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.

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.

Effect of Water Vapor Absorption on Measurements of Atmospheric Nitrate Radical by LP-DOAS

During the measurement of atmospheric nitrate radical by long-path differential optical absorption spectroscopy, water vapor strong absorption could affect the measurement of nitrate radical and detection limits of system. Under the tropospheric condition, the optical density of water vapor absorption is non-linearly dependent on column density. An effective method was developed to eliminate the effect of water vapor absorption. Reference spectra of water vapor based on the daytime atmospheric absorption spectra, when fitted together with change of cross section with water vapor column densities, gave a more accurate fitting of water vapor absorptions, thus its effect on the measurements of nitrate radical could be restricted to a minimum and detection limits of system reached 3.6 ppt. The modified method was applied during an intensive field campaign in the Pearl River Delta, China. The NO3 concentration in polluted air masses varied from 3.6 ppt to 82.5 ppt with an average level of 23.6±1.8 ppt.

Effect of Atmospheric Interfering Absorption on Measurement of BTX by DOAS

It was reported on the elimination of interfering absorption of BTX. the absorption of O2 includes different absorption bands, which change differently when the partial pressure of oxygen is varied. These cause the nonlinear absorption of O2 and the observed band shape to vary with the column density of O2. The absorption ratios of molecular absorption in each of the Herzberg bands and dimer absorptions, as well as the contribution to the correction error of molecular absorption, are studied based on the characteristic of these absorption bands. The optimized way to eliminate the interfering absorption is obtained in the end and the effectiveness of using interpolation proposed by Volkamer et al. to remove O2 absorption is proved again. As to O2 and SO2, the effect of the thermal effect of characteristic spectra on the elimination error of their absorption is studied. Solutions to these problems are discussed and demonstrated together with methods to optimize the interpolation of spectra. As a sample application, differential optical absorption spectroscopy （DOAS） measurements of BTX are carried out. Results show a low detection limit and the good correlation with point instruments are achieved. All these prove the feasibility of using spectral interpolation to improve the accuracy of DOAS measurements of aromatic hydrocarbons for practical purposes.

Temperature Dependence of Atmospheric NO3 Loss Frequency

A new indicator with temperature dependence of the NO3 loss frequency, was developed to study the contribution of NO3 to the oxidation of monoterpenes and NOx removal in the atmosphere. The new indicator arises from the temperature dependence of kinetic constant. The new indicator was applied to data of observation based on differential optical absorption spectroscopy system on the outskirts of Hefei, China. According to the findings, the contribution of monoterpenes to the loss of NO3 was 70%-80%.

Benzene and Toluene Levels Measured with DOAS During Vehicular Restrictions in Beijing

Measurements of atmospheric benzene and toluene were carried out continuously using dif- ferential optical absorption spectroscopy from August 7 to August 28 in Beijing during the period of vehicular restrictions. The correlations between traffic flows and totals of benzene and toluene were studied during the period of vehicular traffic restrictions from August 17 to August 20 and non-traffic restrictions on August 16 and August 21. The correlation coef- ficient was 0.8 between benzene and toluene. And the calculated daily mean value ratios of benzene to toluene were 0.43-0.50. During the period of vehicular restrictions, traffic flows were reduced about 11.8% and the levels of benzene and toluene were reduced by 11.4% and 12.8%, respectively. The vehicle emissions were recognized as the major sources for atmospheric benzene and toluene in Beijing.

Intercomparison of NO_x, SO_2, O_3, and Aromatic Hydrocarbons Measured by a Commercial DOAS System and Traditional Point Monitoring Techniques

A field-based Intercomparison study of a commercial Differential Optical Absorption Spectroscopy (DOAS) instrument (OPSIS AB, Sweden) and different point-sample monitoring techniques (PM, based on an air monitoring station, an air monitoring vehicle, and various chemical methods) was conducted in Beijing from October 1999 to January 2000. The mixing ratios of six trace gases including NO, NO2, SO2, O3, benzene, and toluene were monitored continuously during the four months. A good agreement between the DOAS and PM data was found for NO2 and SO2. However, the concentrations of benzene, toluene, and NO obtained by DOAS were significantly lower than those measured by the point monitors. The ozone levels monitored by the DOAS were generally higher than those measured by point monitors. These results may be attributed to a strong vertical gradient of the NO-O3-NO2 system and of the aromatics at the measurement site. Since the exact data evaluation algorithm is not revealed by the manufacturer of the DOAS system, the error in the DOAS analysis can also not be excluded.

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.

Effect of spectral resolution on the measurement of monoaromatic hydrocarbons by DOAS

The excellent response characteristics and detection sensitivity with much lower operational cost and the capability to discriminate between the isomer of some monoaromatic hydrocarbons （MAHCs） make differential optical absorption spectroscopy （DOAS） a powerful tool to trace concentration variation of MAHCs. But due to the similarity in chemical structure, those MAHCs have the similar overlapped characteristic absorption structures, which make the selection of instrumental parameter critical to the accurate detection of MAHCs. Firstly, the spectral resolution used in DOAS system determines the nonlinear absorption of O2 and the mass dependence of characteristic absorption structure; thereby it determines the effect of elimination error of O2 absorption in the atmospheric spectra for the detection of MAHCs. Secondly, spectral resolution determines the differential absorption characteristics of twelve MAHCs representing major constituents in technical solvents used in the automobile industry and the interference of spectral overlapping. Thirdly, the spectral resolution determines the sensitivity, time resolution and linear range. So the spectral resolution range with the best ratio of signal to noise is used to determine the most suitable spectral resolution range, as well as the spectral resolution range that ensure the characteristic absorption structure of MAHCs and the minimization of O2 absorption interference. Finally, 0.15-0.16 nm （FWHM： full width at half maximum） is assumed to be closest to the optimum spectral resolution and it is confirmed by the results of practical measurement of MAHCs by DOAS.

Observation of the nighttime nitrate radical in Hefei, China

Observation of nighttime nitrate radical （NO3） was performed by using long path differential optical absorption spectroscopy （LP- DOAS）, on the outskirts of Hefei, China. The time series of NO3 and supporting parameters were simultaneously measured for a week （31 May-7 June 2006）. The results indicated that the average concentration of NO3 was 15.6 pptv with an average lifetimes of 96 s, whereas, NO3 production rates varied from 8×10^2/（cm^3·s） to 2.98×10^7/（cm^3·s）. Furthermore, the calculated N2O5 concentration averaged at 380 pptv. Analysis of data indicated that direct sinks were probably dominating the NO3 loss process during this campaign. The results were compared with other campaigns in the boundary layer.

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.

Research of NO_(2) vertical profiles with look-up table method based on MAX-DOAS

Obtaining the vertical distribution profile of trace gas is of great significance for studying the diffusion procedure of air pollution.In this article,a look-up table method based on multi-axis differential optical absorption spectroscopy(MAX-DOAS)technology is established for retrieving the tropospheric NO_(2) vertical distribution profiles.This method retrieves the aerosol extinction profiles with minimum cost function.Then,the aerosol extinction profiles and the atmospheric radiation transfer model(RTM)are employed to establish the look-up table for retrieving the NO_(2) vertical column densities(VCDs)and profiles.The measured NO_(2) differential slant column densities(DSCDs)are compared with the NO_(2) DSCDs simulated by the atmospheric RTM,and the NO_(2) VCDs,the weight factor of NO_(2) in the boundary layer,and the boundary layer height are obtained by the minimization process.The look-up table is established to retrieve NO_(2) VCDs based on MAX-DOAS measurements in Huaibei area,and the results are compared with the data from Copernicus Atmospheric Monitoring Service(CAMS)model.It is found that there are nearly consistent and the correlation coefficient R2 is more than 0.86.The results show that this technology provides a more convenient and accurate retrieval method for the stereoscopic monitoring of atmospheric environment.

A convolution algorithm to calculate differential cross sections of the Ring effect in the Earth's atmosphere based on rotational Raman scattering

The Ring effect refers to the filling in of Fraunhofer lines, which is mainly attributed to the rotational Raman scattering of solar spectra by N2 and O2 molecules in the atmosphere. The Ring effect is one of the most significant factors affecting the accuracy of retrieving concentrations of atmospheric trace gases, such as NO2 and SO2, from satellite observations through differential optical absorption spectroscopy. First in this study, the solar spectrum measured by the Ozone Monitoring Instrument onboard NASA Aura is convolved with the rotational Raman cross section of the atmosphere, which is calculated from the rotational Raman cross sections of N2 and O2 molecules, and divided by the original solar spectrum. The slowly varying term is removed by fitting it with a cubic polynomial to obtain the differential Ring spectrum. The results agree well with the calculations using a radiative transfer model (R2=0.9663). Second, the differential Ring spectrum is computed using two fixed wavelengths of 410 nm and 488 nm, and the resulting differential Ring spectra are similar to that calculated with varying wavelengths and agree well with the calculation using the radiative transfer model (R2=0.9624 and 0.9639 respectively). The computation time using the fixed wavelength is about 0.128% of that using a varying wavelength. Finally, we found that the frequency spectrum of the Raman cross sections for the atmosphere, N2 molecules and O2 molecules are similar; thus, the Raman cross section of N2 or O2 molecules can be used to compute the approximate Ring effect for simplicity.

Study on specific interaction of new ferrocene-substituted carborane conjugates with hemoglobin protein

The interactions between the new organometallic complexes, ferrocenesubstituted dithioocarborane conjugates （denoted as FcSB1, FcSB2 and FcSBCO） and hemoglobin （Hb） are investigated by electrochemistry, fluorescence and UVvis absorption spectroscopy. The results demonstrate that FcSB1, FcSB2 and FcSBCO can bind to the heme iron center through the replacement of the weakly bound H20/02 in the distal heme pocket of Hb by their sulfur donor atoms, inducing the allosteric change from the R state （oxygenated conformation, relax） to T state （deoxygenated conformation, tense）. The binding affinity is in the order of FcSBCO〉FeSB2〉FeSB1. Moreover, the fluorescence study illustrates that the three ferrocenecarborane conjugates differently affect the quarterly and tertiary structures as well as the polarity in the surrounding of the Trp and Tyr residues in Hb. Typically, FcSB2 mainly induces alterations of the microenvironment around the 1337Trp residue which is located on the cql32 interface of Hb. Such distinct influences are attributed to the structural features of FcSB1, FcSB2 and FcSBCO containing hydrophobic ferrocenyl and carboranyl units as well as C=O group. Screening the proteinbinding behavior can signify the potential bioactivity of such molecules and may be helpful in the future development of promising multifunctional metallodrugs.