Network For The Detection Of Atmospheric Composition Change Research Articles

Evaluating modelled tropospheric columns of CH4, CO, and O3 in the Arctic using ground-based Fourier transform infrared (FTIR) measurements

Abstract. This study evaluates tropospheric columns of methane, carbon monoxide, and ozone in the Arctic simulated by 11 models. The Arctic is warming at nearly 4 times the global average rate, and with changing emissions in and near the region, it is important to understand Arctic atmospheric composition and how it is changing. Both measurements and modelling of air pollution in the Arctic are difficult, making model validation with local measurements valuable. Evaluations are performed using data from five high-latitude ground-based Fourier transform infrared (FTIR) spectrometers in the Network for the Detection of Atmospheric Composition Change (NDACC). The models were selected as part of the 2021 Arctic Monitoring and Assessment Programme (AMAP) report on short-lived climate forcers. This work augments the model–measurement comparisons presented in that report by including a new data source: column-integrated FTIR measurements, whose spatial and temporal footprint is more representative of the free troposphere than in situ and satellite measurements. Mixing ratios of trace gases are modelled at 3-hourly intervals by CESM, CMAM, DEHM, EMEP MSC-W, GEM-MACH, GEOS-Chem, MATCH, MATCH-SALSA, MRI-ESM2, UKESM1, and WRF-Chem for the years 2008, 2009, 2014, and 2015. The comparisons focus on the troposphere (0–7 km partial columns) at Eureka, Canada; Thule, Greenland; Ny Ålesund, Norway; Kiruna, Sweden; and Harestua, Norway. Overall, the models are biased low in the tropospheric column, on average by −9.7 % for CH4, −21 % for CO, and −18 % for O3. Results for CH4 are relatively consistent across the 4 years, whereas CO has a maximum negative bias in the spring and minimum in the summer and O3 has a maximum difference centered around the summer. The average differences for the models are within the FTIR uncertainties for approximately 15 % of the model–location comparisons.

Atmospheric N2O and CH4 total columns retrieved from low-resolution Fourier transform infrared (FTIR) spectra (Bruker VERTEX 70) in the mid-infrared region

Abstract. Nitrous oxide (N2O) and methane (CH4) are two important greenhouse gases in the atmosphere. In 2019, mid-infrared (MIR) solar absorption spectra were recorded by a Bruker VERTEX 70 spectrometer and a Bruker IFS 125HR spectrometer at Sodankylä, Finland, at spectral resolutions of 0.2 and 0.005 cm−1, respectively. The N2O and the CH4 retrievals from high-resolution MIR spectra have been well investigated within the Network for the Detection of Atmospheric Composition Change (NDACC) but not for MIR spectra gathered with instruments operating at low spectral resolution. In this study, N2O and CH4 retrieval strategies and retrieval uncertainties from the VERTEX 70 MIR low-resolution spectra are discussed and presented. The accuracy and precision of the VERTEX 70 N2O and CH4 retrievals are assessed by comparing them with the coincident 125HR retrievals and AirCore measurements. The relative differences between the N2O total columns retrieved from 125HR and VERTEX 70 spectra are −0.3 ± 0.7 (1σ) % with a correlation coefficient (R) of 0.93. Regarding the CH4 total column, we first used the same retrieval microwindows for 125HR and VERTEX 70 spectra, but there is an underestimation in the VERTEX 70 retrievals, especially in summer. The relative differences between the CH4 total columns retrieved from the 125HR and VERTEX 70 spectra are -1.3±1.1 (1σ) % with a R value of 0.77. To improve the VERTEX 70 CH4 retrievals, we propose alternative retrieval microwindows. The relative differences between the CH4 total columns retrieved from the 125HR and VERTEX 70 spectra in these new windows become 0.0±0.8 (1σ) %, along with an increase in the R value to 0.87. The coincident AirCore measurements confirm that the VERTEX 70 CH4 retrievals using the latter window choice are better, with relative mean differences between the VERTEX 70 CH4 retrievals and AirCore measurements of −1.9 % for the standard NDACC microwindows and of 0.13 % for the alternative microwindows. This study provides insight into the N2O and CH4 retrievals from the low-resolution (0.2 cm−1) MIR spectra observed with a VERTEX 70 spectrometer, and it demonstrates the suitability of this kind of instrument for contributing to satellite validation, model verification, and other scientific campaigns with the advantage of its transportability and lower cost compared to standard NDACC-type Fourier-transform infrared (FTIR) instruments.

A retrieval of xCO2 from ground-based mid-infrared NDACC solar absorption spectra and comparison to TCCON

Abstract. Two global networks of ground-based Fourier transform spectrometers are measuring abundances of atmospheric trace gases that absorb in the near infrared and mid-infrared: the Network for the Detection of Atmospheric Composition Change (NDACC) and the Total Carbon Column Observing Network (TCCON). The first lacks a CO2 product; therefore, this study focuses on developing an xCO2 retrieval method for NDACC from a spectral window in the 4800 cm−1 region. This retrieval will allow extending ground-based measurements back in time, which we will demonstrate with historical data available from Ny-Ålesund, Svalbard. At this site, both TCCON and NDACC measurements are routinely performed, which is an advantage for collocated comparisons. The results are compared with collocated TCCON measurements of column-averaged dry-air mole fractions of CO2 (denoted by xCO2) in Ny-Ålesund, Svalbard, and only TCCON in Burgos, Philippines. We found that it is possible to retrieve xCO2 from NDACC spectra with a precision of 0.2 %. The comparison between the new retrieval and TCCON showed that the sensitivity of the new retrieval is high in the troposphere and lower in the upper stratosphere, similar to TCCON, as seen in the averaging kernels, and that the seasonality is well captured as seen in the retrieved time series. Additionally, we have included a retrieval strategy suggestion to improve the quality of the xCO2 product.

Network for the Detection of Atmospheric Composition Change (NDACC) Fourier transform infrared (FTIR) trace gas measurements at the University of Toronto Atmospheric Observatory from 2002 to 2020

Abstract. Nineteen years of atmospheric composition measurements made at the University of Toronto Atmospheric Observatory (TAO; 43.66∘ N, 79.40∘ W; 174 m a.s.l.) are presented. These are retrieved from Fourier transform infrared (FTIR) solar absorption spectra recorded with an ABB Bomem DA8 spectrometer from May 2002 to December 2020. The retrievals have been performed for 14 species: O3, HCl, HF, HNO3, CH4, C2H6, CO, HCN, N2O, C2H2, H2CO, CH3OH, HCOOH, and NH3 using the SFIT4 algorithm. The measurements have been archived in the Network for the Detection of Atmospheric Composition Change (NDACC) data repository in Hierarchical Data Format version 4 (HDF4) files following the Generic Earth Observation Metadata Standard (GEOMS) and are also publicly available on Borealis, the Canadian Dataverse Repository (https://doi.org/10.5683/SP2/VC8JMC, Yamanouchi et al., 2022). In this paper, we describe the instrumentation, the retrieval strategy, the vertical sensitivity of the retrievals, the quality assurance process, and the error analysis of the TAO FTIR measurements and present the current version of the time series.

Validation of OMPS Suomi NPP and OMPS NOAA‐20 Formaldehyde Total Columns With NDACC FTIR Observations

AbstractWe validate formaldehyde (HCHO) vertical column densities (VCDs) from Ozone Mapping and Profiler Suite Nadir Mapper (OMPS‐NM) instruments onboard the Suomi National Polar‐orbiting Partnership (Suomi NPP) satellite for 2012–2020 and National Oceanic and Atmospheric Administration‐20 (NOAA‐20) satellite for 2018–2020, hereafter referred to as OMPS‐NPP and OMPS‐N20, with ground‐based Fourier‐Transform Infrared (FTIR) observations of the Network for the Detection of Atmospheric Composition Change (NDACC). OMPS‐NPP/N20 HCHO products reproduce seasonal variability at 24 FTIR sites. Monthly variability of OMPS‐NPP/N20 has a very good agreement with FTIR, showing correlation coefficients of 0.83 and 0.88, respectively. OMPS‐NPP (N20) biases averaged over all sites are −0.9 (4) ± 3 (6)%. However, at clean sites (with VCDs < 4.0 × 1015 molecules cm−2), positive biases of 20 (32) ± 6 (18)% occur for OMPS‐NPP (N20). At sites with HCHO VCDs > 4.0 × 1015 molecules cm−2, negative biases of −15% ± 4% appear for OMPS‐NPP, but OMPS‐N20 shows smaller bias of 0.5% ± 6% due to its smaller ground pixel footprints. Therefore, smaller satellite footprint sizes are important in distinguishing small‐scale plumes. In addition, we discuss a bias correction and provide lower limit for the monthly uncertainty of OMPS‐NPP/N20 HCHO products. The total uncertainty for OMPS‐NPP (N20) at clean sites is 0.7 (0.8) × 1015 molecules cm−2, corresponding to a relative uncertainty of 32 (30)%. In the case of HCHO VCDs > 4.0 × 1015 molecules cm−2, however, the relative uncertainty in HCHO VCDs for OMPS‐NPP (N20) decreases to 31 (18)%.

Atmospheric distribution of HCN from satellite observations and 3-D model simulations

Abstract. Hydrogen cyanide (HCN) is an important tracer of biomass burning, but there are significant uncertainties in its atmospheric budget, especially its photochemical and ocean sinks. Here we use a tracer version of the TOMCAT global 3-D chemical transport model to investigate the physical and chemical processes driving the abundance of HCN in the troposphere and stratosphere over the period 2004–2016. The modelled HCN distribution is compared with version 4.1 of the Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE-FTS) HCN satellite data, which provide profiles up to around 42 km, and with ground-based column measurements from the Network for the Detection of Atmospheric Composition Change (NDACC). The long-term ACE-FTS measurements reveal the strong enhancements in upper-tropospheric HCN due to large wildfire events in Indonesia in 2006 and 2015. Our 3-D model simulations confirm previous lower-altitude balloon comparisons that the currently recommended NASA Jet Propulsion Laboratory (JPL) reaction rate coefficient of HCN with OH greatly overestimates the HCN loss. The use of the rate coefficient proposed by Kleinböhl et al. (2006) in combination with the HCN oxidation by O(1D) gives good agreement between ACE-FTS observations and the model. Furthermore, the model photochemical loss terms show that the reduction in the HCN mixing ratio with height in the middle stratosphere is mainly driven by the O(1D) sink with only a small contribution from a reaction with OH. From comparisons of the model tracers with ground-based HCN observations we test the magnitude of the ocean sink in two different published schemes (Li et al., 2000, 2003). We find that in our 3-D model the two schemes produce HCN abundances which are very different to the NDACC observations but in different directions. A model HCN tracer using the Li et al. (2000) scheme overestimates the HCN concentration by almost a factor of 2, while a HCN tracer using the Li et al. (2003) scheme underestimates the observations by about one-third. To obtain good agreement between the model and observations, we need to scale the magnitudes of the global ocean sinks by factors of 0.25 and 2 for the schemes of Li et al. (2000) and Li et al. (2003), respectively. This work shows that the atmospheric photochemical sinks of HCN now appear well constrained but improvements are needed in parameterizing the major ocean uptake sink.

Retrieval of atmospheric CFC-11 and CFC-12 from high-resolution FTIR observations at Hefei and comparisons with other independent datasets

Abstract. Synthetic halogenated organic chlorofluorocarbons (CFCs) play an important role in stratospheric ozone depletion and contribute significantly to the greenhouse effect. In this work, the mid-infrared solar spectra measured by ground-based high-resolution Fourier transform infrared spectroscopy (FTIR) were used to retrieve atmospheric CFC-11 (CCl3F) and CFC-12 (CCl2F2) at Hefei, China. The CFC-11 columns observed from January 2017 to December 2020 and CFC-12 columns from September 2015 to December 2020 show a similar annual decreasing trend and seasonal cycle, with an annual rate of -0.47±0.06 % yr−1 and -0.68±0.03 % yr−1, respectively. So the decline rate of CFC-11 is significantly lower than that of CFC-12. CFC-11 total columns were higher in summer, and CFC-12 total columns were higher in summer and autumn. Both CFC-11 and CFC-12 total columns reached the lowest in spring. Further, FTIR data of NDACC (Network for the Detection of Atmospheric Composition Change) candidate station Hefei were compared with the ACE-FTS (Atmospheric Chemistry Experiment Fourier transform spectrometer) satellite data, WACCM (Whole Atmosphere Community Climate Model) data, and the data from other NDACC-IRWG (InfraRed Working Group) stations (St. Petersburg, Jungfraujoch, and Réunion). The mean relative difference between the vertical profiles observed by FTIR and ACE-FTS is -5.6±3.3 % and 4.8±0.9 % for CFC-11 and CFC-12 for an altitude of 5.5 to 17.5 km, respectively. The results demonstrate that our FTIR data agree relatively well with the ACE-FTS satellite data. The annual decreasing rate of CFC-11 measured from ACE-FTS and calculated by WACCM is -1.15±0.22 % yr−1 and -1.68±0.18 % yr−1, respectively. The interannual decreasing rates of atmospheric CFC-11 obtained from ACE-FTS and WACCM data are higher than that from FTIR observations. Also, the annual decreasing rate of CFC-12 from ACE-FTS and WACCM is -0.85±0.15 % yr−1 and -0.81±0.05 % yr−1, respectively, close to the corresponding values from the FTIR measurements. The total columns of CFC-11 and CFC-12 at the Hefei and St. Petersburg stations are significantly higher than those at the Jungfraujoch and Réunion (Maïdo) stations, and the two values reached the maximum in local summer or autumn and the minimum in local spring or winter at the four stations. The seasonal variability at the three stations in the Northern Hemisphere is higher than that at the station in the Southern Hemisphere.

Ozone depletion in the Arctic and Antarctic stratosphere induced by wildfire smoke

Abstract. A record-breaking stratospheric ozone loss was observed over the Arctic and Antarctica in 2020. Strong ozone depletion occurred over Antarctica in 2021 as well. The ozone holes developed in smoke-polluted air. In this article, the impact of Siberian and Australian wildfire smoke (dominated by organic aerosol) on the extraordinarily strong ozone reduction is discussed. The study is based on aerosol lidar observations in the North Pole region (October 2019–May 2020) and over Punta Arenas in southern Chile at 53.2∘ S (January 2020–November 2021) as well as on respective NDACC (Network for the Detection of Atmospheric Composition Change) ozone profile observations in the Arctic (Ny-Ålesund) and Antarctica (Neumayer and South Pole stations) in 2020 and 2021. We present a conceptual approach on how the smoke may have influenced the formation of polar stratospheric clouds (PSCs), which are of key importance in the ozone-depleting processes. The main results are as follows: (a) the direct impact of wildfire smoke below the PSC height range (at 10–12 km) on ozone reduction seems to be similar to well-known volcanic sulfate aerosol effects. At heights of 10–12 km, smoke particle surface area (SA) concentrations of 5–7 µm2 cm−3 (Antarctica, spring 2021) and 6–10 µm2 cm−3 (Arctic, spring 2020) were correlated with an ozone reduction in terms of ozone partial pressure of 0.4–1.2 mPa (about 30 % further ozone reduction over Antarctica) and of 2–3.5 mPa (Arctic, 20 %–30 % reduction with respect to the long-term springtime mean). (b) Within the PSC height range, we found indications that smoke was able to slightly increase the PSC particle number and surface area concentration. In particular, a smoke-related additional ozone loss of 1–2 mPa (10 %–20 % contribution to the total ozone loss over Antarctica) was observed in the 14–23 km PSC height range in September–October 2020 and 2021. Smoke particle number concentrations ranged from 10 to 100 cm−3 and were about a factor of 10 (in 2020) and 5 (in 2021) above the stratospheric aerosol background level. Satellite observations indicated an additional mean column ozone loss (deviation from the long-term mean) of 26–30 Dobson units (9 %–10 %, September 2020, 2021) and 52–57 Dobson units (17 %–20 %, October 2020, 2021) in the smoke-polluted latitudinal Antarctic belt from 70–80∘ S.

Impact of instrumental line shape characterization on ozone monitoring by FTIR spectrometry

Abstract. Retrieving high-precision concentrations of atmospheric trace gases from FTIR (Fourier transform infrared) spectrometry requires a precise knowledge of the instrumental performance. In this context, this paper examines the impact on the ozone (O3) retrievals of several approaches used to characterize the instrumental line shape (ILS) function of ground-based FTIR spectrometers within NDACC (Network for the Detection of Atmospheric Composition Change). The analysis has been carried out at the subtropical Izaña Observatory (IZO, Spain) by using the 20-year time series of the high-resolution FTIR solar absorption spectra acquired between 1999 and 2018. The theoretical quality assessment and the comparison to independent O3 observations available at IZO (Brewer O3 total columns and electrochemical concentration cell, ECC, sondes) reveal consistent findings. The inclusion of a simultaneous retrieval of the ILS parameters in the O3 retrieval strategy allows, on the one hand, a rough instrumental characterization to be obtained and, on the other hand, the precision of the FTIR O3 products to be slightly improved. The improvement is of special relevance above the lower stratosphere, where the cross-interference between the O3 vertical distribution and the instrumental performance is more significant. However, it has been found that the simultaneous ILS retrieval leads to a misinterpretation of the O3 variations on daily and seasonal scales. Therefore, in order to ensure the independence of the O3 retrievals and the instrumental response, the optimal approach to deal with the FTIR instrumental characterization is found to be the continuous monitoring of the ILS function by means of independent observations, such as gas cell measurements.

The impact of aerosol fluorescence on long-term water vapor monitoring by Raman lidar and evaluation of a potential correction method

Abstract. The impact of aerosol fluorescence on the measurement of water vapor by UV (355 nm emission) Raman lidar in the upper troposphere and lower stratosphere (UTLS) is investigated using the long-term records of three high-performance Raman lidars contributing to the Network for the Detection of Atmospheric Composition Change (NDACC). Comparisons with co-located radiosondes and aerosol backscatter profiles indicate that laser-induced aerosol fluorescence in smoke layers injected into the stratosphere by pyrocumulus events can introduce very large and chronic wet biases above 15 km, thus impacting on the ability of these systems to accurately estimate long-term water vapor trends in the UTLS. In order to mitigate the fluorescence contamination, a correction method based on the addition of an aerosol fluorescence channel was developed and tested on the water vapor Raman lidar TMWAL located at the JPL Table Mountain Facility in California. The results of this experiment, conducted between 27 August and 4 November 2021 and involving 22 co-located lidar and radiosonde profiles, suggest that the proposed correction method is able to effectively reduce the fluorescence-induced wet bias. After correction, the average difference between the lidar and co-located radiosonde water vapor measurements was reduced to 5 %, consistent with the difference observed during periods of negligible aerosol fluorescence interference. The present results provide confidence that after a correction is applied, long-term water vapor trends can be reasonably well estimated in the upper troposphere, but they also call for further refinements or use of alternate Raman lidar approaches (e.g., 308 nm or 532 nm emission) to confidently detect long-term trends in the lower stratosphere. These findings may have important implications for NDACC's water vapor measurement strategy in the years to come.

Ground-based validation of the MetOp-A and MetOp-B GOME-2 OClO measurements

Abstract. This paper reports on ground-based validation of the atmospheric OClO data record produced within the framework of EUMETSAT's Satellite Application Facility on Atmospheric Chemistry Monitoring (AC SAF) using the Global Ozone Monitoring Experiment (GOME)-2A and GOME-2B instrument measurements, covering the 2007–2016 and 2013–2016 periods, respectively. OClO slant column densities are compared to correlative measurements collected from nine Zenith-Scattered-Light Differential Optical Absorption Spectroscopy (ZSL-DOAS) instruments from the Network for the Detection of Atmospheric Composition Change (NDACC) distributed in both the Arctic and Antarctic. Sensitivity tests are performed on the ground-based data to estimate the impact of the different OClO DOAS analysis settings. On this basis, we infer systematic uncertainties of about 25 % (i.e., about 3.75×1013 molec. cm−2) between the different ground-based data analyses, reaching total uncertainties ranging from about 26 % to 33 % for the different stations (i.e., around 4 to 5×1013 molec. cm−2). Time series at the different sites show good agreement between satellite and ground-based data for both the inter-annual variability and the overall OClO seasonal behavior. GOME-2A results are found to be noisier than those of GOME-2B, especially after 2011, probably due to instrumental degradation effects. Daily linear regression analysis for OClO-activated periods yield correlation coefficients of 0.8 for GOME-2A and 0.87 for GOME-2B, with slopes with respect to the ground-based data ensemble of 0.64 and 0.72, respectively. Satellite minus ground-based offsets are within 8×1013 molec. cm−2, with some differences between GOME-2A and GOME-2B depending on the station. Overall, considering all the stations, a median offset of about -2.2×1013 molec. cm−2 is found for both GOME-2 instruments.

Three decades of remote sensing of NO2 vertical distribution and column content at the A. M. Obukhov Institute of Atmospheric Physics

The paper reviews the results of 30-year spectrometric measurements of vertical distribution and column content of NO2 at the Zvenigorod Scientific Station (ZSS) of the A. M. Obukhov Institute of Atmospheric Physics and presents analysis of NO2 long-term trends and interannual variations. The station is located in the western Moscow region. It is part of the Network for the Detection of Atmospheric Composition Change (NDACC). Measurements are done in the morning and evening twilight by zenith-scattered visible solar radiation. Vertical NO2 profiles are retrieved and column NO2 contents are calculated by profile integration. Long term trends and inter-annual variations of NO2 are analysed by multivariate regression method taking into account autocorrelation of data in a wide range of time scales. Seasonally dependent estimates of NO2 trends and interannual variations due to the quasi-biennial oscillation, El Nino–Southern oscillation, North Atlantic Oscillation, and the 11-year solar cycle are obtained. Most pronounced (in per cent units) trends and circulation and solar cycle effects are peculiar to the winter–spring period of the year. Mutual influence is assessed between the estimates of the trend and the solar cycle effect in stratospheric NO2.

Improved ozone monitoring by ground-based FTIR spectrometry

Abstract. Accurate observations of atmospheric ozone (O3) are essential to monitor in detail its key role in atmospheric chemistry. The present paper examines the performance of different O3 retrieval strategies from FTIR (Fourier transform infrared) spectrometry by using the 20-year time series of the high-resolution solar spectra acquired from 1999 to 2018 at the subtropical Izaña Observatory (IZO, Spain) within NDACC (Network for the Detection of Atmospheric Composition Change). In particular, the effects of two of the most influential factors have been investigated: the inclusion of a simultaneous atmospheric temperature profile fit and the spectral O3 absorption lines used for the retrievals (the broad spectral region of 1000–1005 cm−1 and single micro-windows between 991 and 1014 cm−1). Additionally, the water vapour (H2O) interference in O3 retrievals has been evaluated, with the aim of providing an improved O3 strategy that minimises its impact and, therefore, could be applied at any NDACC FTIR station under different humidity conditions. The theoretical and experimental quality assessments of the different FTIR O3 products (total column (TC) amounts and volume mixing ratio (VMR) profiles) provide consistent results. Combining a simultaneous temperature retrieval with the optimal selection of single O3 micro-windows results in superior FTIR O3 products, with a precision of better than 0.6 %–0.7 % for O3 TCs as compared to coincident NDACC Brewer observations taken as a reference. However, this improvement can only be achieved provided the FTIR spectrometer is properly characterised and stable over time. For unstable instruments, the temperature fit is found to exhibit a strong negative influence on O3 retrievals due to the increase in the cross-interference between the temperature retrieval and instrumental performance (given by the instrumental line shape function and measurement noise), which leads to a worsening of the precision of FTIR O3 TCs of up to 2 %. This cross-interference becomes especially noticeable beyond the upper troposphere/lower stratosphere, as documented theoretically as well as experimentally by comparing FTIR O3 profiles to those measured using electrochemical concentration cell (ECC) sondes within NDACC. Consequently, it should be taken into account for the reliable monitoring of the O3 vertical distribution, especially over long-term timescales.

Nitrous Oxide Profiling from Infrared Radiances (NOPIR): Algorithm Description, Application to 10 Years of IASI Observations and Quality Assessment

Nitrous oxide (N2O) is the third most abundant anthropogenous greenhouse gas (after carbon dioxide and methane), with a long atmospheric lifetime and a continuously increasing concentration due to human activities, making it an important gas to monitor. In this work, we present a new method to retrieve N2O concentration profiles (with up to two degrees of freedom) from each cloud-free satellite observation by the Infrared Atmospheric Sounding Interferometer (IASI), using spectral micro-windows in the N2O ν3 band, the Radiative Transfer for TOVS (RTTOV) tools and the Tikhonov regularization scheme. A time series of ten years (2011–2020) of IASI N2O profiles and integrated partial columns has been produced and validated with collocated ground-based Network for the Detection of Atmospheric Composition Change (NDACC) and Total Carbon Column Observing Network (TCCON) data. The importance of consistency in the ancillary data used for the retrieval for generating consistent time series has been demonstrated. The Nitrous Oxide Profiling from Infrared Radiances (NOPIR) N2O partial columns are of very good quality, with a positive bias of 1.8 to 4% with respect to the ground-based data, which is less than the sum of uncertainties of the compared values. At high latitudes, the comparisons are a bit worse, due to either a known bias in the ground-based data, or to a higher uncertainty in both ground-based and satellite retrievals.

Evaluation and Global-Scale Observation of Nitrous Oxide from IASI on Metop-A

Nitrous oxide (N2O) is a greenhouse gas difficult to estimate by satellite because of its weak spectral signature in the infra-red band and its low variability in the troposphere. Nevertheless, this study presents the evaluation of new tropospheric N2O observations from the Infrared Atmospheric Sounder Interferometer (IASI) on Metop-A using the Toulouse N2O Retrieval Version 2.0 tool. This tool is based on the Radiative Transfer for Tiros Operational Vertical sounder (RTTOV) model version 12.3 coupled to the Levenberg-Marquardt optimal estimation method enabling the simultaneous retrieval of methane, water vapour, temperature profiles together with surface temperature and emissivity within the 1240–1350 cm−1 window. In this study, we focused on the upper troposphere (300 hPa) where the sensitivity of IASI is significant. The IASI N2O data has been evaluated using aircraft N2O observations from the High-performance Instrumented Airborne Platform for Environmental Research Pole-to-Pole Observations (HIPPO) campaigns in 2009, 2010, and 2011 and from the National Oceanic and Atmospheric Administration’s (NOAA) Global Greenhouse Gas Reference Network (GGGRN) in 2011. In addition, we evaluated the IASI N2O using ground-based N2O measurements from 9 stations belonging to the Network for the Detection of Atmospheric Composition Change (NDACC). We found a total random error of ∼2 ppbv (0.6%) for one single retrieval at 300 hPa. Under favorable conditions, this error is also found in the vertical level pressure range 300–500 hPa. It decreases rapidly to ∼0.4 ppbv (0.1%) when we average on a 1° × 1° box. In addition, independent observations allows the estimation of bias with the IASI TN2OR v2.0 N2O. The bias between IASI and aircraft N2O data at 300 hPa is ∼1.0 ppbv (∼0.3%). We found an estimated random error of ∼2.3 ppbv (∼0.75%). This study also shows relatively high correlations between IASI data and aircraft in situ profiles but more varying correlations over the year 2011 depending on the location between IASI and NDACC remote sensing data. Finally, we present daily, monthly, and seasonal IASI N2O horizontal distributions in the upper troposphere as well as cross sections for different seasons that exhibit maxima in the Tropical band especially over Africa and South America.

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).

Twenty years of ground-based NDACC FTIR spectrometry at Izaña Observatory – overview and long-term comparison to other techniques

Abstract. High-resolution Fourier transform infrared (FTIR) solar observations are particularly relevant for climate studies, as they allow atmospheric gaseous composition and multiple climate processes to be monitored in detail. In this context, the present paper provides an overview of 20 years of FTIR measurements taken in the framework of the NDACC (Network for the Detection of Atmospheric Composition Change) from 1999 to 2018 at the subtropical Izaña Observatory (IZO, Spain). Firstly, long-term instrumental performance is comprehensively assessed, corroborating the temporal stability and reliable instrumental characterization of the two FTIR spectrometers installed at IZO since 1999. Then, the time series of all trace gases contributing to NDACC at IZO are presented (i.e. C2H6, CH4, ClONO2, CO, HCl, HCN, H2CO, HF, HNO3, N2O, NO2, NO, O3, carbonyl sulfide (OCS), and water vapour isotopologues H216O, H218O, and HD16O), reviewing the major accomplishments drawn from these observations. In order to examine the quality and long-term consistency of the IZO FTIR observations, a comparison of those NDACC products for which other high-quality measurement techniques are available at IZO has been performed (i.e. CH4, CO, H2O, NO2, N2O, and O3). This quality assessment was carried out on different timescales to examine what temporal signals are captured by the FTIR records, and to what extent. After 20 years of operation, the IZO NDACC FTIR observations have been found to be very consistent and reliable over time, demonstrating great potential for climate research. Long-term NDACC FTIR data sets, such as IZO, are indispensable tools for the investigation of atmospheric composition trends, multi-year phenomena, and complex climate feedback processes, as well as for the validation of past and present space-based missions and chemistry climate models.

First retrievals of peroxyacetyl nitrate (PAN) from ground-based FTIR solar spectra recorded at remote sites, comparison with model and satellite data

Peroxyacetyl nitrate (PAN) is the main tropospheric reservoir of NOx (NO + NO2). Its lifetime can reach several months in the upper cold troposphere. This enables the long-range transport of NOx radicals, under the form of PAN, far from the regions of emission. The subsequent release of NOx through the PAN thermal decomposition leads to the efficient formation of tropospheric ozone (O3), with important consequences for tropospheric oxidative capacity and air quality. The chemical properties of PAN have stimulated the progressive development of remote-sensing products by the satellite community, and recent additions open the prospect for the production of decadal and near-global time series. These products will provide new constraints on the distribution and evolution of this key trace gas in the Earth’s atmosphere, but they will also require reliable measurements for validation and characterization of performance. We present an approach that has been developed to retrieve PAN total columns from ground-based high-resolution solar absorption Fourier transform infrared (FTIR) spectra. This strategy is applied to observations recorded at remote FTIR stations of the Network for the Detection of Atmospheric Composition Change (NDACC). The resulting data sets are compared with total column time series derived from IASI (Infrared Atmospheric Sounding Interferometer) satellite observations and to a global chemical transport model. The results are discussed in terms of their overall consistency, mutual agreement, and seasonal cycles. Noticeable is the fact that the FTIR data point to substantial deficiencies in the global model simulation over high latitudes, a poorly sampled region, with an underestimation of the PAN columns during spring, at the peak of the seasonal cycle. Finally, we suggest avenues for development that should make it possible to limit intra- or intersite biases and extend the retrieval of PAN to other NDACC stations that are more affected by water vapor interferences.

First ground-based Fourier transform infrared (FTIR) spectrometer observations of HFC-23 at Rikubetsu, Japan, and Syowa Station, Antarctica

Abstract. We have developed a procedure for retrieving atmospheric abundances of HFC-23 (CHF3) with a ground-based Fourier transform infrared (FTIR) spectrometer and analyzed the spectra observed at Rikubetsu, Japan (43.5∘ N, 143.8∘ E), and at Syowa Station, Antarctica (69.0∘ S, 39.6∘ E). The FTIR retrievals were carried out with the SFIT4 retrieval program, and the two spectral windows of 1138.5–1148.0 cm−1 and 1154.0–1160.0 cm−1 in the overlapping ν2 and ν5 vibrational–rotational transition bands of HFC-23 were used to avoid strong H2O absorption features. We considered O3, N2O, CH4, H2O, HDO, CFC-12 (CCl2F2), HCFC-22 (CHClF2), peroxyacetyl nitrate (PAN) (CH3C(O)OONO2), HCFC-141b (CH3CCl2F), and HCFC-142b (CH3CClF2) to be interfering species. Vertical profiles of H2O, HDO, and CH4 are preliminarily retrieved with other independent spectral windows because these profiles may induce large uncertainties in the HFC-23 retrieval. Each HFC-23 retrieval has only one piece of vertical information with sensitivity to HFC-23 in the troposphere and the lower stratosphere. Retrieval errors mainly arise from the systematic uncertainties of the spectroscopic parameters used to obtain HFC-23, H2O, HDO, and CH4 abundances. For comparison between FTIR-retrieved HFC-23 total columns and surface dry-air mole fractions provided by AGAGE (Advanced Global Atmospheric Gases Experiment), FTIR-retrieved HFC-23 dry-air column-averaged mole fractions (XHFC-23) were calculated. The FTIR-retrieved XHFC-23 values at Rikubetsu and Syowa Station have negative biases of −15 % to −20 % and −25 % compared to the AGAGE datasets, respectively. These negative biases might mainly come from systematic uncertainties of HFC-23 spectroscopic parameters. The trend of the FTIR-retrieved XHFC-23 data at Rikubetsu was derived for December to February (DJF) observations, which are considered to represent the background values when an air mass reaching Rikubetsu has the least influence by transport of HFC-23 emissions from nearby countries. The DJF trend of Rikubetsu over the 1997–2009 period is 0.810 ± 0.093 ppt yr−1 (ppt: parts per trillion), which is in good agreement with the trend derived from the annual global mean datasets of the AGAGE 12-box model for the same period (0.820 ± 0.013 ppt yr−1). The DJF trend of Rikubetsu over the 2008–2019 period is 0.928 ± 0.108 ppt yr−1, which is consistent with the trend in the AGAGE in situ measurements at Trinidad Head (41.1∘ N, 124.2∘ W) for the same period (0.994 ± 0.001 ppt yr−1). The trend of the FTIR-retrieved XHFC-23 data at Syowa Station over the 2007–2016 period is 0.819 ± 0.071 ppt yr−1, which is consistent with that derived from the AGAGE in situ measurements at Cape Grim (40.7∘ S, 144.7∘ E) for the same period (0.874 ± 0.002 ppt yr−1). Although there are systematic biases in the FTIR-retrieved XHFC-23 at both sites, these results indicate that ground-based FTIR observations have the capability to monitor the long-term trend of atmospheric HFC-23. If this FTIR measurement technique were extended to other Network for the Detection of Atmospheric Composition Change (NDACC) ground-based FTIR sites around world, the measurements reported from these sites would complement the global AGAGE observations by filling spatial and temporal gaps and may lead to improved insights about changes in regional and global emissions of HFC-23 and its role in global warming.

Measurements of CFC-11, CFC-12, and HCFC-22 total columns in the atmosphere at the St. Petersburg site in 2009–2019

Abstract. Monitoring atmospheric anthropogenic halocarbons plays an important role in tracking their atmospheric concentrations in accordance with international agreements on emissions of ozone-depleting substances and, thus, in estimating the ozone layer recovery. Within the Network for the Detection of Atmospheric Composition Change (NDACC), regular Fourier transform infrared (FTIR) measurements can provide information on the abundancies of halocarbons on a global scale. We improved retrieval strategies for deriving the CFC-11 (CCl3F), CFC-12 (CCl2F2), and HCFC-22 (CHClF2) atmospheric columns from IR solar radiation spectra measured by the Bruker IFS125HR spectrometer at the St. Petersburg site (Russia). We used the Tikhonov–Phillips regularization approach for solving the inverse problem with optimized values of regularization parameters. We tested the strategies developed by comparison of the FTIR measurements with independent data. The analysis of the time series of column-averaged dry air mole fractions (Xgas) measured in 2009–2019 gives mean values of 225 pptv (parts per trillion by volume; CFC-11), 493 pptv (CFC-12), and 238 pptv (HCFC-22). Trend values total −0.40 % yr−1 (CFC-11), −0.49 % yr−1 (CFC-12), and 2.12 % yr−1 (HCFC-22). We compared the means, trends, and seasonal variability in XCFC-11, XCFC-12, and XHCFC-22 to that of (1) near-ground volume mixing ratios (VMRs), measured at the observational site Mace Head, Ireland (GVMR), (2) the mean in the 8–12 km layer VMRs, measured by ACE-FTS and averaged over 55–65∘ N latitudes (SVMR), and (3) Xgas values of the Whole Atmosphere Community Climate Model (WACCM) for the St. Petersburg site (WXgas). In general, the comparison of Xgas with the independent data showed a good agreement of their means within the systematic errors of the measurements considered. The trends observed over the St. Petersburg site demonstrate the smaller decrease rates for XCFC-11 and XCFC-12 than that of the independent data and the same increase rate for XHCFC-22. As a whole, Xgas, SVMR, and WXgas showed qualitatively similar seasonal variations, while the GVMR variability is significantly less, and only the WXHCFC-22 variations are essentially smaller than that of XHCFC-22 and SVMRHCFC-22.