerosol extinction coefficient averaged over the optical path. The results are compared with the concurrent results of ground sampling and sunphotometer measurements.     

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     

地基消光测量确定大气气溶胶模型

 分别取大陆型、海洋型、城市型和Junge谱分布气溶胶模型,用6S辐射传输算法计算出对应于太阳光度计测量时的各波段大气气溶胶光学厚度。将模式计算值与测量值进行比较,确定测量地区的大气气溶胶模型。将该方法用于2004年在北京地区测量的太阳光度计数据,结果显示该地区当日实际大气在几种气溶胶模型中较为符合城市型气溶胶模型。     

宽带腔增强吸收光谱技术应用于痕量气体探测及气溶胶消光系数测量

基于氙灯的非相干宽带腔增强吸收光谱系统, 并将其应用于痕量气体及气溶胶消光系数的测量. 该系统的探测灵敏度通过测量NO₂在520—560 nm波长范围内的吸收得到验证, 最小可探测灵敏度为1.8× 10^-7cm^-1 (1σ, 0.12 s积分时间, 50次平均), 对应的NO₂探测极限～33 nmol/mol. 结合标准气溶胶粒子发生系统, 测量了不同浓度的单分散硫酸铵气溶胶粒子在532 nm波长处的消光系数, 得到粒径为600 nm的硫酸铵气溶胶的消光截面为1.12× 10^-8cm², 与文献报道值1.167× 10^-8cm²相一致, 验证了气溶胶测量的可行性和准确性.     

多轴差分吸收光谱技术反演气溶胶消光系数垂直廓线

研究了多轴差分吸收光谱技术(MAX-DOAS)的气溶胶消光系数垂直廓线反演算法. 该算法应用非线性最优估算法, 通过MAX-DOAS测量的氧的二聚体(O₄), 反演气溶胶消光系数垂直廓线和光学厚度(AOD). 首先研究了非线性最优估算法中权重函数、先验廓线协方差矩阵、测量不确定度协方差矩阵的计算方法, 针对中国气溶胶浓度较高且变化剧烈的特征, 设计了非线性迭代方案. 然后在低气溶胶、高气溶胶和抬高型气溶胶三种状态下, 通过计算机仿真模拟验证了MAX-DOAS气溶胶消光系数垂直分布反演算法, 讨论了误差来源. 之后在合肥地区开展了连续观测实验, 并将反演的AOD与CE318太阳光度计对比, 两者的相关性系数达到了0.94. AOD反演的相对误差约为20%. 又将反演的最低层(0–0.3 km)气溶胶消光系数与能见度仪对比, 两者的相关性系数为0.65. 近地面气溶胶消光系数反演的总相对误差约为10%. 模拟验证和对比实验均说明本文研究的气溶胶消光系数垂直廓线反演算法可以较好地获取对流层的气溶胶状态. 关键词： 多轴差分吸收光谱 气溶胶消光系数垂直廓线 气溶胶光学厚度 最优估算法     

地基消光测量确定大气气溶胶模型

分别取大陆型、海洋型、城市型和Junge谱分布气溶胶模型,用6S辐射传输算法计算出对应于太阳光度计测量时的各波段大气气溶胶光学厚度。将模式计算值与测量值进行比较,确定测量地区的大气气溶胶模型。将该方法用于2004年在北京地区测量的太阳光度计数据,结果显示该地区当日实际大气在几种气溶胶模型中较为符合城市型气溶胶模型。     

差分吸收光谱技术监测气溶胶光学厚度及大气能见度的研究

介绍了一种基于闪烁氙灯光源、利用差分光谱吸收(DOAS)技术监测大气气溶胶的新方法。提出用大气能见度确定系统校正参量的可行做法,解决了差分光谱吸收探测气溶胶领域原始光强难以测量的难题。并对350~650 nm范围内的气溶胶光学厚度进行反演,通过与多道太阳光度计的对比证实方法的可行性,实验中发现气溶胶光学厚度与悬浮颗粒物(SPM)浓度具有很好的相关性。同时,利用气溶胶550 nm处的消光系数确定大气能见度。     

基于DOAS技术的气溶胶粒谱分布反演方法研究

大气气溶胶不仅对全球的气候变化产生重大影响,其本身也是一种污染物,另外它在许多污染气体的化学反应中起重要作用。因此,实时监测大气气溶胶已成为环境领域的重要研究方向。差分吸收光谱技术是一种基于痕量气体“指纹”特性反演其浓度的光学遥感方法,同时该方法也可用于大气气溶胶消光系数的测量。文章介绍了利用闪烁差分吸收光谱系统监测大气气溶胶粒谱分布的方法,重点阐述了基于蒙特卡罗方法的粒谱分布反演算法,监测结果通过与PM10、能见度及Angstrom波长指数的对比证实了该方法的可行性,为近地面大气气溶胶监测提供了新的手段,同时也扩展了差分吸收光谱技术的应用范围,该方法对大气化学的研究有着重要的意义。     

Retrieval of aerosol physical and chemical properties from mid-infrared extinction spectra

We report several results that validate the accuracy of a retrieval method for the determination of a number of aerosol particle properties from their mid infrared (600-6000 cm⁻¹) extinction spectra. These properties include the number density, chemical composition, phase, size distribution, and to some extent, shape. The approach is based on information obtained in laboratory studies of micron-sized particles using the aerosol flow tube (AFT) technique. We report here experiments in which our method is used to measure a variety of aerosols including SiO₂ micro-spheres as well as solid NaCl, (NH₄)₂SO₄, ice and liquid water particles. The uncertainties in the retrieved aerosol properties associated with the particle shapes (spheres, spheroids, cylinders, hexagonal and rectangular prisms) as well as the effect of variations in the spectral range were evaluated. To assess the accuracy of the retrieved size distributions and particle shapes, the properties calculated from infrared spectra were compared with corresponding properties determined using alternative methods. We used scanning electron microscopy (SEM) for solid (NH₄)₂SO₄ and NaCl aerosols and direct particle imaging with an optical microscope assembly for liquid water aerosols. On the basis of the validation results, we discuss the boundaries of applicability of the most popular spectral model, single scattering by spherical, homogeneous aerosol particles.     

发光二极管在差分吸收光谱系统中的应用研究

研究了新型发光二极管(LEDs)作为主动差分吸收光谱技术(DOAS)光源的可行性及其应用.分析了LEDs发光特性、谱的形状、光谱范围和谱的稳定性.结果表明LEDs作为主动DOAS光源是可行的,只是当温度不恒定时,LEDs光谱中的法布里-珀罗标准具效应将影响DOAS精确反演,若把其结构提取参与拟合可以很好地去除其影响.并成功地利用LEDs-DOAS系统监测了大气NO₂的浓度,与基于高压氙弧灯为光源DOAS系统测量结果的相关性达到0.99以上.当光程为0.7km时,检测限为1.1×10< 关键词： 发光二极管(LEDs) 差分吸收光谱技术(DOAS) 可行性     

Analysis of influence of atmosphere extinction to Raman lidar monitoring CO2 concentration profile

Lidar （Light detection and ranging） system monitoring of the atmosphere is a novel and powerful technique tool. The Raman lidar is well established today as a leading research tool in the study of numerous important areas in the atmospheric sciences. In this paper, the principle of Raman lidar technique measurement CO2 concentration profile is presented and the errors caused by molecular and aerosol extinction for CO2 concentration profile measurement with Raman lidar are also presented. The standard atmosphere extinction profile and ＇real-time＇ Hefei area extinction profile are used to conduct correction and the corresponding results are yielded. Simulation results with standard atmosphere mode correction indicate that the errors caused by molecule and aerosol extinction should be counted for the reason that they could reach about 8 ppm and 5 ppm respectively. The relative error caused by Hefei area extinction correction could reach about 6%. The errors caused by the two components extinction influence could produce significant changes for CO2 concentration profile and need to be counted in data processing which could improve the measurement accuracies.     

大气气溶胶消光特性和折射率的测量

介绍了一种综合利用能见度仪、微脉冲激光雷达和光学粒子计数器测量大气气溶胶折射率的新方法。首先使用能见度仪和激光雷达测量出大气气溶胶的消光系数和消光后向散射比,然后使用粒子计数器测量出粒子谱分布,结合气溶胶粒子折射率,根据球形粒子的米（Mie）散射理论,可以得到气溶胶消光系数和消光后向散射比。通过分析消光系数、消光后向散射比、粒子谱分布和折射率之间的关系,结合已知的消光系数和消光后向散射比,反演出大气气溶胶粒子的折射率。     

双光路DOAS系统获取大气颗粒物粒谱分布方法研究

当前大气复合污染日趋严重,造成大气氧化性增强,气体向颗粒物的转化加快。大气颗粒物粒径大小及谱分布决定其在大气中的行为,以差分吸收光谱法（DOAS）为基础,结合双光路设计技术,开展实时、在线、获取近地面大气气溶胶颗粒物的粒谱分布的光谱方法研究。首先构建低噪声性能稳定的宽带氙弧灯为光源的双光路差分吸收光谱系统,基于干净天气条件下大气的能见度数据对系统进行校准,通过两个不同光路获得的光谱信号强度之比获取近地面紫外-近红外波段的大气总宽波段消光系数。基于宽波段消光系数,在去除瑞利散射以及气体吸收对消光系数的影响后,解析出气溶胶颗粒物的消光系数。基于核函数准则,利用均匀球型粒子的电磁场Mie理论来反演气溶胶物理特性,获得气溶胶粒子在该测量谱段的体积谱分布,利用体积谱与数密度谱的关系,反演出气溶胶粒子的数密度谱分布。开展利用直方图方法来表现颗粒物的粒谱分布方法研究,首先将DOAS测量波段近似等分为若干谱段,利用谱段处平均值,获取气溶胶粒谱直方分布图。最后把该系统和方法应用于外场实验,获得了气溶胶颗粒物在300～650 nm范围内的消光系数,将测量波段等分为11个谱段,反演了颗粒物的在0.1～1.25 μm粒径范围的数密度谱分布。该研究为整治我国灰霾天气,研究大气气相/粒子非均相化学反应提供科学依据。同时将推动DOAS技术的进一步发展和应用。     

光纤模式混合器在差分吸收光谱系统中的应用研究

差分吸收光谱技术(DOAS)已经发展为监测对流层痕量气体的重要技术，一般采用光电倍增管(PMT)作为探测器.由于光电二极管阵列(PDA)在多道探测及像元灵敏性方面的优势，采用PDA代替扫描探测装置将能改善系统剩余噪声，提高系统性能.但实际应用中由于使用收发一体Cassegrain望远镜造成灯谱与大气谱结构不统一，在消除PDA像元间差异的过程中给系统带来误差，从而导致剩余噪声的标准偏差达到1.4×10^-3.根据光纤扰模原理在系统中加入自制光纤模式混合器很好的解决了上述难题，在实际应用中起到良好的作用，系统剩余噪声的标准偏差为3.4×10^-4. 关键词： 差分吸收光谱 扰模 模式混合器 剩余噪声     

Performance limitations of an optical heterodyne CPFSK transmission system due to self-phase modulation

A detailed theoretical analysis is presented to evaluate the combined influence of self-phase modulation (SPM) and group velocity dispersion (GVD) of optical fiber on the bit error rate (BER) performance of a heterodyne optical CPFSK system. The power penalty suffered by the system due to the combined influence of GVD and SPM is evaluated from the BER performance results. It is found that the penalty due to SPM at a BER of 10⁻⁹ is significant when the input power exceeds 7 dBm. Further, the CPFSK system with modulation index of 0.5 is less sensitive to the effects of GVD and SPM compared to the system with a modulation index of 1. The theoretical results are in conformity with the experimental results reported earlier.     

深圳城市气溶胶物理光学特性的观测研究

气溶胶是影响气候变化和空气污染的重要因子.在深圳地区展开气溶胶观测实验,可以获得可靠的光学物理特征,进而有助于准确评估气溶胶在新型超极城市区域的气像和环境效应.本文利用2010年12月至2011年8月太阳光度计、黑碳和浊度计等气溶胶观测资料,分析了新型超级城市深圳地区的气溶胶物理光学特性.深圳地区气溶胶呈明显季节变化,冬、春季由于城市污染性气溶胶的影响,气溶胶光学厚度和Angstrom波长指数都较大,夏季受海盐气溶胶的影响,光学厚度较小,Angstrom波长指数也较小.光学厚度与Angstrom 波长指数对比表明城市综合性污染是引起深圳气溶胶高光学厚度的主要原因.深圳地区气溶胶的散射系数、吸收系数的平均值(标准偏差)分别为178.7×10^-6 m^-1(126.6×10^-6 m^-1)和32.5×10^-6 m^-1(18.1×10^-6 m^-1),均低于珠三角腹地多年观测平均值的二分之一和国内其他大型城市观测值.而单次散射反照率为0.81,与珠三角其他地区得到的结果接近.此外,气溶胶吸收、散射和单次散射反照率呈明显日变化,可能主要受大气边界层变化的影响.     

可见光到远红外波段气溶胶衰减计算模式

建立了一种根据实测的气溶胶尺度谱分布(Junge指数)、地面能见度、相对湿度和气溶胶衰减廓线计算空间任意两点的气溶胶衰减计算模式,光谱波段范围覆盖了从可见光到远红外(1~25 000 cm-1)。利用该气溶胶模式及国际上流行软件MODTRAN中的气溶胶模式同时和光栅太阳辐射计(pgs100)实测气溶胶衰减进行了对比,这种模式与MODTRAN相比,因考虑了气溶胶的实际尺度谱分布和高度分布,计算结果更接近实测值。利用所建立的气溶胶模式还分析了气溶胶衰减受各参数的影响,结果表明：气溶胶衰减受各参数影响较大,说明实测气溶胶参数在计算气溶胶衰减中起重要作用。将此气溶胶模式嵌入到我们自己研制的通用大气辐射传输软件CART中进行大气透过率和大气辐射传输的计算,有助于提高计算精度和增强功能。     

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.     

Attenuation characteristics of a light attenuator combined by polarizers with different extinction ratios

This paper deals with a systematical analysis and an algorithm of attenuation characteristics of a light attenuator combined by n pieces of polarizers (n-LACP) whose extinction ratios are different from each other.The attenuation ratio expression of a two-LACP is deduced.We find that the monotonic attenuation interval depends on the first polarizer and that the attenuation range depends on the second one.For the three-LACP,a method for obtaining a monotonic attenuation interval is proposed.Moreover,the attenuation ratio expression is demonstrated.Analysis and experiment show that when the initial status of the three-LACP is at the maximum output,if the second or third polarizer rotates alone,the minimum attenuation ratios can reach K-1 2 and K-1 3,respectively,and if the first polarizer rotates,a minimum attenuation ratio of K-1 2 K-1 3 can be obtained (K 1,K 2 and K 3 represent the extinction ratios of the three polarizers in turn).Furthermore,the attenuation ratio expression of n-LACP and the relevant attenuation characteristics are proposed.The minimum attenuation ratio of an n-LACP is (K 2 K 3 ··· K n)-1.     

机载多轴差分吸收光谱技术获取对流层NO2 垂直柱浓度的研究

介绍了一种基于机载平台获取对流层NO₂垂直柱浓度的多轴差分吸收光谱技术. 研究了利用差分吸收光谱技术结合不同观测角度的测量光谱反演差分斜柱浓度, 并利用辐射传输模型SCIATRAN计算对流层NO₂垂直柱浓度的方法. 研究了不同海拔高度、不同地面反照率以及不同太阳天顶角等条件对天顶和天底两个观测角度的大气质量因子的影响. 报道了该系统在2008年12月10日在珠三角地区的实验结果, 结合天顶和天底两个方向反演得到了珠三角地区对流层NO₂垂直柱浓度的分布信息. 同时还将机载测量结果跟安装在珠海市的一台地基多轴差分吸收光谱仪的结果进行了对比, 二者相差仅为8%. 实验结果表明, 机载多轴DOAS技术可以实现对大区域对流层NO₂浓度的快速获取.