Absorption Cross-sections Of NO2 Research Articles

Compact, Fast Cavity Ring-Down Spectroscopy Monitor for Simultaneous Measurement of Ozone and Nitrogen Dioxide in the Atmosphere

A sensitive, compact detector for the simultaneous measurement of O3 and NO2 is presented in this work. There are two channels in the detector, namely the Ox channel and the NO2 channel. In the presence of excess NO, ambient O3 is converted to NO2 in the Ox measurement channel. In both channels, NO2 is directly detected via cavity ring-down spectroscopy (CRDS) at 409 nm. At a 10 s integration time, the Ox and NO2 channels have a 1σ precision of 14.5 and 13.5 pptv, respectively. The Allan deviation plot shows that the optimal sensitivity of O3 and NO2 occurs at an integration time of ~60 s, with values of 10.2 and 8.5 pptv, respectively. The accuracy is 6% for the O3 channel and 5% for the NO2 channel, and the largest uncertainty comes from the effective NO2 absorption cross-section. Intercomparison of the NO2 detection between the NO2 and Ox channels shows good agreement within their uncertainties, with an absolute shift of 0.31 ppbv, a correlation coefficient of R2 = 0.99 and a slope of 0.98. Further intercomparison for ambient O3 measurement between the O3/NO2-CRDS developed in this work and a commercial UV O3 monitor also shows excellent agreement, with linear regression slopes close to unity and an R2 value of 0.99 for 1 min averaged data. The system was deployed to measure O3 and NO2 concentrations in Hefei, China, and the observation results show obvious diurnal variation characteristics. The successful deployment of the system has demonstrated that the instrument can provide a new method for retrieving fast variations in ambient O3 and NO2.

The NO<sub>2</sub> camera based on gas correlation spectroscopy

Abstract. Spectroscopic methods have proven to be reliable and of high selectivity by utilizing the characteristic spectral absorption signature of trace gases such as NO2. However, they typically lack the spatiotemporal resolution required for real-time imaging measurements of NO2 emissions. We propose imaging measurements of NO2 in the visible spectral range using a novel instrument, an NO2 camera based on the principle of gas correlation spectroscopy (GCS). For this purpose two gas cells (cuvettes) are placed in front of two camera modules. One gas cell is empty, while the other is filled with a high concentration of the target gas. The filled gas cell operates as a non-dispersive spectral filter to the incoming light, maintaining the two-dimensional imaging capability of the sensor arrays. NO2 images are generated on the basis of the signal ratio between the two images in the spectral window between 430 and 445 nm, where the NO2 absorption cross section is strongly structured. The capabilities and limits of the instrument are investigated in a numerical forward model. The predictions of this model are verified in a proof-of-concept measurement, in which the column densities in specially prepared reference cells were measured with the NO2 camera and a conventional differential optical absorption spectroscopy (DOAS) instrument. Finally, results from measurements at a large power plant, the Großkraftwerk Mannheim (GKM), are presented. NO2 column densities of the plume emitted from a GKM chimney are quantified at a spatiotemporal resolution of 1/12 frames per second (FPS) and 0.9 m×0.9 m. A detection limit of 2⋅1016 molec. cm−2 was reached. An NO2 mass flux of Fm=(7.4±4.2) kg h−1 was estimated on the basis of wind speeds obtained from consecutive images. The instrument prototype is highly portable for building costs of below EUR 2000.

Advanced NO<sub>2</sub> retrieval technique for the Brewer spectrophotometer applied to the 20-year record in Rome, Italy

Abstract. A re-evaluated data set of nitrogen dioxide (NO2) column densities over Rome for the years 1996 to 2017 is here presented. This long-term record is obtained from ground-based direct sun measurements with a MkIV Brewer spectrophotometer (serial number #067) and further reprocessed using a novel algorithm. Compared to the original Brewer algorithm, the new method includes updated NO2 absorption cross sections and Rayleigh scattering coefficients, and it accounts for additional atmospheric compounds and instrumental artefacts, such as the spectral transmittance of the filters, the alignment of the wavelength scale, and internal temperature. Moreover, long-term changes in the Brewer radiometric sensitivity are tracked using statistical methods for in-field calibration. The resulting series presents only a few (about 30) periods with missing data longer than 1 week and features NO2 retrievals for more than 6100 d, covering nearly 80 % of the considered 20-year period. The high quality of the data is demonstrated by two independent comparisons. In the first intensive campaign, Brewer #067 is compared against another Brewer (#066), recently calibrated at the Izaña Atmospheric Observatory through the Langley method and there compared to reference instrumentation from the Network for the Detection of Atmospheric Composition Change (NDACC). Data from this campaign show a highly significant Pearson's correlation coefficient of 0.90 between the two series of slant column densities (SCDs), slope 0.98 and offset 0.05 DU (Dobson units; 1.3×1015 molec.cm-2). The average bias between the vertical column densities is 0.03 DU (8.1×1014 molec.cm-2), well within the combined uncertainty of both instruments. Brewer #067 is also independently compared with new-generation instrumentation, a co-located Pandora spectrometer (#117), over a 1-year-long period (2016–2017) at Sapienza University of Rome, showing linear correlation indices above 0.96 between slant column densities, slope of 0.97, and offset of 0.02 DU (5.4×1014 molec.cm-2). The average bias between vertical column densities is negligible (−0.002 DU or -5.4×1013 molec.cm-2). This, incidentally, represents the first intercomparison of NO2 retrievals between a MkIV Brewer and a Pandora instrument. Owing to its accuracy and length, the Brewer data set collected in Rome can be useful for satellite calibration/validation exercises, comparison with photochemical models, and better aerosol optical depth estimates (NO2 optical depth climatology). In addition, it can be employed to identify long-term trends in NO2 column densities in a metropolitan environment, over two decades witnessing important changes in environmental policies, emission loads and composition, and the effect of a worldwide economic recession, to offer just a few examples. The method can be replicated on the more than 80 MkIV spectrophotometers operating worldwide in the frame of the international Brewer network. The NO2 data set described in this paper can be freely accessed at https://doi.org/10.5281/zenodo.4715219 (Diémoz and Siani, 2021).

Effect of temperature on inversion concentration of NO2 differential absorption lidar and optimized algorithm

A differential absorption lidar (DIAL) for measurement of atmospheric nitrogen dioxide (NO2) concentration is developed based on atmospheric backscattered signals. Two Nd:YAG lasers are used to pump into two dye lasers to produce two wavelengths λon (448.1 nm) and λoff (446.6 nm), respectively. The NO2 absorption cross section varies with the change of ambient temperature. The changes of NO2 absorption cross section and the influence of inversion concentration are analyzed. The results show that when the horizontal profile is measured with the absorption cross section at room temperature of 20 °C as the reference value, the relative error of 1% can be caused by the temperature change of 1 °C. In vertical profile measurement, on the ground below 3 km, every 100 m increase in altitude can bring a relative error of 0.6%. By correcting the absorption cross section affected by temperature, the relative error of the measured concentration is less than 5%.On this basis, the experimental observation of atmospheric NO2 concentration profiles was carried out, and errors induced by temperature change were corrected. The experimental results show that the system is stable and reliable, and the temperature correction algorithm is effective.

Tropospheric NO<sub>2</sub> measurements using a three-wavelength optical parametric oscillator differential absorption lidar

Abstract. The conventional two-wavelength differential absorption lidar (DIAL) has measured air pollutants such as nitrogen dioxide (NO2). However, high concentrations of aerosol within the planetary boundary layer (PBL) can cause significant retrieval errors using only a two-wavelength DIAL technique to measure NO2. We proposed a new technique to obtain more accurate measurements of NO2 using a three-wavelength DIAL technique based on an optical parametric oscillator (OPO) laser. This study derives the three-wavelength DIAL retrieval equations necessary to retrieve vertical profiles of NO2 in the troposphere. Additionally, two rules to obtain the optimum choice of the three wavelengths applied in the retrieval are designed to help increase the differences in the NO2 absorption cross-sections and reduce aerosol interference. NO2 retrieval relative uncertainties caused by aerosol extinction, molecular extinction, absorption of gases other than the gas of interest and backscattering are calculated using two-wavelength DIAL (438 and 439.5 nm) and three-wavelength DIAL (438, 439.5 and 441 nm) techniques. The retrieval uncertainties in aerosol extinction using the three-wavelength DIAL technique are reduced to less than 2 % of those when using the two-wavelength DIAL technique. Moreover, the retrieval uncertainty analysis indicates that the three-wavelength DIAL technique can reduce more fluctuation caused by aerosol backscattering than the two-wavelength DIAL technique. This study presents NO2 concentration profiles which were obtained using the HU (Hampton University) three-wavelength OPO DIAL. As a first step to assess the accuracy of the HU lidar NO2 profiles, we compared the NO2 profiles to simulated data from the Weather Research and Forecasting Chemistry (WRF-Chem) model. This comparison suggests that the NO2 profiles retrieved with the three-wavelength DIAL technique have similar vertical structure and magnitudes typically within ±0.1 ppb compared to modeled profiles.

A dual-channel incoherent broadband cavity-enhanced absorption spectrometer for sensitive atmospheric NOx measurements.

We describe and characterize a dual-channel incoherent broadband cavity-enhanced absorption spectrometer (DC-IBBCEAS) for the sensitive measurements of NOx: the sum of nitrogen monoxide (NO) and nitrogen dioxide (NO2) in the atmosphere. The instrument employs two 1 m long optical cavities, with air being extracted from a common sampling line. The first channel (cavity-1) spans 340-380 nm and the second channel (cavity-2) spans the 405-460 nm spectral range, both measuring NO2 simultaneously. High absorption cross-sections of NO2 in both channels are effectively utilized for its sensitive quantification. NO is quantified by titrating it with ozone to NO2 in channel-2, where the difference of NO2 measured from that in channel-1 corresponds to the NO concentration in the sampled air. The instrument offers 1-ppb detection sensitivity for both NO and NO2 with a maximum possible uncertainty of ∼9%. The use of close yet different spectral regions in the two channels readily extended measurements to a broader range without compromising its sensitivity to NOx quantification. This would extend the DC-IBBCEAS applicability to simultaneously monitor interfering species with significant absorption cross-sections in the region in either channel, such as glyoxal (CHOCHO), methylglyoxal (CH3COCHO), and nitrous acid (HONO).

Evaluation of systematic errors for the continuous-wave NO2 differential absorption lidar employing a multimode laser diode.

The NO2-differential absorption lidar (NO2-DIAL) technique has been of great interest for atmospheric NO2 profiling. Comprehensive studies on measurement errors in the NO2-DIAL technique are vital for the accurate retrieval of the NO2 concentration. This work investigates the systematic errors of the recently developed continuous-wave (CW) NO2-DIAL technique based on the Scheimpflug principle and a high-power CW multimode laser diode. Systematic errors introduced by various factors, e.g., uncertainty of the NO2 differential absorption cross-section, differential absorption due to other gases, spectral drifting of the λon and λoff wavelengths, wavelength-dependent extinction and backscattering effect, have been theoretically and experimentally studied for the CW-DIAL technique. By performing real-time spectral monitoring on the emission spectrum of the laser diode, the effect of spectral drifting on the NO2 differential absorption cross-section is negligible. The temperature-dependent NO2 absorption cross-section in the region of 220-294 K can be interpolated by employing a linear fitting method based on high-precision absorption spectra at 220, 240, and 294 K. The relative error for the retrieval of the NO2 concentration is estimated to be less than 0.34% when employing the interpolated spectrum. The primary interference molecule is found to be the glyoxal (CHOCHO), which should be carefully evaluated according to its relative concentration in respect to NO2. The systematic error introduced by the backscattering effect is subjected to the spatial variation of the aerosol load, while the extinction-induced systematic error is primarily determined by the difference between the aerosol extinction coefficients at λon and λoff wavelengths. A case study has been carried out to demonstrate the evaluation of systematic errors for practical NO2 monitoring. The comprehensive investigation on systematic errors in this work can be of great value for future NO2 monitoring using the DIAL technique.

Discrete-wavelength DOAS NO<sub>2</sub> slant column retrievals from OMI and TROPOMI

Abstract. The use of satellite NO2 data for air quality studies is increasingly revealing the need for observations with higher spatial and temporal resolution. The study of the NO2 diurnal cycle, global sub-urban-scale observations, and identification of emission point sources are some examples of important applications not possible at the resolution provided by current instruments. One way to achieve increased spatial resolution is to reduce the spectral information needed for the retrieval, allowing both dimensions of conventional 2-D detectors to be used to record spatial information. In this work we investigate the use of 10 discrete wavelengths with the well-established differential optical absorption spectroscopy (DOAS) technique for NO2 slant column density (SCD) retrievals. To test the concept we use a selection of individual OMI and TROPOMI Level 1B swaths from various regions around the world, which contain a mixture of clean and heavily polluted areas. To discretise the data we simulate a set of Gaussian optical filters centred at various key wavelengths of the NO2 absorption cross section. We perform SCD retrievals of the discrete data using a simple implementation of the DOAS algorithm and compare the results with the corresponding Level 2 SCD products, namely QA4ECV for OMI and the operational TROPOMI product. For OMI the overall results from our discrete-wavelength retrieval are in very good agreement with the Level 2 data (mean difference <5 %). For TROPOMI the agreement is good (mean difference <11 %), with lower uncertainty owing to its higher signal-to-noise ratio. These discrepancies can be mostly explained by the differences in retrieval implementation. There are some larger differences around the centre of the swath and over water. While further research is needed to address specific retrieval issues, our results indicate that our method has potential. It would allow for simpler, more economic satellite instrument designs for NO2 monitoring at high spatial and temporal resolution. Constellations of small satellites with such instruments on board would be a valuable complement to current and upcoming high-budget hyperspectral instruments.

Simultaneous measurement of NO and NO<sub>2</sub> by a dual-channel cavity ring-down spectroscopy technique

Abstract. Nitric oxide (NO) and nitrogen dioxide (NO2) are relevant to air quality due to their roles in tropospheric ozone (O3) production. In China, NOx emissions are very high and NOx emissions exhausted from on-road vehicles make up 20 % of total NOx emissions. In order to detect the NO and NO2 emissions on road, a dual-channel cavity ring-down spectroscopy (CRDS) system for NO2 and NO detection has been developed. In the system, NO is converted to NO2 by its reaction with excess O3 in the NOx channel, such that NO can be determined through the difference between two channels. The detection limits of NO2 and NOx for the system are estimated to be about 0.030 (1σ, 1 s) and 0.040 ppb (1σ, 1 s), respectively. Considering the error sources of NO2 absorption cross section and RL determination, the total uncertainty of NO2 measurements is about 5%. The performance of the system was validated against a chemiluminescence (CL) analyser (42i, Thermo Scientific, Inc.) by measuring the NO2 standard mixtures. The measurement results of NO2 showed a linear correction factor (R2) of 0.99 in a slope of 1.031±0.006, with an offset of (-0.940±0.323) ppb. An intercomparison between the system and a cavity-enhanced absorption spectroscopy (CEAS) instrument was also conducted separately for NO2 measurement in an ambient environment. Least-squares analysis showed that the slope and intercept of the regression line are 1.042±0.002 and (-0.393±0.040) ppb, respectively, with a linear correlation factor of R2=0.99. Another intercomparison conducted between the system and the CL analyser for NO detection also showed a good agreement within their uncertainties, with an absolute shift of (0.352±0.013) ppb, a slope of 0.957±0.007 and a correlation coefficient of R2=0.99. The system was deployed on the measurements of on-road vehicle emission plumes in Hefei, and the different emission characteristics were observed in the different areas of the city. The successful deployment of the system has demonstrated that the instrument can provide a new method for retrieving fast variations in NO and NO2 plumes.

The use of NO<sub>2</sub> absorption cross section temperature sensitivity to derive NO<sub>2</sub> profile temperature and stratospheric–tropospheric column partitioning from visible direct-sun DOAS measurements

Abstract. This paper presents a temperature sensitivity method (TESEM) to accurately calculate total vertical NO2 column, atmospheric slant NO2 profile-weighted temperature (T), and to separate stratospheric and tropospheric columns from direct-sun (DS), ground-based measurements using the retrieved T. TESEM is based on differential optical absorption spectroscopy (DOAS) fitting of the linear temperature-dependent NO2 absorption cross section, σ (T), regression model (Vandaele et al., 2003). Separation between stratospheric and tropospheric columns is based on the primarily bimodal vertical distribution of NO2 and an assumption that stratospheric effective temperature can be represented by temperature at 27 km ± 3 K, and tropospheric effective temperature is equal to surface temperature within 3–5 K. These assumptions were derived from the Global Modeling Initiative (GMI) chemistry-transport model (CTM) simulations over two northern midlatitude sites in 2011. TESEM was applied to the Washington State University Multi-Function DOAS instrument (MFDOAS) measurements at four midlatitude locations with low and moderate NO2 anthropogenic emissions: (1) the Jet Propulsion Laboratory's Table Mountain Facility (JPL-TMF), CA, USA (34.38° N/117.68° W); (2) Pullman, WA, USA (46.73° N/117.17° W); (3) Greenbelt, MD, USA (38.99° N/76.84° W); and (4) Cabauw, the Netherlands (51.97° N/4.93° E) during July 2007, June–July 2009, July–August and October 2011, November 2012–May 2013, respectively. NO2 T and total, stratospheric, and tropospheric NO2 vertical columns were determined over each site.

Measurement of Atmospheric Ozone by Cavity Ring-down Spectroscopy

Ozone plays a key role in both the Earth's radiative budget and photochemistry. Accurate, robust analytical techniques for measuring its atmospheric abundance are of critical importance. Cavity ring-down spectroscopy has been successfully used for sensitive and accurate measurements of many atmospheric species. However, this technique has not been used for atmospheric measurements of ozone, because the strongest ozone absorption bands occur in the ultraviolet spectral region, where Rayleigh and Mie scattering cause significant cavity losses and dielectric mirror reflectivities are limited. Here, we describe a compact instrument that measures O3 by chemical conversion to NO2 in excess NO, with subsequent detection by cavity ring-down spectroscopy. This method provides a simple, accurate, and high-precision measurement of atmospheric ozone. The instrument consists of two channels. The sum of NO2 and converted O3 (defined as Ox) is measured in the first channel, while NO2 alone is measured in the second channel. NO2 is directly detected in each channel by cavity ring-down spectroscopy with a laser diode light source at 404 nm. The limit of detection for O3 is 26 pptv (2 sigma precision) at 1 s time resolution. The accuracy of the measurement is ±2.2%, with the largest uncertainty being the effective NO2 absorption cross-section. The linear dynamic range of the instrument has been verified from the detection limit to above 200 ppbv (r2>99.99%). The observed precision on signal (2 sigma) with 41 ppbv O3 is 130 pptv in 1 s. Comparison of this instrument to UV absorbance instruments for ambient O3 concentrations shows linear agreement (r2=99.1%) with slope of 1.012±0.002.

First Direct Detection of HONO in the Reaction of Methylnitrite (CH3ONO) with OH Radicals

We report on the development of a new environmental simulation chamber coupled with an in situ continuous wave cavity ring-down spectrometer operating in the near IR (∼1.5 μm). The first application reported in this paper dealt with the chemical mechanism of UV photolysis of methyl nitrite (CH(3)ONO) in air. HONO has been detected for the first time and shown to be formed in the OH + CH(3)ONO reaction. A dense spectrum of cis-HONO absorption lines has been observed near 1.5 μm, in agreement with a previous study (Guilmot et al.). CH(2)O has been measured as primary product with good sensitivity and time resolution. In contrast to Zhao et al., we did not detect any NO(2) absorption features in this wavelength range. Calibration experiments provided very low NO(2) absorption cross sections in this region (∼10(-25) cm(2)), leading to conclude that NO(2) cannot be observed in this wavelength range in the presence of equal amounts of CH(2)O.

Absolute Measurements of Total Peroxy Nitrate Mixing Ratios by Thermal Dissociation Blue Diode Laser Cavity Ring-Down Spectroscopy

Peroxycarboxylic nitric anhydrides (PANs) have long been recognized as important trace gas constituents of the troposphere. Here, we describe a blue diode laser thermal dissociation cavity ring-down spectrometer for rapid and absolute measurements of total peroxyacyl nitrate (SigmaPAN) abundances at ambient concentration levels. The PANs are thermally dissociated and detected as NO2, whose mixing ratios are quantified by optical absorption at 405 nm relative to a reference channel kept at ambient temperature. The effective NO2 absorption cross-section at the diode laser emission wavelength was measured to be 6.1 x 10(-19) cm2 molecule(-1), in excellent agreement with a prediction based on a projection of a high-resolution literature absorption spectrum onto the laser line width. The performance, i.e., accuracy and precision of measurement and matrix effects, of the new 405 nm thermal dissociation cavity ring-down spectrometer was evaluated and compared to that of a 532 nm thermal dissociation cavity ring-down spectrometer using laboratory-generated air samples. The new 405 nm spectrometer was considerably more sensitive and compact than the previously constructed version. The key advantage of laser thermal dissociation cavity ring-down spectroscopy is that the measurement can be considered absolute and does not need to rely on external calibration.

A Sensitive and Versatile Detector for Atmospheric NO2 and NOX Based on Blue Diode Laser Cavity Ring-Down Spectroscopy

A sensitive, small detector was developed for atmospheric NO2 and NOx concentration measurements. NO2 is directly detected by laser diode based cavity ring-down spectroscopy (CRDS) at 404 nm. The sum of NO and NO2 (=NOx) is simultaneously measured in a second cavity by quantitative conversion of ambient NO to NO2 in excess ozone. Interferences due to absorption by other trace gases at 404 nm, such as ozone and water vapor, are either negligible or small and are easily quantified. The limit of detection is 22 pptv (2sigma precision) for NO2 at 1 s time resolution. The conversion efficiency of NO to NO2 is 99% in excess O3. The accuracy of the NO2 measurement is mainly limited by the NO2 absorption cross section to +/-3%. Because of the formation of undetectable higher nitrogen oxides in subsequent reactions of NO2 with ozone in the NOx channel, the (1sigma) accuracy of the NOx measurement is increased to approximately +/-5% depending on the level of NOx. The new instrument was designed to be easily deployed in the field with respect to size, weight and consumables. Measurements were validated against a photolysis/chemiluminescence detector during six days of sampling ambient air with colocated inlets. The data sets for NO2, NO and NOx exhibit high correlation and good agreement within the combined accuracies of both methods. Linear fits for all three species give similar slopes of 0.99 in ambient air.

High‐resolution Fourier transform measurement of the NO2 visible and near‐infrared absorption cross sections: Temperature and pressure effects

High‐resolution NO2 absorption cross sections have been obtained in the near‐IR (NIR) and visible regions using a Fourier transform spectrometer coupled to a multiple reflection cell. Spectra were recorded at 0.05 cm−1 in the NIR region (10,800–15,100 cm−1) and at 0.1 cm−1 in the visible region (13,800–26,000 cm−1), under various pressure conditions (pure NO2 and NO2/air mixtures) and at three temperatures (220, 240, and 294 K). The effects of the temperature and the pressure on the NO2 cross sections have been investigated. As expected, an increase of temperature results in a decrease of the absorption at the maxima of the absorption bands and an increase at the minima. From the measurements performed with pure NO2 at different temperatures a linear regression of the cross section with temperature has been carried out. This enabled the cross sections to be reproduced within 2% at room temperature and 7% at the lower temperatures. The variation of the cross sections with the total pressure of NO2/air mixtures has also been investigated at high resolution.

NO2 absorption cross section and its temperature dependence

Presented in this text is a compilation of existing absorption cross sections of NO2, mainly at room temperature but also at lower and higher temperatures, with a quantitative comparison of their cross sections and wavelength calibrations. From this, we concatenate three selected cross sections (slightly corrected) in order to cover the widest possible spectral range from 300 to 708 nm, at a resolution of 0.05 nm. At longer wavelengths, λ>708 nm, the (much weaker) cross section exists only at low‐resolution (≅1 nm), giving a low‐resolution cross section from 300 to 908 nm. We show that the cross‐section temperature dependence (data exist from 200 to 673 K) can be decomposed into two parts, a bell‐shaped envelope and superimposed spectral fluctuations. The envelope broaden slightly with increasing temperature, while the amplitude of the fluctuations decreases (increases) with increasing (decreasing) temperature. Finally, we sketch the “reflection” model, which allows us to get the cross‐section envelope from the shapes of the ground state vibrational wave function and of the potential energy surface of the first excited state.

Temperature dependent NO2 cross sections at high spectral resolution

The importance of nitrogen dioxide in both the troposphere and the stratosphere has been known for some years, and since the early 1970s, spectroscopic determinations have played an important role in understanding NOX chemistry. Spectroscopic measurements of the atmosphere have improved in quality in recent years to the point that an accurate determination of the NO2 absorption cross section is essential to accurate retrievals of not only NO2 but also less abundant species in the troposphere and stratosphere. NO2 is such a large absorber (approximately 1% at large air mass) in the stratosphere at twilight or in the troposphere under even mildly polluted conditions, that if it is not properly removed from observed spectra, the spectra of the more subtle species are masked and cannot be measured at all. We present cross sections of NO2 in the spectral region 350–585 nm at four temperatures between 217 and 298 K and total pressures between 100 and 600 torr at a mixing ratio of 84.1 ppmv and at a spectral resolution sufficient for accurate convolution with instruments typically used to measure atmospheric NO2. Data will be presented to demonstrate the presence of NO2 pressure dependence in high resolution. A detailed comparison with commonly used literature cross sections is made to show how such instrument parameters as wavelength accuracy, resolution, spectrograph scattered light, and data sampling affect the usefulness of the observed cross section.

The NO2 Absorption Spectrum. IV: The 200-400 nm Region at 220 K

Previous experiments in the 400–500 nm region (Coquart et al., 1995) have been extended to the 200–400 nm region to determine the absorption cross-sections of NO2 at 220 K. The NO2 and N2O4 cross-sections are obtained simultaneously from a calculation applied to the data resulting from measurements at low pressures. A comparison between the NO2 cross-sections at 220 K and at ambient temperature shows that the low temperature cross-sections are generally lower, except in the region of the absorption peaks. Comparisons are also made with previous data at temperature close to 220 K.

Fourier transform measurement of NO2 absorption cross-section in the visible range at room temperature

New laboratory measurements of NO2 absorption cross-section were performed using a Fourier transform spectrometer at 2 and 16 cm-1 (0.03 and 0.26 nm at 400 nm) in the visible range (380–830 nm) and at room temperature. The use of a Fourier transform spectrometer leads to a very accurate wavenumber scale (0.005 cm-1, 8×10-5 nm at 400 nm). The uncertainty on the new measurements is better than 4%. Absolute and differential cross-sections are compared with published data, giving an agreement ranging from 2 to 5% for the absolute values. The discrepancies in the differential cross-sections can however reach 18%. The influence of the cross-sections on the ground-based measurement of the stratospheric NO2 total amount is also investigated.

The NO2 absorption spectrum. II. Absorption cross-sections at low temperatures in the 400?500 nm region

With improved experimental conditions already used for measurements at ambient temperature (Merienneet al., 1994), new values have been found for the absorption cross-sections of NO2 at 240 and 220 K in the 400–500 nm spectral region. Using a better resolution than in previous studies we show that the temperature effect is not negligible and should be taken into account for the optical measurements of atmospheric NO2 amounts by differential absorption methods.