Impact of COVID-19 containment and closure policies on tropospheric nitrogen dioxide: A global perspective
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A previous study demonstrated two-photon consecutive absorption as being the most probable mechanism for the photodissociation of NO2 using a pulsed ruby laser at 6943 A. Additional data discussed here confirmed this and also examined an associated phenomenon, that of multiphoton induced fluorescence. The dissociation of NO2 by ON-O bond cleavage requires 3.4 eV, while the laser energy corresponds to 1.785 eV. The pooling of the energy of two photons would give more than enough energy to dissociate the NO2 into NO + O. Several mechanisms including (1) simultaneous absorption of two photons; (2) reaction of two singly excited NO2; (3) reaction of a singly excited NO2 with a ground state NO2; and (4) consecutive absorption of two photons were examined.
A radiative-convective model is proposed for estimating the sensitivity of the atmospheric radiative heating rates and atmospheric and surface temperatures to perturbations in the concentration of O3 and NO2 in the stratosphere. Contribution to radiative energy transfer within the atmosphere from H2O, CO2, O3, and NO2 is considered. It is found that the net solar radiation absorbed by the earth-atmosphere system decreases with a reduction in O3; if the reduction of O3 is accompanied by an increase in NO2, there is a compensating effect due to solar absorption by NO2. The surface temperature and atmospheric temperature decrease with decreasing stratospheric O3. Another major conclusion is the strong sensitivity of surface temperature to the vertical distribution of O3 within the atmosphere. The results should be considered as reflecting the sensitivity of the proposed model rather than the sensitivity of the actual earth-atmosphere system.
The sensitization of stoichiometric hydrogen-air ignition by NO, NO2 and a mixture of NO and NO2 was investigated behind reflected shock waves in a shock tube. Induction times were measured in pressure range 0.27 to 2.0 atm, temperature range 800 to 1500 K, and for NO or NO2 mole percent between 0.0 and 4.5. Addition of both NO and NO2 reduced the measured induction times. The experimental data are interpreted in terms of H2-O2-NO(x) oxidation reaction mechanisms. The influence of NO(x) upon a supersonic combustion ramjet combustor test, conducted in an arc-heated facility, is assessed.
While it is generally thought that the bactericidal effects of NO and NO2 derive from their reaction with water to form nitrous and nitric acids (Shank et al., 1962), this appears to be true only at high concentrations. The data presented here suggest that at low NO and NO2 concentrations, acids are not present in high enough concentrations to act as toxic agents. Reference is made to a study by Grant et al. (1979), which found that exposing acid forest soil to 1 ppm of NO2 did not cause the soil pH to drop. The results presented here show that at low concentrations of NO and NO2, the NO is bacteriostatic for some organisms and not for others, whereas NO2 may protect some bacteria from the inhibitory effects of NO. Since it has been shown that bacteria can divide while airborne (Dimmick et al., 1979), the present results suggest that NO at the low concentrations found in the atmosphere can select for resistant bacteria in the air and affect the viable airborne bacterial population.
Measurements of limb radiance from the Solar Mesosphere Explorer (SME) satellite are used to infer the NO2 density at the 10- and 16-mbar pressure levels from January 1 to March 31 of 1982. A photochemical-dynamical model is developed using the presently accepted chemistry of the NO(x) family. The dynamical model produces isentropic trajectories which simulate the history of air parcels. From the trajectories the photochemical model calculates NO2 densities, which are compared to those observed by SME. Although the model generally reproduces the spatial and temporal variations rather well, some disagreement was noted for conditions of exceptionally low temperatures. Further analysis indicates that the temperature sensitivity of the N2O5 photolysis cross sections may be overestimated at low temperatures.
Observations of NO2 from the limb infrared monitor of the stratosphere (LIMS) experiment in high-latitude summer are presented. Appropriate selection of latitude and days during the month of May yields NO2 observations obtained during the afternoon and evening at solar zenith angles ranging from about 35-110 deg. These data show that the NO2 abundances in the stratosphere become strongly dependent on the solar zenith angle for angles exceeding about 80 deg. Model calculations and other observations suggest that from about 80-95 deg this dependence probably reflects variations in the propagation of the visible radiation that photodissociates NO2. The data obtained at zenith angles greater than about 95 deg provide clear evidence for the night decay of NO2 to form N2O5, and the observed decay rate is shown to be consistent with present theory.
Simultaneous vertical profiles of O3, NO2, and aerosol extinction obtained with the Stratospheric Aerosol Measurement II, Stratospheric Aerosol and Gas Experiment (SAGE), and SAGE II satellite instruments across the southern polar vortex show that significant differences exist at all altitudes. Both gaseous species display lower concentrations within the vortex over measurement altitudes ranging from the tropopause to 60 km and 20 to 40 km for O3 and NO2, respectively. Aerosol extinction above 15-18 km and total aerosol stratospheric column are also lower inside the vortex than outside. Total column amounts of O3 and NO2 are found to be strongly coupled to spatial location within the vortex, with minimum total values located around the vortex center. Vertical profiles selected to emphasize the observed difference across the circumpolar vortex are presented for October 13, 1981, and October 13, 1985, near 70 and 68 deg S latitude, respectively.
Data from the 6.9-micron H2O channel and the 6.2-micron NO2 channel of the Nimbus 7 Limb Infrared Monitor of the Stratosphere (LIMS) have been used to investigate the daytime enhancement to H2O; the high concentration of H2O sometimes observed in the polar night mesosphere; and the high ratio of daytime to nighttime NO2 in the upper stratosphere. These three phenomena deviate noticeably from the predictions of photochemical theory. The 20 to 30 percent diurnal variation in stratospheric H2O apparent in LIMS data cannot be reconciled with a photochemical lifetime in excess of four months. This is attributed to departure from local thermodynamic equilibrium of daytime emission which had not been accounted for in retrievals. Speculative possibilities of NLTE emission from the H2O nu2 and NO2 nu3 hot bands are discussed. It is found that the nonthermal emission from NO2 significantly affects retrieval of H2O in the polar nighttime and NO2 in the daytime stratosphere at low latitudes.
This paper provides the rationale, objectives, approach, and a brief description of the instrumentation included in the second airborne Chemical Instrumentation Test and Evaluation (CITE 2) mission conducted on NASA's Electra aircraft. CITE 2 intercompared data from instruments measuring NO2, HNO3, and PAN in the troposphere. This study, conducted in August 1986, encountered marine and continental air with free tropospheric mixing ratios of NO2, HNO3, and PAN typically less than 120, 150, and 200 parts per trillion by volume, respectively.
Results on NO2 instruments are reported from the NASA Global Tropospheric Experiment Chemical Instrumentation Test and Evaluation 2 (CITE 2) program in summer 1986. The instruments tested were (1) a two-photon LIF system using a laser for NO2-NO photolysis, (2) a chemiluminescence (CL) detector using FeSO4 for NO2-NO conversion, (3) a CL detector using an arc lamp for NO2-NO photolysis, and (4) a tunable-laser-diode multipath-absorption system. The procedures for the CITE 2 ground-based and flight tests are described in detail, and the results are presented in extensive graphs. Instrument (2) was eliminated because the FeSO4 converted atmospheric PAN to NO, resulting in spuriously high NO2 values. The remaining instruments gave readings in 30-40-percent agreement at NO2 mixing ratios of 100-200 parts per trillion by volume (pptv). At ratios below 50 pptv, the correlation among the measurements was very poor, with a tendency for system (4) to give higher values than (1) or (3).
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Under the auspices of the World Meteorological Organization, Environment Canada hosted an international comparison of visible light spectrophotometers at Mt. Kobau, British Columbia in August of 1991. Instruments from four countries were involved. The intercomparison results have indicated that some significant differences exist in the responses of the various instruments, and have provided a basis for the comparison of the historical data sets which currently exist as a result of the independent researches carried out in the past in the former Soviet Union, New Zealand, and Canada.
Instruments such as the Global Ozone Monitoring Experiment (GOME, on the European Remote Sensing Satellite (ERS-2), launched 1995), the Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY, on ENVISAT, to be launched July 2001) and the Ozone Monitoring Instrument (OMI on EOS Aura, to be launched 2003) make measurements of the total column of NO2. There is interest in separating the stratospheric and tropospheric contributions to the column, as the tropospheric column provides a measure of pollution. We are using a 3D chemistry and transport model driven by winds from the Goddard Space Flight Center Data Assimilation System to examine variability in the stratospheric NO2 column. Model results for NOx = NO + NO2 + 2N2O5 will be shown to compare well with sunset observations from the Halogen Occultation Experiment on the Upper Atmosphere Research Satellite, and to exhibit similar temporal and spatial dependence. Partitioning between NO, NO2, and N2O5 is also shown to compare well with observations. This good agreement supports the use of simulated fields in the stratosphere to derive the tropospheric column from the total column. Preliminary comparisons of the tropospheric column with model simulations for the troposphere will also be shown.
NO2 column amounts were measured for the past 2 years at Goddard Space Flight Center, Greenbelt, Maryland, using a Brewer spectrometer in direct Sun mode. A new bootstrap method to calibrate the instrument is introduced and described. This technique selects the cleanest days from the database to obtain the solar reference spectrum. The main advantage for direct Sun measurements is that the conversion uncertainty from slant column to vertical column is negligible compared to the standard scattered light observations where it is typically on the order of 100% (2sigma) at polluted sites. The total 2sigma errors of the direct Sun retrieved column amounts decrease with solar zenith angle and are estimated at 0.2 to 0.6 Dobson units (DU, 1 DU approx. equal to 2.7 10(exp 16) molecules cm(exp -2)), which is more accurate than scattered light measurements for high NO2 amounts. Measured NO2 column amounts, ranging from 0 to 3 DU with a mean of 0.7 DU, show a pronounced daily course and a strong variability from day to day. The NO2 concentration typically increases from sunrise to noon. In the afternoon it decreases in summer and stays constant in winter. As expected from the anthropogenic nature of its source, NO2 amounts on weekends are significantly reduced. The measurements were compared to satellite retrievals from Scanning Image Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY). Satellite data give the same average NO2 column and show a seasonal cycle that is similar to the ground data in the afternoon. We show that NO2 must be considered when retrieving aerosol absorption properties, especially for situations with low aerosol optical depth.
The at-launch version of the OM1 NO2 total and tropospheric NO2 algorithm made a number of assumptions about instrument performance. Our knowledge of tropospheric NO2 has increased in the 3 years since the inital version was delivered. The results of the post-launch validation campaigns and improved atmospheric modelling has lead to changes in the NO2 retrieval algorithm. The algorithm changes and the impacts on the data products will be presented.