Study of a Laser Wavelength Correction Method Applied to the Measurement of OH Radical with Laser-Induced Fluor.

A method for dye laser wavelength correction applied for the measurement of OH radical with FAGE (Fluorescence Assay by Gas Expansion) is researched in this article. Sufficiently stable concentration of OH radical is produced with thermal dissociation of H2O by using an alumel filament and the fluorescence is excited with 282 nm laser in a low pressure cell. The fluorescence is detected with a photomultiplier and a high speed data acquisition card, while the laser light is monitored by a photodiode, and both signals are handled by a LabVIEW program for further analysis. The data acquisition card is triggered by a positive TTL pulse generated by a digital delay generator, which is triggered by a rising edge of a synchronized output pulse of the dye laser. The LabVIEW program is used to determine the location of the OH excited line according to the fluorescence intensity of OH radical when the frequency of the dye laser is scanned. By scanning dye laser wavelength range in 281.97~282.28 nm, excitation spectrum of OH radical is recorded. In order to optimize system parameters and achieve a high signal-to-noise ratio, the effects of the humidity, oxygen concentration, mass flow and pumping speed on fluorescence intensity and lifetime are studied at Q12 line and less than ±1.9% fluctuations of the fluorescence intensity is obtained. With analysis of the reaction mechanism of the thermal dissociation of H2O, it is concluded that reaction of oxygen and water is a major source of OH radical. Laser output wavelength is scanned in a small range around Q12 line to find out the exact exciting line and then correct the laser's output, which might slightly shift due to the environmental change and leads to reduction of fluorescence intensity. The wavelength correction procedure is implemented many times and the results show that the systematic error of the instrument is less than 0.1 pm. According to the experimental results, this method meets the needs of quantitative accurate measuring tropospheric OH radical by FAGE.

[Quality Optimization Method for Ambient CO(2) Inversion of High Resolution Fourier Transform Infrared Spectrum].

CO(2) retrievals with high quality facilitate resolving the sources and sinks of CO(2) are helpful in predicting the trend in climate change and understanding the global carbon cycle. Based on a nonlinear least squares spectral fitting algorithm, we investigate the optimization method for CO2 products derived from ground-based high resolution Fourier transform infrared spectra. The CO(2) vertical column densities (VCDs) are converted into column-averaged dry air mole fraction XCO(2) by using the fitted O(2) VCDs, and thus the system errors (e. g. pointing errors, ILS errors, zero-level offset) are corrected greatly. The virtual daily variation which is related to air mass factor is corrected with an empirical model. The spectra screening rule proposed in this paper can greatly improve the XCO2 quality. The CO(2) retrievals before and after the optimized method are compared using a typical CO(2) daily time series. After using the optimized method, the fitting error is reduced by 60%, and the two-hours-averaged precision is ~0.071% (equals to ~0.28 ppm), which is perfectly in line with the TCCON (the total carbon column observing network) threshold, i. e., less than 0.1%.

Nocturnal Atmospheric NO3 Radical Monitoring and Analysis in Beijing with Cavity Ring Down System .

The oxidizability of NO3 radical in the nocturnal atmosphere is comparable with that of diurnal OH radical. Given the importance of NO3 radical in the nocturnal chemical process, accurate measurement of its concentration and analysis its nocturnal chemical process have important significance. The article introduces cavity ring-down spectroscopy (CRDS) instrument which is applied to measure atmospheric NO3 radical. Light from a red laser diode (the wavelength is 662 nm and line width is 0.3 nm) is coupled on-axis into an optical cavity formed by a pair of high-reflectivity mirrors (R≥99.998 5%) to achieve an effective absorption path length of approximately 20km. And it researches nocturnal chemical process of NO3 radical in view of the fall and winter heavy traffic areas. The measurement of NO3 radical with cavity ring-down spectroscopy was performed in Beijing from October 29 to November 15, 2014. During the observation, the concentration of NO3 radical is relatively low with the maximum of NO3 radical concentration of 50pptv and the average of its concentration of approximately10 pptv. Combining of NO2, O3 and NO data, the observation results are analyzed. The NO3 production rates ranging from 0.04 to 1.03 pptv·s-1 were calculated throughout the observation, and NO3 lifetime averaged at 68 s. The NO3 loss process in the atmosphere is further analyzed. Combining of related auxiliary data, the influence of different humidity as well as particulate matter concentrates on the atmospheric NO3 removal is researched. When atmospheric RH≥60% and PM2.5 concentration mainly greater than 60 µg·m-3，the correlation coefficient of the logarithmic correlation between NO3 lifetime and NO2 mixing ratio is 0.79，NO3 is mainly removed by the indirect loss process; however, when atmospheric RH≤40% and the concentration of PM2.5 mainly smaller than 60 µg·m-3, because of the observation site is close to national highway and influenced by local pollution source, the direct loss process is main; When atmospheric 40%

[An Incoherent Broadband Optical Cavity Spectroscopy for Measuring Weak Absorption Cross Section of Sulfur Dioxide].

As a highly sensitive detection technology, incoherent broadband cavity enhanced absorption spectroscopy (IBBCEAS) have successfully measured a variety of trace gases. According to the principle of cavity enhanced absorption spectroscopy, if the accurate concentration of the target gas, the curve of the mirror reflectance, effective absorption path length, the light intensity of the absorbing gas and non-absorbing gas are known, the absorption cross section of the absorption gas can be measured. The accurate measurements of absorption cross section are necessary for satellite retrievals of atmospheric trace gases and the atmospheric research. This paper describes an incoherent broadband cavity enhanced absorption spectroscopy(IBBCEAS) instrument with 365 nm LED as the light source for measuring absorption cross section of SO2 from 357 to 385 nm which is arising from the spin-forbidden a ³B1--X¹A1 transition. In comparison to the literature absorption cross section of SO2, and correlation coefficient r is 0.997 3. The result shows the potential of the IBBCEAS system for measuring weak absorption cross section.

[Fast and accurate extraction of ring-down time in cavity ring-down spectroscopy].

Research is conducted to accurate and efficient algorithms for extracting ring-down time (r) in cavity ring-down spectroscopy (CRDS) which is used to measure NO3 radical in the atmosphere. Fast and accurate extraction of ring-down time guarantees more precise and higher speed of measurement. In this research, five kinds of commonly used algorithms are selected to extract ring-down time which respectively are fast Fourier transform (FFT) algorithm, discrete Fourier transform (DFT) algorithm, linear regression of the sum (LRS) algorithm, Levenberg-Marquardt (LM) algorithm and least squares (LS) algorithm. Simulated ring-down signals with various amplitude levels of white noises are fitted by using five kinds of the above-mentioned algorithms, and comparison and analysis is conducted to the fitting results of five kinds of algorithms from four respects: the vulnerability to noises, the accuracy and precision of the fitting, the speed of the fitting and preferable fitting ring-down signal waveform length The research results show that Levenberg-Marquardt algorithm and linear regression of the sum algorithm are able to provide more precise results and prove to have higher noises immunity, and by comparison, the fitting speed of Leven- berg-Marquardt algorithm turns out to be slower. In addition, by analysis of simulated ring-down signals, five to ten times of ring-down time is selected to be the best fitting waveform length because in this case, standard deviation of fitting results of five kinds of algorithms proves to be the minimum. External modulation diode laser and cavity which consists of two high reflectivity mirrors are used to construct a cavity ring-down spectroscopy detection system. According to our experimental conditions, in which the noise level is 0.2%, linear regression of the sum algorithm and Levenberg-Marquardt algorithm are selected to process experimental data. The experimental results show that the accuracy and precision of linear regression of the sum algorithm is considerably close to those of Levenberg-Marquardt algorithm, and on the other hand, the fitting speed of linear regression of the sum algorithm is faster than that of Levenberg-Marquardt algorithm about five times. The experimental results are consistent with the simulation analysis, and it indicates that linear regression of the sum algorithm is the desirable fitting method, as far as our experimental conditions are concerned.

Coarse particles compensate for missing daytime sources of nitrous acid and enhance atmospheric oxidation capacity in a coastal atmosphere.

Large missing sources of daytime atmospheric nitrous acid (HONO), a vital source of hydroxyl radicals (OH) through its photolysis, frequently exist in global coastal regions. In this study, ambient HONO and relevant species were measured at a coastal site in the Pearl River Delta (PRD), China, during October 2019. Relatively high concentrations (0.32 ± 0.19 ppbv) and daytime peaks at approximately 13:00 of HONO were observed, and HONO photolysis was found to be the dominant (55.5 %) source of the primary OH production. A budget analysis of HONO based on traditional sources suggested large unknown sources during the daytime (66.4 %), which had a significant correlation with the mass of coarse particles (PM2.5-10) and photolysis frequency (J(NO2)). When incorporating photolysis of the abundant nitrate measured in coarse particles with a reasonable enhancement factor relative to fine particles due to favorable aerosol conditions, the missing daytime sources of HONO could be fully compensated by coarse particles serving as the largest source at this coastal site. Our study revealed great potential of coarse particles as a strong daytime HONO source, which has been ignored before but can efficiently promote NOx recycling and thus significantly enhance atmospheric oxidation capacity.

[Research on the influence of LED temperature shifts on differential optical absorption spectroscopy for measuring NO2].

Influences of LEDs (without etalon structure and center wavelengths are respectively 370 nm (near-UV), 452 nm (blue) and 660 nm(red)) temperature shifts on differential optical absorption spectroscopy(DOAS) for measuring NO2 were studied. NO2 absorption spectra were formed using LED emitting spectra at 10 degrees C. The measured LED spectra at other temperatures were used as reference spectra of DOAS. Thus, NO2 differential optical densities under different LED temperature shifts were acquired and then NO2 differential cross-sections were fitted to the acquired differential optical densities. From fitting results, the linear relations of 0.995, 0.945 and 0.989 correlation between delta of fitting residual and near-UV, blue and red LEDs temperature shifts were found and their slopes are respectively 1.12 x 10(-3), 5.25 x 10(-5) and 7.45 x 10(-4) degrees C(-1). The fitting results show that the influence of temperature shifts of blue LED on DOAS retrieval is negligible and the temperature shifts of near-UV and red LED are impressible to DOAS measurement resulting in degradation of detection sensitivity. The retrieval results of blue LED with and without etalon with similar temperature properties were compared and showed that etalon of LED will greatly increase the influence of temperature shifts of LED on DOAS retrieval.

[Measurement of OH radicals in flame with XeCl excimer laser].

The present paper describes how to measure OH radicals in the flame of alcohol burner flame by using XeCl excimer laser. The instrument consists of a XeCl excimer laser as light source, a multiple-reflection cell with whole path length of light achieving 2 560 meters, and a double pass high resolution echelle spectrometer with resolution 3.3 pm. This paper describes the reason for using the XeCl excimer laser without spectral etaloning and how to get rid of the water in reactor chamber. The results of the experiment get some absorption peak of OH radicals from 308.145 to 308.175 nm. By choosing the appropriate fit area and fitting, the results contrast with the measure data by using Xe lamp as light source.

[Studies on the data processing method in chlorine measurement by differential optical absorption spectroscopy technology].

In this paper, based on Differential Optical Absorption Spectroscopy (DOAS) technique, experimental measurements of chlorine was carried out in the laboratory with a small self-built experimental system. In dealing with the standard cross-section of chlorine, we presented two different methods: triangle filtering and polynomial fitting. Experiments showed that the concentration of chlorine could be accurately retrieved by the latter one. Simulation results showed that the error of retrieval result by fifth-order polynomial fitting was smaller than by other orders and an actual retrieval example shows that the fitting spectrums were nearly coincident with the measured spectrums with a residual delta(peak to peak) below 5 per hundred; The results measured in different sample pools displayed a high linearity of 0.9961 by this method. The main sources of errors during the entire experiment were simply analyzed. According to the experimental result above, it is feasible to detect chlorine using DOAS technology by polynomial fitting.

[Measurement of OH radicals in flame with high resolution differential optical absorption spectroscopy].

The present paper describes a new developed high resolution differential optical absorption spectroscopy instrument used for the measurement of OH radicals in flame. The instrument consists of a Xenon lamp for light source; a double pass high resolution echelle spectrometer with a resolution of 3.3 pm; a multiple-reflection cell of 20 meter base length, in which the light reflects in the cell for 176 times, so the whole path length of light can achieve 3 520 meters. The OH radicals'6 absorption lines around 308 nm were simultaneously observed in the experiment. By using high resolution DOAS technology, the OH radicals in candles, kerosene lamp, and alcohol burner flames were monitored, and their concentrations were also inverted.