Measurements of Nighttime Nitrate Radical Concentrations in the Atmosphere by Long-Path Differential Optical Absorption Spectroscopy

The long-path differential optical absorption spectroscopy （LP-DOAS） technique was developed to mea- sure nighttime atmospheric nitrate radical （NO3） concentrations. An optimized retrieval method, resulting in a small residual structure and low detection limits, was developed to retrieve NO3. The time series of the NO3 concentration were collected from 17 to 24 March, 2006, where a nighttime average value of 15.8 ppt was observed. The interfering factors and errors are also discussed. These results indicate that the DOAS technique provides an essential tool for the quantification of NO3 concentration and in the study of its effects upon nighttime chemistry.

Analysis of spectrum characteristics of optical scintillation in stack gas flow

Based on the analysis of spectrum characteristics of intensity fluctuations while light beams pass through stack gas flow in an industrial setting, this paper puts emphasis upon discussing the spectrum of optical intensity fluctuations by the variety of particle concentration in stack gas flow. This paper also gives the primary theoretical explanation of the measurement results in the stack of coal-fired utility boilers. Meanwhile, the cross-correlation formula is given as the theoretical basis of velocity measurement by using particle concentration scintillation.

Observation of tropospheric NO_2 by airborne multi-axis differential optical absorption spectroscopy in the Pearl River Delta region,south China

An airborne multi-axis differential optical absorption spectroscopic （AMAX-DOAS） instrument was developed and applied to measure tropospheric NO2 in the Pearl River Delta region in the south of China. By combining the measurements in nadir and zenith directions and analyzing the UV and visible spectral region using the DOAS method, information about tropospheric NO2 vertical columns was obtained. Strong tropospheric NO2 signals were detected when flying over heavilly polluted regions and point sources like plants. The AMAX-DOAS results were compared with ground-based MAX-DOAS observations in the southwest of Zhuhai city using the same parameters for radiative transport calculations. The difference in vertical column data between the two instruments is about 8%. Our data were also compared with those from OMI and fair agreement was obtained with a correlation coefficient R of 0.61. The difference between the two instruments can be attributed to the different spatial resolution and the temporal mismatch during the measurements.

Influence of laser intensity in second-harmonic detection with tunable diode laser multi-pass absorption spectroscopy

Tunable diode laser absorption spectroscopy （TDLAS） has been widely employed in atmospheric trace gases detection. The ratio of the second-harmonic signal to the intensity of laser beam incident to the multi-pass cell is proved to be proportional to the product of the path length and the gas concentration under any condition. A new calibration method based on this relation in TDLAS system for the measurement of trace gas concentration is proposed for the first time. The detection limit and the sensitivity of the system are below 110 and 31ppbv （parts-per-billion in volume）, respectively.

Application of α-β-γ filtering to real-time atmosphere methane concentration measurement

A real time α-β-γ filtering technique is applied to the monitoring of atmosphere CH4 based on a tunable diode laser spectrum system operating at 1.654μm. This technique is developed for improving the sensitivity and precision of CH4 concentration measurement with slow concentration change. The effectiveness of this technique is evaluated by performing CH4 concentration measurement and using it to monitor the varying methane level in the atmosphere. It was proved that signal noise ratio enhancement factor is 4.25. The comparison between this filter and moving average is also included in this article. It indicates the advantage of the α-β-γ real time filter.

Simulation studies of multi-line line-of-sight tunable-diode-laser absorption spectroscopy performance in measuring temperature probability distribution function

Line-of-sight tunable-diode-laser absorption spectroscopy（LOS-TDLAS） with multiple absorption lines is introduced for non-uniform temperature measurement. Temperature binning method combined with Gauss–Seidel iteration method is used to measure temperature probability distribution function（PDF） along the line-of-sight（LOS）. Through 100 simulated measurements, the variation of measurement accuracy is investigated with the number of absorption lines, the number of temperature bins and the magnitude of temperature non-uniformity. A field model with 2-T temperature distribution and15 well-selected absorption lines are used for the simulation study. The Gauss–Seidel iteration method is discussed for its reliability. The investigation result about the variation of measurement accuracy with the number of temperature bins is different from the previous research results.

Determination of aerosol extinction coefficient and mass extinction efficiency by DOAS with a flashlight source

With the method of differential optical absorption spectroscopy （DOAS）, average concentrations of aerosol particles along light path were measured with a flashlight source in Chiba area during the period of one month. The optical thickness at 550 nm is compared with the concentration of ground-measured suspended particulate matter （SPM）. Good correlations are found between the DOAS and SPM data, leading to the determination of the aerosol mass extinction efficiency （MEE） to be possible in the lower troposphere. The average MEE value is about 7.6m^2.g^-1 , and the parameter exhibits a good correlation with the particle size as determined from the wavelength dependence of the DOAS signal intensity.

Retrieval algorithm of quantitative analysis of passive Fourier transform infrared (FTRD) remote sensing measurements of chemical gas cloud from measuring the transmissivity by passive remote Fourier transform infrared

Passive Fourier transform infrared （FTIR） remote sensing measurement of chemical gas cloud is a vital technology. It takes an important part in many fields for the detection of released gases. The principle of concentration measurement is based on the Beer-Lambert law. Unlike the active measurement, for the passive remote sensing, in most cases, the difference between the temperature of the gas cloud and the brightness temperature of the background is usually a few kelvins. The gas cloud emission is almost equal to the background emission, thereby the emission of the gas cloud cannot be ignored. The concentration retrieval algorithm is quite different from the active measurement. In this paper, the concentration retrieval algorithm for the passive FTIR remote measurement of gas cloud is presented in detail, which involves radiative transfer model, radiometric calibration, absorption coefficient calculation, et al. The background spectrum has a broad feature, which is a slowly varying function of frequency. In this paper, the background spectrum is fitted with a polynomial by using the Levenberg-Marquardt method which is a kind of nonlinear least squares fitting algorithm. No background spectra are required. Thus, this method allows mobile, real-time and fast measurements of gas clouds.

Accuracy improvement of calibration-free laser-induced breakdown spectroscopy

Calibration-free laser-induced breakdown spectroscopy can overcome the matrix effect and the huge application prospects of in situ and on-line measurement, so it has been studied and applied to many analytical samples by numerous researchers since it was first proposed in 1999.However, its accuracy is always lower than other analytical techniques and traditional quantitative analysis methods of laser-induced breakdown spectroscopy. The goal of this paper is to review the improvement of accuracy in the experimental setup and spectral analysis,especially after 2010, but not limited to it. The main contents include the accurate measurement of spectral intensity, the spatial and temporal window of local thermodynamic equilibrium and the accurate calculation of temperature and electron density. Due to the requirement of one or more standard samples, the combination of standard samples and CF-LIBS is discussed as a separate section. Finally, a simple conclusion is offered to relevant researchers who want to use CF-LIBS for quantitative analysis.

Correlation Study Between Suspended Particulate Matter and DOAS Data

Continuous data of aerosol optical thickness monitored using differential optical absorption spectroscopy （DOAS） are correlated with the concentration of ground-measured suspended particulate matter （SPM）. A high correlation is found between the DOAS and the ground SPM data, making it possible to calculate the mass extinction efficiency of the aerosols in the atmosphere. It is found that the value of mean mass extinction efficiency （MEE） varies over a range of 2.6-13.7 m^2 g^-1, with smaller and larger values occurring for size distributions dominated by coarse and fine particles, respectively.

Covariance analysis of the Coulomb explosion of ammonia induced by intense nanosecond laser at 532 nm

The Coulomb explosion of ammonia clusters induced by nanosecond laser at 532 nm with an intensity of ~1012 Wcm-2 has been studied by time of flight mass spectrometry. The dominant multiply charged ions are N3+ and N2+ with kinetic energies of 110 and 50 eV respectively. The electrons generated from the multiphoton ionization are heated through inverse bremsstrahlung by the laser field when colliding with neutral or ionic particles. When their energies surpass the corresponding ionization potentials of the molecules or ions, the subsequent electron impact ionization may take place thus resulting in multi-charged nitrogen ions. Covariance analysis is made to study the possible pathways of the Coulomb explosion.

Hydrogen Bonding Interaction of Formic Acid-, Formaldehyde-, Formylfluoride-Nitrosyl Hydride： Theoretical Study on the Geometries, Interaction Energies and Blue- or Red-Shifted Hydrogen Bonds

The hydrogen bonding interaction of formic acid-, formaldehyde-, formylfluoride-nitrosyl hydride complexes was investigated by the density functional theory （DFT） and ab inito method in conjunction with 6-311＋＋G（2d,2p） basis set. The geometries, vibrational frequencies and interaction energies of the complexes were calculated by both standard and CP-corrected methods respectively. Moreover, G3B3 method was employed to estimate the interaction energies. There are C--H…O, N--H…O, N--H…F blue-shifted H-bonds and red-shifted O----H…O H-bond in the complexes. Electron density redistribution and rehybridization contribute to the N--H and C--H blue shifts. All geometric reorganizations contribute to the N--H blue shifts and partial geometric reorganizations contribute to the C--H blue shifts. The geometric reorganizations of the complex C except ZH（5）-O（4）-C（1） contribute to the O----H red shift. For the N--H blue shifts, the effect of r（N--O） variation on the N--H blue shifts is larger than that of ZH-N-O variation. Rehybridization plays a dominant role in the degree of N--H blue shifts, whereas the electron density redistribution contributes more to the degree of C--H blue shifts than the other effects do.

Large scale gas leakage monitoring with tunable diode laser absorption spectroscopy

Tunable diode laser absorption spectroscopy （TDLAS） has been widely employed in atmospheric trace gases detecting and industrial control due to its high sensitivity, selectivity, and rapidity of response. An open path TDLAS system is developed for monitoring large scale methane leakage around the oil refinery. The tunable distributed feedback （DFB） diode laser emits at 1.65 pro. In order to enhance the sensitivity, a system combining long open path and second harmonic detection technique is developed. The test results show that the time resolution is less than 0.1 second and the detection limit is lower than 3.6 ppmv. This system is adapted for monitoring a large scale methane concentration changing trend instead of measuring its absolute concentration.

A high sensitivity spectrometer with tunable diode laser for ambient methane monitoring

Tunable diode laser absorption spectroscopy （TDLAS） has been widely employed in atmospheric trace gases detection. In the measurement of these trace gases, harmonic detection combined with a multi-pass white cell could remarkably enhance the detection sensitivity. In this paper, a portable TDLAS system built specifically for long time monitoring methane in the atmosphere is introduced. The detection limit is below 100 ppb that is enough for the monitoring of ambient methane, and the long time monitoring results obtained in Beijing are given, which is well coincident with that of the Fourier transform infrared （FTIR） spectroscopy.

Fiber-distributed multi-channel open-path H_2S sensor based on tunable diode laser absorption spectroscopy

Tunable diode laser based gas detectors are now being used in a wide variety of applications for safety and environmental interest. A fiber-distributed multi-channel open-path H2S sensor based on tunable diode laser absorption spectroscopy （TDLAS） is developed, the laser used is a telecommunication near infrared distributed feed-back （DFB） tunable diode laser, combining with wavelength modulation spectroscopy technology, a detection limit of 20 ppm-m is demonstrated. Multi-channel detection is achieved by combining optical fiber technique. An on-board reference cell provides on-line sensor calibration and almost maintenance-free operation. The sensor is suitable for large area field H2S monitoring application.