Cross-interference correction and simultaneous multi-gas analysis based on infrared absorption

In this paper, we present simultaneous multiple pollutant gases (CO 2 , CO, and NO) measurements by using the non-dispersive infrared (NDIR) technique. A cross-correlation correction method is proposed and used to correct the cross-interferences among the target gases. The calculation of calibration curves is based on least-square fittings with third-order polynomials, and the interference functions are approximated by linear curves. The pure absorbance of each gas is obtained by solving three simultaneous equations using the fitted interference functions. Through the interference correction, the signal created at each filter channel only depends on the absorption of the intended gas. Gas mixture samples with different concentrations of CO 2 , CO, and NO are pumped into the sample cell for analysis. The results show that the measurement error of each gas is less than 4.5%.     

单组分双分析通道红外气体检测方法研究

基于单分析通道非分散红外(non-dispersive infrared, NDIR)气体分析技术, 提出一种单组分双分析通道气体检测方法. 根据SO₂的红外吸收特征, 采用逐线积分气体吸收模型和方法, 选择洛伦兹展宽线型并考虑温度和气压对积分线强、线型的影响, 确定了两个分析通道的滤波参数.使用7.32 μm和4 μm波段分别反演小于等于 280 ppm与大于280 ppm的SO₂浓度;使用最小二乘法, 以三阶多项式为拟合模型, 获得了两个分析通道的定标曲线.对系统的测量线性度、检测限和测量准确度进行了分析. 两个分析通道的联合可以实现约几ppm至10000 ppm的宽动态范围的SO₂测量, 且系统测量线性度大于0.99, 测量误差小于5%.既克服了NDIR气体分析技术检测灵敏度和宽动态测量范围不能同时兼顾的缺陷, 良好的系统测量线性度还为多组分气体分析的干扰修正提供了非常必要的前提条件.     

非线性吸收对多组分气体分析的影响及其修正方法

利用非分散红外(NDIR)技术研究了非线性吸收现象对多组分气体分析交叉干扰扣除的影响及其修正方法。理论上推导了由于非线性吸收导致的干扰系数变化对系统测量准确度的影响。对常规的干扰方程组进行了修正,使用干扰函数来定量分析气体间的交叉干扰,当测量气体存在非线性吸收时,干扰函数也会发生相应变化。基于最小二乘法,以三阶多项式为拟合模型,拟合出了系统的干扰函数。利用拟合的干扰函数,通过实验证明了提出的修正方法在系统存在非线性吸收现象时仍能有效地扣除气体间的交叉干扰。     

Recent improvements on atmospheric CO2 measurements at Mt. Cimone observatory, Italy

Summary Continuous atmospheric CO₂ measurements have been carried out at Mt. Cimone from 1979 up to the present. Omitting here a measurement presentation, in this paper we show the current experimental procedures adopted and NDIR apparatus performances. Quality measurements have been recently improved by introducing an ULTRAMAT-5E (SIEMENS) NDIR analyzer controlled, for operating mode, by computer: the routine precision attained is ±0.1 p.p.m. An interesting performance of the analyzer is its nondetectable sensitivity to water vapour infrared absorption, enabling us also to determine CO₂ measurements in wet air. A flask sampling technique and an investigation of the flask deterioration risk, against storing time, are presented. Results of the investigation validate the use of electropolished stainless-steel flasks for high-quality measurements.     

NDIR多组分气体分析的干扰修正方法研究

介绍了非分散红外(Non-Dispersive Infrared,NDIR)多组分气体分析的一种干扰修正方法.根据逐次积分气体吸收模型和方法,并考虑温度和气压对积分线强和线型的影响,选择洛伦兹展宽线型,得到了CO,CO2,NO和H2O在各个滤波通道的响应系数.利用响应系数建立了用于干扰修正的四元线性回归方程组,通过求解...     

Selectivity of the optical-absorption method based on an instrumental pick out of Fourier components in the absorption spectrum

The introduction of interference–polarization filters (IPFs) in the structure of an optical–absorption analyzer makes it possible to pick out a harmonic (a Fourier component of the absorption spectrum) providing measurement with the highest sensitivity. The selectivity of such a method of analysis is determined by overlapping the oscillations of the measured and interfering components. By the example of measurement in benzene in the presence of an interfering component (toluene), the possibility is considered for the optimization of selectivity due to the variation of the path-difference dispersion for ordinary and extraordinary interfering rays. The metrological characteristics of the interference–polarization analyzer of C₆H₆ confirming the results of calculations are given.     

NO2分子高灵敏度痕量探测技术研究

 搭建了一台基于蓝光LED的非相干宽带腔增强吸收光谱系统,并将其应用于NO2分子的高灵敏度痕量探测研究。在3 s采样时间下, 系统探测灵敏度为3.2×10-9 cm-1（1 σ）,对应NO2的探测极限约为187 pmol/mol。利用Allan方差对系统最佳采样时间及系统稳定性进行分析,当采样时间延长至30 s时,系统的探测极限可提高至44 pmol/mol。将该系统应用于实际大气中NO2的连续测量,其测量结果与商业化NOx分析仪（Thermo 42i）进行了比对测试。     

Resonant optoacoustic detector in nondispersive gas analyzer scheme

A nondispersive gas analyzer scheme is suggested, in which the resonant optoacoustic device is used for detection of air sample absorption, where modulation with the appropriate spectral filtration is carried out with the help of pure detecting gas cells. Analyzer performance for CO₂, CO, CH₄, SO₂ and NO is studied. The modulation depth for gas cells was found to be between 0.45 for NO and 0.84 for CO₂. Trace-gas detectivity is limited by acoustical noise, originating from light beam chopper at a level of 10⁻²%. Information about the influence of spectral interference on detection selectivity was obtained.     

萃取分离-石墨炉原子吸收光谱法测定盐卤中痕量铯的研究

采用墨炉原子吸收光谱法（ＧＦＡＡＳ）研究盐卤中铯原子化行为和机理,建立了热解石墨管、ＫＮＯ３－ＮＨ４ＮＯ３基体改进剂、１８－冠－６、溴百里香酚蓝、氯仿萃取分离－ＧＦＡＡＳ测定盐卤中铯的方法。用于测定盐卤中痕量铯,特征质量１．４×１０－１０ｇ／０．００４４Ａ;加标回收率８９％～１０５％;相对标准偏差４．１３％。     

Feasibility study of Zeeman modulation spectrometry with a hollow capillary fiber based gas cell

For paramagnetic gases (e.g., O2, NO, NO2, OH) Zeeman modulation spectrometry is a method for spectrometric gas sensing with extraordinary selectivity. In this Letter it is combined with a hollow capillary based gas cell, where the gas is filled in long light-guiding capillary that is placed inside a toroidal coil. Over conventional Zeeman spectrometry this has the advantage of lower power consumption at long optical path length, since several loops of the hollow capillary fiber can be placed in the coil. Compared to wavelength modulation spectrometry the advantage is insensitivity to interference by multimode propagation in the fiber and absorption by other nonparamagnetic gases, which should enhance both sensor stability and sensitivity. Experimental and theoretical results are presented, showing the feasibility of the approach.     

遗传规划用于非分散红外吸收光谱的CO浓度测量

非分散红外吸收光谱法(NDIR)是CO浓度测量的主要手段之一.设计了NDIR的开放式CO气体测量系统及连续测量实验装置,对10种不同浓度的标准CO气体进行测量实验,分析了获取的40个实测数值.将遗传规划(GP)用于CO光强采样数据的建模,得到验证集的相关系数为0.999 7,验证集的相对误差最大值和平均相对误差分别为4...     

L-M非线性拟合的TDLAS氧气测量研究

氧气浓度是工业生产过程中重要监测参数,采用可调谐二极管激光吸收光谱法(tunable diode laser absorption spectroscopy,TDLAS),结合波长调制技术,可以实现对现场氧气浓度的高精度在线监测,利用氧气位于760 nm处的特征吸收峰进行了氧气浓度的测量。由于激光具有很强的相干性,所以TDLAS技术的检测灵敏度受到光学干涉噪声的严重制约,特别在低浓度时,光学干涉引起的基线起伏使得提取吸收峰波形信号时出现较大误差,影响了TDLAS分析仪的监测灵敏度。针对这一情况,采用了Levenberg-Marquardt非线性拟合算法,并且利用了吸收谱线线型——洛伦兹线型的导数形式对波长调制后获得的二次谐波波形信号进行拟合,提取波形信息。另一方面Levenberg-Marquardt非线性拟合方法需要有大量的计算,为了使研制的TDLAS分析仪能够实现现场的实时监测,采用了支持浮点运算的DSP的C28系列芯片进行数据处理,实现仪器在现场实时监测的功能。实验结果表明,该算法能够有效提取二次谐波信号的吸收峰特征值、克服背景噪声影响,由算法反演得到的氧气浓度与实际浓度的线性比值为1.01,浓度测量的线性误差为1.18%。     

基于同步光解的OH自由基标定方法

OH自由基是大气中最重要的氧化剂,准确测量对流层OH自由基的浓度是厘清我国二次污染形成机理的关键.本文介绍了一种基于同步光解的OH自由基便携式标定方法,使用汞灯的185 nm线辐射处于层流状态下的具有一定水汽浓度的合成空气,光解HO2和O2定量产生确定浓度的OH, HO2自由基和O3.开展了臭氧浓度及廓线分布因子P和氧气吸收截面等影响因素的准确测量,降低该标定方法的不确定度.进一步构建便携式标定装置,建立应用于实际外场标定的OH自由基浓度快速获取方法.开展基于激光诱导荧光技术OH自由基(LIF-OH)探测系统的准确标定测试,准确产生3×10^8-2.8×10^9 cm^-3浓度的OH自由基, LIF-OH探测系统的荧光信号与自由基浓度具有非常好的相关性.在综合外场观测(STORM)的应用中该标定装置的不确定度为13.0%,具有良好的稳定性和准确性,可以用于复杂外场环境下LIF-OH系统的快速标定.     

可调谐半导体激光吸收光谱监测农田气体通量特性研究

可调谐半导体激光吸收光谱(TDLAS)具有高选择性,高灵敏度等特性,非常适合监测农田痕量气体交换过程。采用开放式光程的可调半导体激光吸收光谱和非分散红外光谱技术,在封丘农田进行了一个月监测试验。选择CO2作为目标气体,用两种不同光谱技术选择不同的通量计算方法,分别获取农田排放通量。根据实验条件,提出了TDLAS的通量印痕模型,对比分析了两种技术的空间代表性特性,同时分析了数据误差来源和不同外界因素对通量测量的影响特性。结果发现在相同的气象条件下,仪器架设高度越高,光学路径越长,开放光路的TDLAS通量贡献区就越大。这些结果对通量监测中仪器安装有很好的指导意义。     

采用离轴入射的腔增强吸收光谱研究

为了改善腔增强吸收光谱的探测灵敏度和光谱分辨率,通过将激光光束离轴注入光学谐振腔中,减小了谐振腔内振荡,提高了模式密度,使得谐振腔被近似看作为“怀特池”。采用记录波长在扫描过程中实际变化的方法,对光谱数据进行了非线性校正,省去了参考光路的布置,简化了实验光路。对二氧化碳在1．572μm处的一条弱吸收谱线进行了测量,得到了大小为1．98×10^-7cm^-1的最小探测灵敏度。实验结果表明同等实验条件下,光束离轴入射时比正轴入射时的腔增强吸收光谱具有更高的信噪比和光谱分辨率。     

An optical system for measuring nitric oxide using spectral separation techniques

An optical sensor based on differential absorption spectroscopy for real-time monitoring of industrial nitric oxide (NO) gas emission is described. The influence of gas absorption interference from sulfur dioxide (SO₂) in the environment was considered and a spectral separation technique was developed in order to eliminate this interference effect. The absorption spectrum of SO₂ around 226 nm was evaluated by the SO₂ concentration obtained using the experimentally recorded absorption spectrum around 300 nm. The absorption spectrum of NO around 226 nm was obtained by subtracting the absorption of SO₂ from the integral absorption spectrum of SO₂ and NO. The concentration measurements were performed at atmospheric pressure. The technique was found to have a lower detection limit of 0.8 ppm for NO per meter path length (SNR=2) and be immune from the influence from SO₂ on the NO measurement. The sensor based on this technique was successfully employed for in situ measurement of SO₂ and NO concentrations in the flue gas emitted from an industrial coal-fired boiler.     

火焰原子吸收法测定钢铁中钴时的背景吸收及消除

对于背景校正装置的原子吸收分光光度计,用火焰原子吸收法测定钴时,由于铁等有背景吸收（指铁的背景通过吸收池以后的背景,称为背景吸收）,故无法用标准加入法测定钢铁中低含量钴。本文对测钴时的背景吸收及铁的干扰做了详细的研究,用金２４２．８ｎｍ谱线做为测钴时背景吸收校正线,可完全扣除背景吸收。用标准加入法测定了钢及高温合金中低含量钴。     

Selected optoelectronic sensors in medical applications

Optoelectronic technology plays an important role in medical diagnosis. In the paper a review of some optoelectronic sensors for invasive and non-invasive human health test is presented. The main attention is paid on their basic operation principle and medical usefulness. The paper presents also own research related to developing of tools for human breath analysis. Breath sample unit and three gaseous biomarkers analyzer employing laser absorption spectroscopy designed for clinical diagnostics were described. The analyzer is equipped with sensors for CO, CH₄ and NO detection. The sensors operate using multi-pass spectroscopy with wavelength modulation method (MUPASS-WMS) and cavity enhanced spectroscopy (CEAS).     

太阳光谱方法测量成都地区大气二氧化氮浓度

文章报道的是用太阳光谱方法测量成都地区NO2浓度的实验研究,使用CCD光学多道分析器采集成都市区和西岭雪山的太阳光谱,以大气上界太阳光谱为参考,对五个分立光谱段以最小二乘法进行数据拟合,应用差分吸收原理解谱,获得了成都市区和西岭雪山NO2浓度.成都市区NO2浓度(垂直柱体密度)在3.1×1016至5.8×1016(molecule·cm-2)之间,西岭雪山的NO2浓度在0.7×1016至1.0×1016(mole-cule·cm-2)之间.随大气温度的上升,NO2浓度有上升趋势.     

中红外谐波检测背景信号漂移的修正方法

可调谐半导体激光吸收光谱（TDLAS）由于具有高灵敏度、高分辨率、非侵入及实时检测等特点,被广泛应用于燃烧诊断、痕量气体监测、工业过程控制等领域中。波长调制光谱（WMS）的二次谐波（2f）检测是最常用的TDLAS气体传感方法之一。激光器作为TDLAS-WMS在线检测系统中最核心的部件之一,在长期运行过程中会由于其工作温度等因素变化,引起输出激光波长漂移和2f背景信号基线变化,从而导致气体浓度反演的精确度和TDLAS-WMS在线检测系统的稳定性降低。针对上述问题,根据NO气体分子在中红外波段5.176~5.189 μm的基频吸收特性,选择峰值发射波长位于5.184 μm的分布反馈式连续波量子级联激光器（DFB-CW QCL）,分析了输出激光中心波长对应的峰值采样点位置随采样时间变化的漂移规律和2f吸收及其背景信号的漂移特性。基于上述分析,提出了以2f信号平均峰峰值替代2f信号峰值建立气体浓度反演模型以修正2f背景信号基线漂移,并结合以信噪比最优为2f背景信号波长漂移修正原则的2f背景信号漂移综合修正方法,以消除TDLAS-WMS在线检测系统长期连续检测过程中2f背景信号漂移对气体浓度反演结果的不利影响。研究结果表明,2f信号平均峰峰值随配置的NO样气浓度的增加而增大,这两者呈现较好的线性关系,其拟合曲线的线性拟合度R2达到了0.999 9。在使用体积浓度为20×10-6 NO气体样品开展的连续60 min监测实验中,波长漂移修正后,反演浓度的标准偏差由波长漂移修正前的0.19×10-6下降到了0.07×10-6,反演浓度的最大相对误差由波长漂移修正前的6.30%下降到了3.85%,相对误差均方值由波长漂移修正前的24.39%下降到了9.99%。结果显示,该2f背景信号漂移综合修正方法可以有效地抑制2f背景信号漂移对气体浓度反演结果的影响,显著提高了TDLAS-WMS在线检测系统连续监测的灵敏度、精确度和稳定性。