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We introduce the new Global Ozone Monitoring Experiment-2 (GOME-2) daily and monthly level-3 product of total column ozone (O3), total and tropospheric column nitrogen dioxide (NO2), total column water vapour, total column bromine oxide (BrO), total column formaldehyde (HCHO), and total column sulfur dioxide (SO2) (daily products https://doi.org/10.15770/EUM_SAF_AC_0048, AC SAF, 2023a; monthly products https://doi.org/10.15770/EUM_SAF_AC_0049, AC SAF, 2023b). The GOME-2 level-3 products aim to provide easily translatable and user-friendly data sets to the scientific community for scientific progress as well as to satisfy public interest. The purpose of this paper is to present the theoretical basis as well as the verification and validation of the GOME-2 daily and monthly level-3 products. The GOME-2 level-3 products are produced using the overlapping area-weighting method. Details of the gridding algorithm are presented. The spatial resolution of the GOME-2 level-3 products is selected based on the sensitivity study. The consistency of the resulting level-3 products among three GOME-2 sensors is investigated through time series of global averages, zonal averages, and bias. The accuracy of the products is validated by comparison to ground-based observations. The verification and validation results show that the GOME-2 level-3 products are consistent with the level-2 data. Small discrepancies are found among three GOME-2 sensors, which are mainly caused by the differences in the instrument characteristic and level-2 processor. The comparison of GOME-2 level-3 products to ground-based observations in general shows very good agreement, indicating that the products are consistent and fulfil the requirements to serve the scientific community and general public.

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).

The Brewer ozone spectrophotometer (the Brewer) was designed at Environment and Climate Change Canada (ECCC) in the 1970s to make accurate automated total ozone column measurements. Since the 1980s, the Brewer instrument has become a World Meteorological Organization (WMO) Global Atmosphere Watch (GAW) standard ozone monitoring instrument. Now, more than 230 Brewers have been produced. To assure the quality of the Brewer measurements, a calibration chain is maintained, i.e., first, the reference instruments are independently absolutely calibrated, and then the calibration is transferred from the reference instrument to the travelling standard, and subsequently from the travelling standard to field instruments. ECCC has maintained the world Brewer reference instruments since the 1980s to provide transferable calibration to field instruments at monitoring sites. Three single-monochromator (Mark II) type instruments (serial numbers 008, 014, and 015) formed this world Brewer reference triad (BrT) and started their service in Toronto, Canada, in 1984. In the 1990s, the Mark III type Brewer (known as the double Brewer) was developed, which has two monochromators to reduce the internal instrumental stray light. The double-Brewer world reference triad (BrT-D) was formed in 2013 (serial numbers 145, 187 and 191), co-located with the BrT. The first assessment of the BrT's performance was made in 2005, covering the period between 1984 and 2004 (Fioletov et al., 2005). The current work provides an updated assessment of the BrT's performance (from 1999 to 2019) and the first comprehensive assessment of the BrT-D. The random uncertainties of individual reference instruments are within the WMO/GAW requirement of 1 % (WMO, 2001): 0.49 % and 0.42 % for BrT and BrT-D, respectively, as estimated in this study. The long-term stability of the reference instruments is also evaluated in terms of uncertainties of the key instrument characteristics: the extraterrestrial calibration constant (ETC) and effective ozone absorption coefficients (both having an effect of less than 2 % on total column ozone). Measurements from a ground-based instrument (Pandora spectrometer), satellites (11 datasets, including the most recent high-resolution satellite, TROPOspheric Monitoring Instrument), and reanalysis model (the second Modern-Era Retrospective analysis for Research and Applications, MERRA-2) are used to further assess the performance of world Brewer reference instruments and to provide a context for the requirements of stratospheric ozone observations during the last two decades.

Nitrogen oxides (NOx≡NO+NO2) in the NOx-limited upper troposphere (UT) are long-lived and so have a large influence on the oxidizing capacity of the troposphere and formation of the greenhouse gas ozone. Models misrepresent NOx in the UT, and observations to address deficiencies in models are sparse. Here we obtain a year of near-global seasonal mean mixing ratios of NO2 in the UT (450–180 hPa) at 1∘×1∘ by applying cloud-slicing to partial columns of NO2 from TROPOMI. This follows refinement of the cloud-slicing algorithm with synthetic partial columns from the GEOS-Chem chemical transport model. TROPOMI, prior to cloud-slicing, is corrected for a 13 % underestimate in stratospheric NO2 variance and a 50 % overestimate in free-tropospheric NO2 determined by comparison to Pandora total columns at high-altitude free-tropospheric sites at Mauna Loa, Izaña, and Altzomoni and MAX-DOAS and Pandora tropospheric columns at Izaña. Two cloud-sliced seasonal mean UT NO2 products for June 2019 to May 2020 are retrieved from corrected TROPOMI total columns using distinct TROPOMI cloud products that assume clouds are reflective boundaries (FRESCO-S) or water droplet layers (ROCINN-CAL). TROPOMI UT NO2 typically ranges from 20–30 pptv over remote oceans to >80 pptv over locations with intense seasonal lightning. Spatial coverage is mostly in the tropics and subtropics with FRESCO-S and extends to the midlatitudes and polar regions with ROCINN-CAL, due to its greater abundance of optically thick clouds and wider cloud-top altitude range. TROPOMI UT NO2 seasonal means are spatially consistent (R=0.6–0.8) with an existing coarser spatial resolution (5∘ latitude × 8∘ longitude) UT NO2 product from the Ozone Monitoring Instrument (OMI). UT NO2 from TROPOMI is 12–26 pptv more than that from OMI due to increase in NO2 with altitude from the OMI pressure ceiling (280 hPa) to that for TROPOMI (180 hPa), but possibly also due to altitude differences in TROPOMI and OMI cloud products and NO2 retrieval algorithms. The TROPOMI UT NO2 product offers potential to evaluate and improve representation of UT NOx in models and supplement aircraft observations that are sporadic and susceptible to large biases in the UT.

The second Cabauw Intercomparison of Nitrogen Dioxide measuring Instruments (CINDI-2) took place in Cabauw (the Netherlands) in September 2016 with the aim of assessing the consistency of multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements of tropospheric species (NO2, HCHO, O3, HONO, CHOCHO and O4). This was achieved through the coordinated operation of 36 spectrometers operated by 24 groups from all over the world, together with a wide range of supporting reference observations (in situ analysers, balloon sondes, lidars, long-path DOAS, direct-sun DOAS, Sun photometer and meteorological instruments). In the presented study, the retrieved CINDI-2 MAX-DOAS trace gas (NO2, HCHO) and aerosol vertical profiles of 15 participating groups using different inversion algorithms are compared and validated against the colocated supporting observations, with the focus on aerosol optical thicknesses (AOTs), trace gas vertical column densities (VCDs) and trace gas surface concentrations. The algorithms are based on three different techniques: six use the optimal estimation method, two use a parameterized approach and one algorithm relies on simplified radiative transport assumptions and analytical calculations. To assess the agreement among the inversion algorithms independent of inconsistencies in the trace gas slant column density acquisition, participants applied their inversion to a common set of slant columns. Further, important settings like the retrieval grid, profiles of O3, temperature and pressure as well as aerosol optical properties and a priori assumptions (for optimal estimation algorithms) have been prescribed to reduce possible sources of discrepancies. The profiling results were found to be in good qualitative agreement: most participants obtained the same features in the retrieved vertical trace gas and aerosol distributions; however, these are sometimes at different altitudes and of different magnitudes. Under clear-sky conditions, the root-mean-square differences (RMSDs) among the results of individual participants are in the range of 0.01–0.1 for AOTs, (1.5–15) ×1014molec.cm-2 for trace gas (NO2, HCHO) VCDs and (0.3–8)×1010molec.cm-3 for trace gas surface concentrations. These values compare to approximate average optical thicknesses of 0.3, trace gas vertical columns of 90×1014molec.cm-2 and trace gas surface concentrations of 11×1010molec.cm-3 observed over the campaign period. The discrepancies originate from differences in the applied techniques, the exact implementation of the algorithms and the user-defined settings that were not prescribed. For the comparison against supporting observations, the RMSDs increase to a range of 0.02–0.2 against AOTs from the Sun photometer, (11–55)×1014molec.cm-2 against trace gas VCDs from direct-sun DOAS observations and (0.8–9)×1010molec.cm-3 against surface concentrations from the long-path DOAS instrument. This increase in RMSDs is most likely caused by uncertainties in the supporting data, spatiotemporal mismatch among the observations and simplified assumptions particularly on aerosol optical properties made for the MAX-DOAS retrieval. As a side investigation, the comparison was repeated with the participants retrieving profiles from their own differential slant column densities (dSCDs) acquired during the campaign. In this case, the consistency among the participants degrades by about 30 % for AOTs, by 180 % (40 %) for HCHO (NO2) VCDs and by 90 % (20 %) for HCHO (NO2) surface concentrations. In former publications and also during this comparison study, it was found that MAX-DOAS vertically integrated aerosol extinction coefficient profiles systematically underestimate the AOT observed by the Sun photometer. For the first time, it is quantitatively shown that for optimal estimation algorithms this can be largely explained and compensated by considering biases arising from the reduced sensitivity of MAX-DOAS observations to higher altitudes and associated a priori assumptions.

This paper reports on consolidated ground-based validation results of the atmospheric NO2 data produced operationally since April 2018 by the TROPOspheric Monitoring Instrument (TROPOMI) on board of the ESA/EU Copernicus Sentinel-5 Precursor (S5P) satellite. Tropospheric, stratospheric, and total NO2 column data from S5P are compared to correlative measurements collected from, respectively, 19 Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS), 26 Network for the Detection of Atmospheric Composition Change (NDACC) Zenith-Scattered-Light DOAS (ZSL-DOAS), and 25 Pandonia Global Network (PGN)/Pandora instruments distributed globally. The validation methodology gives special care to minimizing mismatch errors due to imperfect spatio-temporal co-location of the satellite and correlative data, e.g. by using tailored observation operators to account for differences in smoothing and in sampling of atmospheric structures and variability and photochemical modelling to reduce diurnal cycle effects. Compared to the ground-based measurements, S5P data show, on average, (i) a negative bias for the tropospheric column data, of typically −23 % to −37 % in clean to slightly polluted conditions but reaching values as high as −51 % over highly polluted areas; (ii) a slight negative median difference for the stratospheric column data, of about −0.2 Pmolec cm−2, i.e. approx. −2 % in summer to −15 % in winter; and (iii) a bias ranging from zero to −50 % for the total column data, found to depend on the amplitude of the total NO2 column, with small to slightly positive bias values for columns below 6 Pmolec cm−2 and negative values above. The dispersion between S5P and correlative measurements contains mostly random components, which remain within mission requirements for the stratospheric column data (0.5 Pmolec cm−2) but exceed those for the tropospheric column data (0.7 Pmolec cm−2). While a part of the biases and dispersion may be due to representativeness differences such as different area averaging and measurement times, it is known that errors in the S5P tropospheric columns exist due to shortcomings in the (horizontally coarse) a priori profile representation in the TM5-MP chemical transport model used in the S5P retrieval and, to a lesser extent, to the treatment of cloud effects and aerosols. Although considerable differences (up to 2 Pmolec cm−2 and more) are observed at single ground-pixel level, the near-real-time (NRTI) and offline (OFFL) versions of the S5P NO2 operational data processor provide similar NO2 column values and validation results when globally averaged, with the NRTI values being on average 0.79 % larger than the OFFL values.

Analysis of formaldehyde measurements by the Pandora spectrometer systems between 2016 and 2019 suggested that there was a temperature-dependent process inside the Pandora head sensor that emitted formaldehyde. Some parts in the head sensor were manufactured from the thermal plastic polyoxymethylene homopolymer (E.I. Du Pont de Nemour & Co., USA; POM-H Delrin®) and were responsible for formaldehyde production. Laboratory analysis of the four Pandora head sensors showed that internal formaldehyde production had exponential temperature dependence with a damping coefficient of 0.0911±0.0024 ∘C−1 and the exponential function amplitude ranging from 0.0041 to 0.049 DU. No apparent dependency on the head sensor age and heating and cooling rates was detected. The total amount of formaldehyde internally generated by the POM-H Delrin components and contributing to the direct-sun measurements were estimated based on the head sensor temperature and solar zenith angle of the measurements. Measurements in winter, during colder (< 10 ∘C) days in general, and at high solar zenith angles (> 75∘) were minimally impacted. Measurements during hot days (> 28 ∘C) and small solar zenith angles had up to 1 DU (2.69×1016 molec. cm−2) contribution from POM-H Delrin parts. Multi-axis differential slant column densities were minimally impacted ( DU) due to the reference spectrum being collected within a short time period with a small difference in head sensor temperature. Three new POM-H Delrin free Pandora head sensors (manufactured in summer 2019) were evaluated for temperature-dependent attenuation across the entire spectral range (300 to 530 nm). No formaldehyde absorption or any other absorption above the instrumental noise was observed across the entire spectral range.

Airborne and ground-based Pandora spectrometer NO2 column measurements were collected during the 2018 Long Island Sound Tropospheric Ozone Study (LISTOS) in the New York City/Long Island Sound region, which coincided with early observations from the Sentinel-5P TROPOspheric Monitoring Instrument (TROPOMI) instrument. Both airborne- and ground-based measurements are used to evaluate the TROPOMI NO2 Tropospheric Vertical Column (TrVC) product v1.2 in this region, which has high spatial and temporal heterogeneity in NO2. First, airborne and Pandora TrVCs are compared to evaluate the uncertainty of the airborne TrVC and establish the spatial representativeness of the Pandora observations. The 171 coincidences between Pandora and airborne TrVCs are found to be highly correlated (r2= 0.92 and slope of 1.03), with the largest individual differences being associated with high temporal and/or spatial variability. These reference measurements (Pandora and airborne) are complementary with respect to temporal coverage and spatial representativity. Pandora spectrometers can provide continuous long-term measurements but may lack areal representativity when operated in direct-sun mode. Airborne spectrometers are typically only deployed for short periods of time, but their observations are more spatially representative of the satellite measurements with the added capability of retrieving at subpixel resolutions of 250 m × 250 m over the entire TROPOMI pixels they overfly. Thus, airborne data are more correlated with TROPOMI measurements (r2=0.96) than Pandora measurements are with TROPOMI (r2=0.84). The largest outliers between TROPOMI and the reference measurements appear to stem from too spatially coarse a priori surface reflectivity (0.5∘) over bright urban scenes. In this work, this results during cloud-free scenes that, at times, are affected by errors in the TROPOMI cloud pressure retrieval impacting the calculation of tropospheric air mass factors. This factor causes a high bias in TROPOMI TrVCs of 4 %–11 %. Excluding these cloud-impacted points, TROPOMI has an overall low bias of 19 %–33 % during the LISTOS timeframe of June–September 2018. Part of this low bias is caused by coarse a priori profile input from the TM5-MP model; replacing these profiles with those from a 12 km North American Model–Community Multiscale Air Quality (NAMCMAQ) analysis results in a 12 %–14 % increase in the TrVCs. Even with this improvement, the TROPOMI-NAMCMAQ TrVCs have a 7 %–19 % low bias, indicating needed improvement in a priori assumptions in the air mass factor calculation. Future work should explore additional impacts of a priori inputs to further assess the remaining low biases in TROPOMI using these datasets.

Multi-axis differential optical absorption spectroscopy (MAX-DOAS) and direct sun NO2 vertical column network data are used to investigate the accuracy of tropospheric NO2 column measurements of the GOME-2 instrument on the MetOp-A satellite platform and the OMI instrument on Aura. The study is based on 23 MAX-DOAS and 16 direct sun instruments at stations distributed worldwide. A method to quantify and correct for horizontal dilution effects in heterogeneous NO2 field conditions is proposed. After systematic application of this correction to urban sites, satellite measurements are found to present smaller biases compared to ground-based reference data in almost all cases. We investigate the seasonal dependence of the validation results as well as the impact of using different approaches to select satellite ground pixels in coincidence with ground-based data. In optimal comparison conditions (satellite pixels containing the station) the median bias between satellite tropospheric NO2 column measurements and the ensemble of MAX-DOAS and direct sun measurements is found to be significant and equal to −34 % for GOME-2A and −24 % for OMI. These biases are further reduced to −24 % and −18 % respectively, after application of the dilution correction. Comparisons with the QA4ECV satellite product for both GOME-2A and OMI are also performed, showing less scatter but also a slightly larger median tropospheric NO2 column bias with respect to the ensemble of MAX-DOAS and direct sun measurements.

Satellite data from the Ozone Measuring Instrument (OMI) and Earth Polychromatic Imaging Camera (EPIC) are used to study long-term changes and global distribution of UV erythemal irradiance E(ζ,φ,z,t) (mW m−2) and the dimensionless UV index E ∕ (25 m Wm−2) over major cities as a function of latitude ζ, longitude φ, altitude z, and time t. Extremely high amounts of erythemal irradiance (12 < UV index ) are found for many low-latitude and high-altitude sites (e.g., San Pedro, Chile, 2.45 km; La Paz, Bolivia, 3.78 km). Lower UV indices at some equatorial or high-altitude sites (e.g., Quito, Ecuador) occur because of persistent cloud effects. High UVI levels (UVI > 6) are also found at most mid-latitude sites during the summer months for clear-sky days. OMI time-series data starting in January 2005 to December 2018 are used to estimate 14-year changes in erythemal irradiance ΔE, total column ozone ΔTCO3, cloud and haze transmission ΔCT derived from scene reflectivity LER, and reduced transmission from absorbing aerosols ΔCA derived from absorbing aerosol optical depth τA for 191 specific cities in the Northern Hemisphere and Southern Hemisphere from 60∘ S to 60∘ N using publicly available OMI data. A list of the sites showing changes at the 1 standard deviation level 1σ is provided. For many specific sites there has been little or no change in E(ζ,φ,z,t) for the period 2005–2018. When the sites are averaged over 15∘ of latitude, there are strong correlation effects of both short- and long-term cloud and absorbing aerosol change as well as anticorrelation with total column ozone change ΔTCO3. Estimates of changes in atmospheric transmission ΔCT (ζ, φ, z, t) derived from OMI-measured cloud and haze reflectivity LER and averaged over 15∘ of latitude show an increase of 1.1±1.2 % per decade between 60 and 45∘ S, almost no average 14-year change of 0.03±0.5 % per decade from 55∘ S to 30∘ N, local increases and decreases from 20 to 30∘ N, and an increase of 1±0.9 % per decade from 35 to 60∘ N. The largest changes in E(ζ,φ,z,t) are driven by changes in cloud transmission CT. Synoptic EPIC radiance data from the sunlit Earth are used to derive ozone and reflectivity needed for global images of the distribution of E(ζ,φ,z,t) from sunrise to sunset centered on the Americas, Europe–Africa, and Asia. EPIC data are used to show the latitudinal distribution of E(ζ,φ,z,t) from the Equator to 75∘ for specific longitudes. EPIC UV erythemal images show the dominating effect of solar zenith angle (SZA), the strong increase in E with altitude, and the decreases caused by cloud cover. The nearly cloud-free images of E(ζ,φ,z,t) over Australia during the summer (December) show regions of extremely high UVI (14–16) covering large parts of the continent. Zonal averages show a maximum of UVI = 14 in the equatorial region seasonally following latitudes where SZA = 0∘. Dangerously high amounts of erythemal irradiance (12 < UV index < 18) are found for many low-latitude and high-altitude sites. High levels of UVI are known to lead to health problems (skin cancer and eye cataracts) with extended unprotected exposure, as shown in the extensive health statistics maintained by the Australian Institute of Health and Welfare and the United States National Institute of Health National Cancer Institute.

In September 2016, 36 spectrometers from 24 institutes measured a number of key atmospheric pollutants for a period of 17 d during the Second Cabauw Intercomparison campaign for Nitrogen Dioxide measuring Instruments (CINDI-2) that took place at Cabauw, the Netherlands (51.97∘ N, 4.93∘ E). We report on the outcome of the formal semi-blind intercomparison exercise, which was held under the umbrella of the Network for the Detection of Atmospheric Composition Change (NDACC) and the European Space Agency (ESA). The three major goals of CINDI-2 were (1) to characterise and better understand the differences between a large number of multi-axis differential optical absorption spectroscopy (MAX-DOAS) and zenith-sky DOAS instruments and analysis methods, (2) to define a robust methodology for performance assessment of all participating instruments, and (3) to contribute to a harmonisation of the measurement settings and retrieval methods. This, in turn, creates the capability to produce consistent high-quality ground-based data sets, which are an essential requirement to generate reliable long-term measurement time series suitable for trend analysis and satellite data validation. The data products investigated during the semi-blind intercomparison are slant columns of nitrogen dioxide (NO2), the oxygen collision complex (O4) and ozone (O3) measured in the UV and visible wavelength region, formaldehyde (HCHO) in the UV spectral region, and NO2 in an additional (smaller) wavelength range in the visible region. The campaign design and implementation processes are discussed in detail including the measurement protocol, calibration procedures and slant column retrieval settings. Strong emphasis was put on the careful alignment and synchronisation of the measurement systems, resulting in a unique set of measurements made under highly comparable air mass conditions. The CINDI-2 data sets were investigated using a regression analysis of the slant columns measured by each instrument and for each of the target data products. The slope and intercept of the regression analysis respectively quantify the mean systematic bias and offset of the individual data sets against the selected reference (which is obtained from the median of either all data sets or a subset), and the rms error provides an estimate of the measurement noise or dispersion. These three criteria are examined and for each of the parameters and each of the data products, performance thresholds are set and applied to all the measurements. The approach presented here has been developed based on heritage from previous intercomparison exercises. It introduces a quantitative assessment of the consistency between all the participating instruments for the MAX-DOAS and zenith-sky DOAS techniques.

The TROPOspheric Monitoring Instrument (TROPOMI) aboard the Sentinel-5 Precursor satellite (launched on 13 October 2017) is a nadir-viewing spectrometer measuring reflected sunlight in the ultraviolet, visible, near-infrared, and shortwave infrared spectral ranges. The measured spectra are used to retrieve total columns of trace gases, including nitrogen dioxide (NO2). For ground validation of these satellite measurements, Pandora spectrometers, which retrieve high-quality NO2 total columns via direct-sun measurements, are widely used. In this study, Pandora NO2 measurements made at three sites located in or north of the Greater Toronto Area (GTA) are used to evaluate the TROPOMI NO2 data products, including a standard Royal Netherlands Meteorological Institute (KNMI) tropospheric and stratospheric NO2 data product and a TROPOMI research data product developed by Environment and Climate Change Canada (ECCC) using a high-resolution regional air quality forecast model (in the air mass factor calculation). It is found that these current TROPOMI tropospheric NO2 data products (standard and ECCC) met the TROPOMI design bias requirement (NO2 emissions, which can be used to evaluate regional air quality changes. The TROPOMI ECCC NO2 research data product shows improved agreement with Pandora measurements compared to the TROPOMI standard tropospheric NO2 data product (e.g., lower multiplicative bias at the suburban and urban sites by about 10 %), demonstrating benefits from the high-resolution regional air quality forecast model.

NASA deployed the GeoTASO airborne UV–visible spectrometer in May–June 2017 to produce high-resolution (approximately 250 m×250 m) gapless NO2 datasets over the western shore of Lake Michigan and over the Los Angeles Basin. The results collected show that the airborne tropospheric vertical column retrievals compare well with ground-based Pandora spectrometer column NO2 observations (r2=0.91 and slope of 1.03). Apparent disagreements between the two measurements can be sensitive to the coincidence criteria and are often associated with large local variability, including rapid temporal changes and spatial heterogeneity that may be observed differently by the sunward-viewing Pandora observations. The gapless mapping strategy executed during the 2017 GeoTASO flights provides data suitable for averaging to coarser areal resolutions to simulate satellite retrievals. As simulated satellite pixel area increases to values typical of TEMPO (Tropospheric Emissions: Monitoring Pollution), TROPOMI (TROPOspheric Monitoring Instrument), and OMI (Ozone Monitoring Instrument), the agreement with Pandora measurements degraded, particularly for the most polluted columns as localized large pollution enhancements observed by Pandora and GeoTASO are spatially averaged with nearby less-polluted locations within the larger area representative of the satellite spatial resolutions (aircraft-to-Pandora slope: TEMPO scale =0.88; TROPOMI scale =0.77; OMI scale =0.57). In these two regions, Pandora and TEMPO or TROPOMI have the potential to compare well at least up to pollution scales of 30×1015 molecules cm−2. Two publicly available OMI tropospheric NO2 retrievals are found to be biased low with respect to these Pandora observations. However, the agreement improves when higher-resolution a priori inputs are used for the tropospheric air mass factor calculation (NASA V3 standard product slope =0.18 and Berkeley High Resolution product slope =0.30). Overall, this work explores best practices for satellite validation strategies with Pandora direct-sun observations by showing the sensitivity to product spatial resolution and demonstrating how the high-spatial-resolution NO2 data retrieved from airborne spectrometers, such as GeoTASO, can be used with high-temporal-resolution ground-based column observations to evaluate the influence of spatial heterogeneity on validation results.

Pandora spectrometers can retrieve nitrogen dioxide (NO2) vertical column densities (VCDs) via two viewing geometries: direct Sun and zenith sky. The direct-Sun NO2 VCD measurements have high quality (0.1 DU accuracy in clear-sky conditions) and do not rely on any radiative transfer model to calculate air mass factors (AMFs); however, they are not available when the Sun is obscured by clouds. To perform NO2 measurements in cloudy conditions, a simple but robust NO2 retrieval algorithm is developed for Pandora zenith-sky measurements. This algorithm derives empirical zenith-sky NO2 AMFs from coincident high-quality direct-Sun NO2 observations. Moreover, the retrieved Pandora zenith-sky NO2 VCD data are converted to surface NO2 concentrations with a scaling algorithm that uses chemical-transport-model predictions and satellite measurements as inputs. NO2 VCDs and surface concentrations are retrieved from Pandora zenith-sky measurements made in Toronto, Canada, from 2015 to 2017. The retrieved Pandora zenith-sky NO2 data (VCD and surface concentration) show good agreement with both satellite and in situ measurements. The diurnal and seasonal variations of derived Pandora zenith-sky surface NO2 data also agree well with in situ measurements (diurnal difference within ±2 ppbv). Overall, this work shows that the new Pandora zenith-sky NO2 products have the potential to be used in various applications such as future satellite validation in moderate cloudy scenes and air quality monitoring.

The Korea–United States Air Quality Study (KORUS-AQ) conducted during May–June 2016 offered the first opportunity to evaluate direct-sun observations of formaldehyde (HCHO) total column densities with improved Pandora spectrometer instruments. The measurements highlighted in this work were conducted both in the Seoul megacity area at the Olympic Park site (37.5232° N, 27.1260° E; 26 m a.s.l.) and at a nearby rural site downwind of the city at the Mount Taehwa research forest site (37.3123° N, 127.3106° E; 160 m a.s.l.). Evaluation of these measurements was made possible by concurrent ground-based in situ observations of HCHO at both sites as well as overflight by the NASA DC-8 research aircraft. The flights provided in situ measurements of HCHO to characterize its vertical distribution in the lower troposphere (0–5 km).Diurnal variation in HCHO total column densities followed the same pattern at both sites, with the minimum daily values typically observed between 6:00 and 7:00 local time, gradually increasing to a maximum between 13:00 and 17:00 before decreasing into the evening. Pandora vertical column densities were compared with those derived from the DC-8 HCHO in situ measured profiles augmented with in situ surface concentrations below the lowest altitude of the DC-8 in proximity to the ground sites. A comparison between 49 column densities measured by Pandora vs. aircraft-integrated in situ data showed that Pandora values were larger by 16 % with a constant offset of 0.22 DU (Dobson units; R2 = 0.68). Pandora HCHO columns were also compared with columns calculated from the surface in situ measurements over Olympic Park by assuming a well-mixed lower atmosphere up to a ceilometer-measured mixed-layer height (MLH) and various assumptions about the small residual HCHO amounts in the free troposphere up to the tropopause. The best comparison (slope = 1.03±0.03; intercept = 0.29±0.02 DU; and R2 = 0.78±0.02) was achieved assuming equal mixing within ceilometer-measured MLH combined with an exponential profile shape. These results suggest that diurnal changes in HCHO surface concentrations can be reasonably estimated from the Pandora total column and information on the mixed-layer height. More work is needed to understand the bias in the intercept and the slope relative to columns derived from the in situ aircraft and surface measurements.

Nine Pandora spectrometer instruments (PSI) were installed at eight sites in South Korea as part of the KORUS-AQ (Korea U.S.-Air Quality) field study integrating information from ground, aircraft, and satellite measurements for validation of remote sensing air-quality studies. The PSI made direct-sun measurements of total vertical column NO2, C(NO2), with high precision (0.05 DU, where 1 DU  = 2.69 × 1016 molecules cm−2) and accuracy (0.1 DU) that were retrieved using spectral fitting techniques. Retrieval of formaldehyde C(HCHO) total column amounts were also obtained at five sites using the recently improved PSI optics. The C(HCHO) retrievals have high precision, but possibly lower accuracy than for NO2 because of uncertainty about the optimum spectral window for all ground-based and satellite instruments. PSI direct-sun retrieved values for C(NO2) and C(HCHO) are always significantly larger than OMI (AURA satellite Ozone Monitoring Instrument) retrieved C(NO2) and C(HCHO) for the OMI overpass local times (KST = 13.5 ± 0.5 h). In urban areas, PSI C(NO2) 30-day running averages are at least a factor of two larger than OMI averages. Similar differences are seen for C(HCHO) in Seoul and nearby surrounding areas. Late afternoon values of C(HCHO) measured by PSI are even larger, implying that OMI early afternoon measurements underestimate the effect of poor air quality on human health. The primary cause of OMI underestimates is the large OMI field of view (FOV) that includes regions containing low values of pollutants. In relatively clean areas, PSI and OMI are more closely in agreement. C(HCHO) amounts were obtained for five sites, Yonsei University in Seoul, Olympic Park, Taehwa Mountain, Amnyeondo, and Yeoju. Of these, the largest amounts of C(HCHO) were observed at Olympic Park and Taehwa Mountain, surrounded by significant amounts of vegetation. Comparisons of PSI C(HCHO) results were made with the Compact Atmospheric Multispecies Spectrometer CAMS during overflights on the DC-8 aircraft for Taehwa Mountain and Olympic Park. In all cases, PSI measured substantially more C(HCHO) than obtained from integrating the CAMS altitude profiles. PSI C(HCHO) at Yonsei University in Seoul frequently reached 0.6 DU and occasionally exceeded 1.5 DU. The semi-rural site, Taehwa Mountain, frequently reached 0.9 DU and occasionally exceeded 1.5 DU. Even at the cleanest site, Amnyeondo, C(HCHO) occasionally exceeded 1 DU.

Ten wavelength channels of calibrated radiance image data from the sunlit Earth are obtained every 65 min during Northern Hemisphere summer from the EPIC (Earth Polychromatic Imaging Camera) instrument on the DSCOVR (Deep Space Climate Observatory) satellite located near the Earth–Sun Lagrange 1 point (L1), about 1.5 million km from the Earth. The L1 location permitted seven observations of the Moon's shadow on the Earth for about 3 h during the 21 August 2017 eclipse. Two of the observations were timed to coincide with totality over Casper, Wyoming, and Columbia, Missouri. Since the solar irradiances within five channels (λi = 388, 443, 551, 680, and 780 nm) are not strongly absorbed in the atmosphere, they can be used for characterizing the eclipse reduction in reflected radiances for the Earth's sunlit face containing the eclipse shadow. Five channels (λi = 317.5, 325, 340, 688, and 764 nm) that are partially absorbed in the atmosphere give consistent reductions compared to the non-absorbed channels. This indicates that cloud reflectivities dominate the 317.5–780 nm radiances reflected back to space from the sunlit Earth's disk with a significant contribution from Rayleigh scattering for the shorter wavelengths. An estimated reduction of 10 % was obtained for spectrally integrated radiance (387 to 781 nm) reflected from the sunlit Earth towards L1 for two sets of observations on 21 August 2017, while the shadow was in the vicinity of Casper, Wyoming (42.8666° N, 106.3131° W; centered on 17:44:50 UTC), and Columbia, Missouri (38.9517° N, 92.3341° W; centered on 18:14:50 UTC). In contrast, when non-eclipse days (20 and 23 August) are compared for each wavelength channel, the change in reflected light is much smaller (less than 1 % for 443 nm compared to 9 % (Casper) and 8 % (Columbia) during the eclipse). Also measured was the ratio REN(λi) of reflected radiance on adjacent non-eclipse days divided by radiances centered in the eclipse totality region with the same geometry for all 10 wavelength channels. The measured REN(443 nm) was smaller for Columbia (169) than for Casper (935), because Columbia had more cloud cover than Casper. REN(λi) forms a useful test of a 3-D radiative transfer models for an eclipse in the presence of optically thin clouds. Specific values measured at Casper with thin clouds are REN(340 nm) = 475, REN(388 nm) = 3500, REN(443 nm) = 935, REN(551 nm) = 5455, REN(680 nm) = 220, and REN(780 nm) = 395. Some of the variability is caused by changing cloud amounts within the moving region of totality during the 2.7 min needed to measure all 10 wavelength channels.

EPIC (Earth Polychromatic Imaging Camera) on board the DSCOVR (Deep Space Climate Observatory) spacecraft is the first earth science instrument located near the earth–sun gravitational plus centrifugal force balance point, Lagrange 1. EPIC measures earth-reflected radiances in 10 wavelength channels ranging from 317.5 to 779.5 nm. Of these channels, four are in the UV range 317.5, 325, 340, and 388 nm, which are used to retrieve O3, 388 nm scene reflectivity (LER: Lambert equivalent reflectivity), SO2, and aerosol properties. These new synoptic quantities are retrieved for the entire sunlit globe from sunrise to sunset multiple times per day as the earth rotates in EPIC's field of view. Retrieved ozone amounts agree with ground-based measurements and satellite data to within 3 %. The ozone amounts and LER are combined to derive the erythemal irradiance for the earth's entire sunlit surface at a nadir resolution of 18 × 18 km2 using a computationally efficient approximation to a radiative transfer calculation of irradiance. The results show very high summertime values of the UV index (UVI) in the Andes and Himalayas (greater than 18), and high values of UVI near the Equator at equinox.

A one-time-calibrated (in December 2013) Pandora spectrometer instrument (Pan #034) has been compared to a periodically calibrated Dobson spectroradiometer (Dobson #061) co-located in Boulder, Colorado, and compared with two satellite instruments over a 3-year period (December 2013–December 2016). The results show good agreement between Pan #034 and Dobson #061 within their statistical uncertainties. Both records are corrected for ozone retrieval sensitivity to stratospheric temperature variability obtained from the Global Modeling Initiative (GMI) and Modern-Era Retrospective analysis for Research and Applications (MERRA-2) model calculations. Pandora #034 and Dobson #061 differ by an average of 2.1 ± 3.2 % when both instruments use their standard ozone absorption cross sections in the retrieval algorithms. The results show a relative drift (0.2 ± 0.08 % yr−1) between Pandora observations against NOAA Dobson in Boulder, CO, over a 3-year period of continuous operation. Pandora drifts relative to the satellite Ozone Monitoring Instrument (OMI) and the Ozone Mapping Profiler Suite (OMPS) are +0.18 ± 0.2 % yr−1 and −0.18 ± 0.2 % yr−1, respectively, where the uncertainties are 2 standard deviations. The drift between Dobson #061 and OMPS for a 5.5-year period (January 2012–June 2017) is −0.07 ± 0.06 % yr−1.

This study evaluates the performance of the recently developed Pandora spectrometer by comparing it with the Brewer reference triad. This triad was established by Environment and Climate Change Canada (ECCC) in the 1980s and is used to calibrate Brewer instruments around the world, ensuring high-quality total column ozone (TCO) measurements. To reduce stray light, the double Brewer instrument was introduced in 1992, and a new reference triad of double Brewers is also operational at Toronto. Since 2013, ECCC has deployed two Pandora spectrometers co-located with the old and new Brewer triads, making it possible to study the performance of three generations of ozone-monitoring instruments. The statistical analysis of TCO records from these instruments indicates that the random uncertainty for the Brewer is below 0.6 %, while that for the Pandora is below 0.4 %. However, there is a 1 % seasonal difference and a 3 % bias between the standard Pandora and Brewer TCO data, which is related to the temperature dependence and difference in ozone cross sections. A statistical model was developed to remove this seasonal difference and bias. It was based on daily temperature profiles from the European Centre for Medium-Range Weather Forecasts ERA-Interim data over Toronto and TCO from the Brewer reference triads. When the statistical model was used to correct Pandora data, the seasonal difference was reduced to 0.25 % and the bias was reduced to 0.04 %. Pandora instruments were also found to have low air mass dependence up to 81.6° solar zenith angle, comparable to double Brewer instruments.

Vertical column densities (VCDs) of SO2 retrieved by a Pandora spectral sun photometer at Fort McKay, Alberta, Canada, from 2013 to 2015 were analysed. The Fort McKay site is located in the Canadian oil sands region, approximately 20 km north of two major SO2 sources (upgraders), with total emission of about 45 kt yr−1. Elevated SO2 VCD values were frequently recorded by the instrument, with the highest values of about 9 Dobson Units (DU; DU = 2.69 × 1016 molecules cm−2). Comparisons with co-located in situ measurements demonstrated that there was a very good correlation between VCDs and surface concentrations in some cases, while in other cases, elevated VCDs did not correspond to high surface concentrations, suggesting the plume was above the ground. Elevated VCDs and surface concentrations were observed when the wind direction was from south to southeast, i.e. from the direction of the two local SO2 sources. The precision of the SO2 measurements, estimated from parallel measurements by two Pandora instruments at Toronto, is 0.17 DU. The total uncertainty of Pandora SO2 VCD, estimated using measurements when the wind direction was away from the sources, is less than 0.26 DU (1σ). Comparisons with integrated SO2 profiles from concurrent aircraft measurements support these estimates.

Brewer spectrophotometers are widely used instruments which perform spectral measurements of the direct, the scattered and the global solar UV irradiance. By processing these measurements a variety of secondary products can be derived such as the total columns of ozone (TOC), sulfur dioxide and nitrogen dioxide and aerosol optical properties. Estimating and limiting the uncertainties of the final products is of critical importance. High-quality data have a lot of applications and can provide accurate estimations of trends.The dead time is specific for each instrument and improper correction of the raw data for its effect may lead to important errors in the final products. The dead time value may change with time and, with the currently used methodology, it cannot always be determined accurately. For specific cases, such as for low ozone slant columns and high intensities of the direct solar irradiance, the error in the retrieved TOC, due to a 10 ns change in the dead time from its value in use, is found to be up to 5 %. The error in the calculation of UV irradiance can be as high as 12 % near the maximum operational limit of light intensities. While in the existing documentation it is indicated that the dead time effects are important when the error in the used value is greater than 2 ns, we found that for single-monochromator Brewers a 2 ns error in the dead time may lead to errors above the limit of 1 % in the calculation of TOC; thus the tolerance limit should be lowered. A new routine for the determination of the dead time from direct solar irradiance measurements has been created and tested and a validation of the operational algorithm has been performed. Additionally, new methods for the estimation and the validation of the dead time have been developed and are analytically described. Therefore, the present study, in addition to highlighting the importance of the dead time for the processing of Brewer data sets, also provides useful information for their quality control and re-evaluation.

A comparison of retrieved total column ozone (TCO) amounts between the Pandora #34 spectrometer system and the Dobson #061 spectrophotometer from direct-sun observations was performed on the roof of the Boulder, Colorado, NOAA building. This paper, part of an ongoing study, covers a 1-year period starting on 17 December 2013. Both the standard Dobson and Pandora TCO retrievals required a correction, TCOcorr = TCO (1 + C(T)), using a monthly varying effective ozone temperature, TE, derived from a temperature and ozone profile climatology. The correction is used to remove a seasonal difference caused by using a fixed temperature in each retrieval algorithm. The respective corrections C(TE) are CPandora = 0.00333(TE-225) and CDobson = -0.0013(TE-226.7) per degree K. After the applied corrections removed most of the seasonal retrieval dependence on ozone temperature, TCO agreement between the instruments was within 1 % for clear-sky conditions. For clear-sky observations, both co-located instruments tracked the day-to-day variation in total column ozone amounts with a correlation of r2 = 0.97 and an average offset of 1.1 ± 5.8 DU. In addition, the Pandora TCO data showed 0.3 % annual average agreement with satellite overpass data from AURA/OMI (Ozone Monitoring Instrument) and 1 % annual average offset with Suomi-NPP/OMPS (Suomi National Polar-orbiting Partnership, the nadir viewing portion of the Ozone Mapper Profiler Suite).

The collision-induced O2 complex, O2O2, is a very important trace gas for understanding remote sensing measurements of aerosols, cloud properties and atmospheric trace gases. Many ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements of the O2O2 optical depth require correction factors of 0.75 ± 0.1 to reproduce radiative transfer modeling (RTM) results for a nearly pure Rayleigh atmosphere. One of the potential causes of this discrepancy is uncertainty in laboratory-measured O2O2 absorption cross section temperature and pressure dependencies due to difficulties in replicating atmospheric conditions in the laboratory environment. This paper presents ground-based direct-sun (DS) and airborne multi-axis (AMAX) DOAS measurements of O2O2 absorption optical depths under actual atmospheric conditions in two wavelength regions (335–390 and 435–490 nm). DS irradiance measurements were made by the Washington State University research-grade Multi-Function Differential Spectroscopy Instrument instrument from 2007 to 2014 at seven sites with significant pressure (778 to 1013 hPa) and O2O2 profile-weighted temperature (247 to 275 K) differences. Aircraft MAX-DOAS measurements were conducted by the University of Colorado (CU) AMAX-DOAS instrument on 29 January 2012 over the Southern Hemispheric subtropical Pacific Ocean. Scattered solar radiance spectra were collected at altitudes between 9 and 13.2 km, with O2O2 profile-weighted temperatures of 231 to 244 K and nearly pure Rayleigh scattering conditions. Due to the well-defined DS air-mass factors during ground-based measurements and extensively characterized atmospheric conditions during the aircraft AMAX-DOAS measurements, O2O2 "pseudo" absorption cross sections, σ, are derived from the observed optical depths and estimated O2O2 column densities. Vertical O2O2 columns are calculated from the atmospheric sounding temperature, pressure and specific humidity profiles. Based on the ground-based atmospheric DS observations, there is no pressure dependence of the O2O2 σ within the measurement errors (3%). Two data sets are combined to derive the peak σ temperature dependence of the 360 and 477 nm dimer absorption bands from 231 to 275 K. DS and AMAX-derived peak σ ( O2O2) as a function of T can be described by a quadratic function at 360 nm and linear function at 477 nm with about 9% ± 2.5% per 44 K rate. Recent laboratory-measured O2O2 cross sections by Thalman and Volkamer (2013) agree with these "DOAS apparent" peak σ( O2O2) at 233, 253 and 273 K within 3%. Changes in the O2O2 spectral band shape at colder temperatures are observed for the first time in field data. Temperature effects on spectral band shapes can introduce errors in the retrieved O2O2 column abundances if a single room temperature σ( O2O2) is used in the DOAS analysis. Simultaneous fitting of σ( O2O2) at temperatures that bracket the ambient temperature range can reduce such errors. Our results show that laboratory-measured σ( O2O2) (Hermans, 2011, at 296 K and Thalman and Volkamer, 2013) are applicable for observations over a wide range of atmospheric conditions. Column densities derived using Hermans (2011) σ at 296 K require very small correction factors (0.94 ± 0.02 at 231 K and 0.99 ± 0.02 at 275 K) to reproduce theoretically calculated slant column densities for DS and AMAX-DOAS measurements. Simultaneous fitting of σ( O2O2) at 203 and 293 K further improved the results at UV and visible wavelengths for AMAX-DOAS.

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.

We assess the standard operational nitrogen dioxide (NO2) data product (OMNO2, version 2.1) retrieved from the Ozone Monitoring Instrument (OMI) onboard NASA's Aura satellite using a combination of aircraft and surface in~situ measurements as well as ground-based column measurements at several locations and a bottom-up NOx emission inventory over the continental US. Despite considerable sampling differences, NO2 vertical column densities from OMI are modestly correlated (r = 0.3–0.8) with in situ measurements of tropospheric NO2 from aircraft, ground-based observations of NO2 columns from MAX-DOAS and Pandora instruments, in situ surface NO2 measurements from photolytic converter instruments, and a bottom-up NOx emission inventory. Overall, OMI retrievals tend to be lower in urban regions and higher in remote areas, but generally agree with other measurements to within ± 20%. No consistent seasonal bias is evident. Contrasting results between different data sets reveal complexities behind NO2 validation. Since validation data sets are scarce and are limited in space and time, validation of the global product is still limited in scope by spatial and temporal coverage and retrieval conditions. Monthly mean vertical NO2 profile shapes from the Global Modeling Initiative (GMI) chemistry-transport model (CTM) used in the OMI retrievals are highly consistent with in situ aircraft measurements, but these measured profiles exhibit considerable day-to-day variation, affecting the retrieved daily NO2 columns by up to 40%. This assessment of OMI tropospheric NO2 columns, together with the comparison of OMI-retrieved and model-simulated NO2 columns, could offer diagnostic evaluation of the model.

We present intercomparison results for formaldehyde (HCHO) slant column measurements performed during the Cabauw Intercomparison campaign of Nitrogen Dioxide measuring Instruments (CINDI) that took place in Cabauw, the Netherlands, in summer 2009. During two months, nine atmospheric research groups simultaneously operated MAX-DOAS (MultiAXis Differential Optical Absorption Spectroscopy) instruments of various designs to record UV-visible spectra of scattered sunlight at different elevation angles that were analysed using common retrieval settings. The resulting HCHO data set was found to be highly consistent, the mean difference between instruments generally not exceeding 15% or 7.5 × 1015 molec cm−2, for all viewing elevation angles. Furthermore, a sensitivity analysis was performed to investigate the uncertainties in the HCHO slant column retrieval when varying key input parameters such as the molecular absorption cross sections, correction terms for the Ring effect or the width and position of the fitting interval. This study led to the identification of potentially important sources of errors associated with cross-correlation effects involving the Ring effect, O4, HCHO and BrO cross sections and the DOAS closure polynomial. As a result, a set of updated recommendations was formulated for HCHO slant column retrieval in the 336.5–359 nm wavelength range. To conclude, an error budget is proposed which distinguishes between systematic and random uncertainties. The total systematic error is estimated to be of the order of 20% and is dominated by uncertainties in absorption cross sections and related spectral cross-correlation effects. For a typical integration time of one minute, random uncertainties range between 5 and 30%, depending on the noise level of individual instruments.

From June to July 2009 more than thirty different in-situ and remote sensing instruments from all over the world participated in the Cabauw Intercomparison campaign for Nitrogen Dioxide measuring Instruments (CINDI). The campaign took place at KNMI's Cabauw Experimental Site for Atmospheric Research (CESAR) in the Netherlands. Its main objectives were to determine the accuracy of state-of-the-art ground-based measurement techniques for the detection of atmospheric nitrogen dioxide (both in-situ and remote sensing), and to investigate their usability in satellite data validation. The expected outcomes are recommendations regarding the operation and calibration of such instruments, retrieval settings, and observation strategies for the use in ground-based networks for air quality monitoring and satellite data validation. Twenty-four optical spectrometers participated in the campaign, of which twenty-one had the capability to scan different elevation angles consecutively, the so-called Multi-axis DOAS systems, thereby collecting vertical profile information, in particular for nitrogen dioxide and aerosol. Various in-situ samplers and lidar instruments simultaneously characterized the variability of atmospheric trace gases and the physical properties of aerosol particles. A large data set of continuous measurements of these atmospheric constituents has been collected under various meteorological conditions and air pollution levels. Together with the permanent measurement capability at the CESAR site characterizing the meteorological state of the atmosphere, the CINDI campaign provided a comprehensive observational data set of atmospheric constituents in a highly polluted region of the world during summertime. First detailed comparisons performed with the CINDI data show that slant column measurements of NO2, O4 and HCHO with MAX-DOAS agree within 5 to 15%, vertical profiles of NO2 derived from several independent instruments agree within 25% of one another, and MAX-DOAS aerosol optical thickness agrees within 20–30% with AERONET data. For the in-situ NO2 instrument using a molybdenum converter, a bias was found as large as 5 ppbv during day time, when compared to the other in-situ instruments using photolytic converters.

In June 2009, 22 spectrometers from 14 institutes measured tropospheric and stratospheric NO2 from the ground for more than 11 days during the Cabauw Intercomparison Campaign of Nitrogen Dioxide measuring Instruments (CINDI), at Cabauw, NL (51.97° N, 4.93° E). All visible instruments used a common wavelength range and set of cross sections for the spectral analysis. Most of the instruments were of the multi-axis design with analysis by differential spectroscopy software (MAX-DOAS), whose non-zenith slant columns were compared by examining slopes of their least-squares straight line fits to mean values of a selection of instruments, after taking 30-min averages. Zenith slant columns near twilight were compared by fits to interpolated values of a reference instrument, then normalised by the mean of the slopes of the best instruments. For visible MAX-DOAS instruments, the means of the fitted slopes for NO2 and O4 of all except one instrument were within 10% of unity at almost all non-zenith elevations, and most were within 5%. Values for UV MAX-DOAS instruments were almost as good, being 12% and 7%, respectively. For visible instruments at zenith near twilight, the means of the fitted slopes of all instruments were within 5% of unity. This level of agreement is as good as that of previous intercomparisons, despite the site not being ideal for zenith twilight measurements. It bodes well for the future of measurements of tropospheric NO2, as previous intercomparisons were only for zenith instruments focussing on stratospheric NO2, with their longer heritage.

The transmittance of cloudiness was examined for the daily totals of global erythemal effective irradiance and global total irradiance in Innsbruck (577 m a.s.l., Western Austria) for the periods 1981-88 and 1993-94. The influence of varying cloudiness on the daily totals of global erythemal effective irradiance was found to be considerably greater than the influence of varying ozone. The lowest transmittance for daily totals of global erythemal effective irradiance was 9.4 %, the median and the 25-75 percentile range at 10/10 cloudiness 41.8 % (28.9-56.7 %). Similar transmittances were obtained for the daily totals of global total irradiance (300-3000 nm) as a function of cloudiness.

No abstract available.

Accurate representation of the hourly variation of the NO2 column-to-surface relationship is needed to interpret geostationary constellation observations of tropospheric NO2 columns. Prior work has revealed inconsistency in the hourly variation in NO2 columns and surface concentrations. In this study, we use the high-performance configuration of the GEOS-Chem model (GCHP) to interpret the daytime hourly variation in NO2 total columns and surface concentrations during summer. We use summer-time Pandora sun photometers and aircraft measurements during the Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) field campaign over Maryland, Texas, and Colorado as well as 50 sites (31: contiguous USA, 10: Europe, 9: Asia) from the Pandonia Global Network (PGN). We correct the Pandora columns for 1) hourly variation in the column effective temperature driven by the fractional boundary layer contribution to the total column, and 2) change in local solar time along the line-of-sight of the Pandora instrument. The corrected Pandora observations are increased by about 5-6 × 1014 molecules cm-2 at 9 AM and 6 PM across all Pandora sites. We conduct fine resolution (~12 km) simulations over the contiguous US, Europe, and East Asia using the stretched grid capability of GCHP. We also examine the effect of planetary boundary layer height (PBLH) corrections on the total columns. We first evaluate the GCHP simulated absolute NO2 concentration with Pandora and aircraft observations. We find that fine resolution simulations at 12 km compared with moderate resolution ~55 km reduce the Normalized Bias (NB) versus Pandora total columns (19% to 10%) and versus aircraft measurements (25% to 13%) over Maryland, Texas, and Colorado. Fine resolution simulations at 12 km compared with moderate resolution at 55 km reduce the NB versus Pandora total columns over the eastern US (17% to 9%), western US (22% to 14%), Europe (24% to 15%), and Asia (29% to 21%). We next use the 12 km simulation to examine the hourly variation in the NO2 column and surface concentrations. We explain the weaker hourly variation in NO2 columns than at the surface as a function of 1) hourly variation in the column effective temperature, 2) hourly variation in the local solar time along the Pandora line-of sight and 3) the integral of weakly connected layers; with the lowest 500 m exhibiting greater NO2 concentrations in morning and evening than midday, while the residual column above 500 m dominates the total column with weaker variability. [ABSTRACT FROM AUTHOR]

Since the 1980s, the paddlewheel effect has been suggested as a mechanism to boost lithium- ion diffusion in inorganic materials via the rotation of rotor- like anion groups. However, it remains unclear whether the paddlewheel effect, defined as large- angle anion group rotations assisting Li hopping, indeed exists; furthermore, the physical mechanism by which the anion- group dynamics affect lithium- ion diffusion has not yet been established. In this work, we differentiate various types of rotational motions of anion groups and develop quaternion- based algorithms to detect, quantify, and relate them to lithium- ion motion in ab initio molecular dynamics simulations. Our analysis demonstrates that, in fact, the paddlewheel effect, where an anion group makes a large angle rotation to assist a lithium- ion hop, does not exist and thus is not responsible for the fast lithium- ion diffusion in superionic conductors, as historically claimed. Instead, we find that materials with topologically isolated anion groups can enhance lithium- ion diffusivity via a more classic nondynamic soft- cradle mechanism, where the anion groups tilt to provide optimal coordination to a lithium ion throughout the hopping process to lower the migration barrier. This anion- group disorder is static in nature, rather than dynamic and can explain most of the experimental observations. Our work substantiates the nonexistence of the long- debated paddlewheel effect and clarifies any correlation that may exist between anion- group rotations and fast ionic diffusion in inorganic materials. [ABSTRACT FROM AUTHOR]

Purpose: The aim of this pilot exploratory cohort study was to assess the value of buccal augmentation in immediate implant placement and immediate restoration of anterior teeth in maxillae with missing buccal lamellar bone with regard to esthetic parameters, as well as soft and hard tissue level changes. Materials and Methods: This study compared three groups of 10 patients each with immediate implant placement and immediate restoration in the anterior maxilla: (1) patients with partially to totally missing buccal bone with simultaneous augmentation with bovine collagen (test group augmented [TGA]); (2) patients with partially to totally missing buccal bone without augmentation (test group nonaugmented [TNA]); and (3) patients with intact buccal lamellar bone (control group [CG]). The pink esthetic score (PES) and the course of the peri-implant bone level after 1, 3, and 12 months were used as assessment criteria. Results: Af ter 12 months, the PES in the TGA was assessed as being better than it was preoperatively (mean ± SD: 8 ± 3.09 vs 9.25 ± 3.01, respectively, P = .8243), while it remained almost identical in the other two groups (TNA = 8.75 ± 2.7 vs 8.6 ± 3.3, P = .4098; CG = 10.6 ± 2.41 vs 10.6 ± 2.22, P = .7085). A significant difference among the PES values of the three groups was not observed at any point in time (preoperative: P = .118, 12 months: P = .383). In total, the TNA and CG showed an improvement in 3 out of 7 parameters of the PES after 12 months, while this was the case in 5 out of 7 parameters in the TGA. No significant difference among the three groups could be seen at any time point regarding peri-implant bone level. In the CG and TGA patients, a nonsignificant improvement in peri-implant bone level was seen after 12 months (respectively: 1.6 mm to 0.99 mm; P = .08068; 1.89 mm to 1.73 mm; P = .5866). In contrast, TNA patients showed a nonsignificant deterioration vs the postoperative situation (1.16 mm to 1.45 mm; P = .08208). Conclusion: Within the limitations of this pilot study, it can be concluded that a missing buccal lamellar bone appears to be no contraindication for immediate implant placement and immediate restoration, provided the baseline esthetic situation is accepted. As compared to the nonaugmented defect group or the group with intact lamellar bone, neither the esthetic nor the radiologic results could be improved significantly by augmentation with bovine collagen. [ABSTRACT FROM AUTHOR]

Ground-based remote sensing instruments have been widely used for atmospheric research but applications for air quality monitoring remain limited. Compared to an in situ instrument that provides air quality conditions at the ground level, most remote sensing instruments are sensitive to a broad range of altitudes, often providing only integrated column observations. These column data can be more difficult to interpret and to relate to surface values and hence to "nose-height-level" health factors. This research utilized ground-based remote sensing and in situ air quality observations in the Canadian Oil Sands Region to investigate some of their differences. Vertical column densities (VCDs) of SO2 and NO2 retrieved by Pandora spectrometers located at the Oski-Otin site at Fort McKay, (Alberta, Canada), from 2013–2019 were analyzed along with measurements of SO2 and NO2 surface concentrations and meteorological data. Aerosol optical depth (AOD) observations by CIMEL sunphotometer were compared with surface PM2.5 data. The Oski-Otin site is surrounded by several large bitumen mining operations within the Athabasca Oil Sands Region (AOSR) with significant NO2 emissions from the mining fleet. Two major bitumen upgraders that are 20 km south-east of the site have total SO2 and NO2 emissions of about 40 kt yr-1 and 20 kt yr-1 respectively. It was demonstrated that remote sensing data from Pandora and CIMEL combined with high vertical resolution wind profiles can provide information about pollution sources and plume characteristics. Elevated SO2 VCDs are clearly observed for times with south and south-eastern winds, particularly at 200–300 m altitude (above ground level). High NO2 VCD values were observed from other directions (e.g., north-west) with less prominent impacts from 200–300 m winds. In situ ground observations of SO2 and NO2 show a different sensitivity with wind profiles, indicating they are less sensitive to elevated plumes than remote sensing instruments. In addition to measured wind data and lidar observed boundary layer height (BLH), modelled wind profiles and BLH from ERA-5 have been used to further examine the correlation between column and surface observations. The results show that the ratio of measured column and surface concentration values could show positive or negative correlation with BLH, which depends on the height of emission sources (e.g., emissions from high stacks or near surface). This study explores differences between remote sensing and in situ instruments in terms of their vertical, horizontal, and temporal sampling differences. Understanding and resolving these differences are critical for future analyses linking satellite, ground-based remote sensing, and in situ observations in air quality monitoring and research. [ABSTRACT FROM AUTHOR]