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.

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.

Research Progress on Photocatalytic Reduction of the Nitrate Radical

Due to a large number of application of the nitrogen fertilizer, unreasonable treatments of the animal wastes, domestic sewage and industrial sewage including nitrogen, and garbage stacking in recent years, the concentration of NO; that was toxic to humans in worldwide ground water presented rise trend at different degrees. Photocatalytic removal technology of the nitrogen had many advantages and was widely valued. Cost was low, and there was no secondary pollution. Reaction condition was mild, and reaction time was short. The photocatalytic reduction re. search of nitrate at home and abroad was reviewed in detail, including photocatalyst, scavenger and reaction mechanism. In particular, perspectives for photocatalytic reduction of the nitrate were detailedly analyzed.

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.

Reaction Kinetics and Secondary Organic Aerosol Composition Analysis of 2-Cyclohexen-1-one with NO_(3) Radicals

Unsaturated ketones are typical oxygenated volatile organic compounds(OVOCs)with high reactivity,and are important precursors in air pollution.The sources of OVOCs are complex and include direct emissions and secondary oxidation formation of VOCs in the atmosphere.2-Cyclohexen-1-one is a widespread substance,and is derived from the industrial catalytic oxidation of cyclohexene.In this paper,we investigated the rate constants of the chemical reactions of 2-cyclohexen-1-one with NO_(3) radicals,which is(7.25±0.29)×10^(-15) cm^(3)·molecule^(-1)·s^(-1) at 298 K and under 1 atm(1 atm=101325Pa).It supplemented the kinetics of NO_(3) radicals database,and revealed its effects in the nighttime atmosphere.In addition,the reaction products of 2-cyclohexen-1-one with NO_(3) radicals were detected by Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS),which revealed a series of nitrate esters in the composition of the secondary organic aerosol(SOA),which may reduce atmospheric visibility.Finally,the possible pathways for the generation of the products were developed.

Cavity Ring-Down Spectroscopy Measurements of Ambient NO3 and N2O5

NO3 and N2O5 are important participants in nocturnal atmospheric chemical processes,and their concentrations are of great significance in the study of the mechanism of nocturnal atmospheric chemical reactions.A two-channel diode laser based cavity ring-down spectroscopy(CRDS)instrument was developed to monitor the concentrations of NO3 and N2O5 in the atmosphere.The effective absorption length ratio and the total loss coefficient of the instrument were calibrated using laboratory standard samples.The effective absorption cross section of NO3 at 662 nm was derived.A detection sensitivity of 1.1 pptv NO3 in air was obtained at a time resolution of 1 s.N2O5 was converted to NO3 and detected online in the second CRDS channel.The instrument was used to monitor the concentrations of NO3 and N2O5 in the atmosphere of winter in Hefei in real time.By comparing the concentration changes of pollutants such as nitrogen oxides,ozone,PM2:5 in a rapid air cleaning process,the factors affecting the concentrations of NO3 and N2O5 in the atmosphere were discussed.

Nocturnal atmospheric chemistry of NO_(3) and N_(2)O_(5) over Changzhou in the Yangtze River Delta in China

Comprehensive observations of the nocturnal atmospheric oxidation of NO_(3)and N_(2)O_(5)were conducted at a suburban site in Changzhou in the YRD using cavity ring-down spectroscopy(CRDS)from 27 May to 24 June,2019.High concentrations of NO_(3)precursors were observed,and the nocturnal production rate of NO_(3)was determined to be 1.7±1.2 ppbv/hr.However,the nighttime NO_(3)and N_(2)O_(5)concentrations were relatively low,with maximum values of 17.7 and 304.7 pptv,respectively,illustrating the rapid loss ofNO_(3)andN_(2)O_(5).Itwas found that NO_(3)dominated the nighttime atmospheric oxidation,accounting for 50.7%,whileO3 andOH only contributed 34.1%and 15.2%,respectively.For the reactions of NO_(3)with volatile organic compounds(VOCs),styrenewas found to account for 60.3%,highlighting its dominant role in the NO_(3)reactivity.In general,the contributions of the reactions between NO_(3)and VOCs and the N_(2)O_(5)uptake to NO_(3)losswere found to be about 39.5%and 60.5%,respectively,indicating that N_(2)O_(5)uptake also played an important role in the loss of NO_(3)and N_(2)O_(5),especially under the high humidity conditions in China.The formation of nitrate at night mainly originated from N_(2)O_(5)uptake,and the maximum production rate of NO_(3)^(-)reached 6.5 ppbv/hr.The average NOx consumption rate via NO_(3)and N_(2)O_(5)chemistry was found to be 0.4 ppbv/h,accounting for 47.9%of the total NO_(x)removal.The predominant roles of NO_(3)and N_(2)O_(5)in nitrate formation and NO_(x)removal in the YRD region was highlighted in this study.