Gas phase dicyanoacetylene (C4N2) on Titan: New experimental and theoretical spectroscopy results applied to Cassini CIRS data

International audienceDicyanoacetylene has not been observed so far in the gas phase in Titan’s atmosphere but this molecule is still on the list of the detected species, on the basis of the correspondence between a solid phase feature measured at 478 cm−1 in the laboratory and a spectral feature observed by Voyager. In this work, the infrared spectrum of gaseous C4N2 has been investigated to improve our knowledge of the band intensities and the line parameters for this molecule. Results of previously investigated bands have been revised and the intensity of the ν9 band at 107 cm−1, measured for the first time, was found to be the strongest absorption in the whole infrared domain. We have also improved the analysis of the complex rotational and hot band structure of C4N2 in order to obtain the first line lists for both bending modes ν8 and ν9. Using our radiative transfer code including the new line list of the strong ν9 band, we have searched for the signature of C4N2 at 107 cm−1 in the atmosphere of Titan utilizing Titan CIRS far infrared spectra. Despite averaging a large number of CIRS spectra at northern latitudes during the very favorable Titan winter, no gaseous C4N2 could be detected. At the 1-σ level we obtain an abundance upper limit of 5.3 × 10−10 for the limb average which is lower than or comparable to previously inferred values. As a consequence, the absence or very low amount of gaseous C4N2 makes quite puzzling its presence in the solid phase with an abundance compatible with the observed spectral feature at 478 cm−

Retrieval of stratospheric and tropospheric BrO profiles and columns using ground-based zenith-sky DOAS observations at Harestua, 60° N

A profiling algorithm based on the optimal estimation method is applied to ground-based zenith-sky UV-visible measurements from Harestua, Southern Norway (60&deg; N, 11&deg; E) in order to retrieve BrO vertical profiles. The sensitivity of the zenith-sky observations to the tropospheric BrO detection is increased by using for the spectral analysis a fixed reference spectrum corresponding to clear-sky noon summer conditions. The information content and retrieval errors are characterized and it is shown that the retrieved stratospheric profiles and total columns are consistent with correlative balloon and satellite observations, respectively. Tropospheric BrO columns are derived from profiles retrieved at 80&deg; solar zenith angle during sunrise and sunset for the 2000&ndash;2006 period. They show a marked seasonality with mean column value ranging from 1.52&plusmn;0.62&times;10¹³ molec/cm² in late winter/early spring to 0.92&plusmn;0.38&times;10¹³ molec/cm² in summer, which corresponds to 1.0&plusmn;0.4 and 0.6&plusmn;0.2 pptv, respectively, if we assume that BrO is uniformly mixed in the troposphere. These column values are also consistent with previous estimates made from balloon, satellite, and other ground-based observations. Daytime (10:30 LT) tropospheric BrO columns are compared to the <i>p</i>-TOMCAT 3-D tropospheric chemical transport model (CTM) for the 2002&ndash;2003 period. <i>p</i>-TOMCAT shows a good agreement with the retrieved columns except in late winter/early spring where an underestimation by the model is obtained. This finding could be explained by the non-inclusion of sea-ice bromine sources in the current version of <i>p</i>-TOMCAT. Therefore the model cannot reproduce the possible transport of air-masses with enhanced BrO concentration due to bromine explosion events from the polar region to Harestua. The daytime stratospheric BrO columns are compared to the SLIMCAT stratospheric 3-D-CTM. The model run used in this study, which assumes 21.2 pptv for the Br_y loading (15 pptv for long-lived bromine species and additional 6 pptv for very short-lived species (VSLS) added by a scaling of CH₃Br), significantly underestimates the retrieved BrO columns. A sensitivity study shows that a good agreement can only be obtained if 6 to 8 pptv accounting for VSLS are added directly (and not by a scaling of CH₃Br) to the SLIMCAT long-lived bromine species profile. This contribution of the VSLS to the total bromine loading is also consistent with recently published studies

The Cabauw Intercomparison Campaign for Nitrogen Dioxide Measuring Instruments (CINDI): Design, Execution, and Early Results

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-ofthe- 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

Validation of ACE and OSIRIS ozone and NO2 measurements using ground-based instruments at 80 degrees N

The Optical Spectrograph and Infra-Red Imager System (OSIRIS) and the Atmospheric Chemistry Experiment (ACE) have been taking measurements from space since 2001 and 2003, respectively. This paper presents intercomparisons between ozone and NO2 measured by the ACE and OSIRIS satellite instruments and by ground-based instruments at the Polar Environment Atmospheric Research Laboratory (PEARL), which is located at Eureka, Canada (80A degrees N, 86A degrees W) and is operated by the Canadian Network for the Detection of Atmospheric Change (CANDAC). The ground-based instruments included in this study are four zenith-sky differential optical absorption spectroscopy (DOAS) instruments, one Bruker Fourier transform infrared spectrometer (FTIR) and four Brewer spectrophotometers. Ozone total columns measured by the DOAS instruments were retrieved using new Network for the Detection of Atmospheric Composition Change (NDACC) guidelines and agree to within 3.2%. The DOAS ozone columns agree with the Brewer spectrophotometers with mean relative differences that are smaller than 1.5%. This suggests that for these instruments the new NDACC data guidelines were successful in producing a homogenous and accurate ozone dataset at 80A degrees N. Satellite 14-52 km ozone and 17-40 km NO2 partial columns within 500 km of PEARL were calculated for ACE-FTS Version 2.2 (v2.2) plus updates, ACE-FTS v3.0, ACE-MAESTRO (Measurements of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation) v1.2 and OSIRIS SaskMART v5.0x ozone and Optimal Estimation v3.0 NO2 data products. The new ACE-FTS v3.0 and the validated ACE-FTS v2.2 partial columns are nearly identical, with mean relative differences of 0.0 +/- 0.2% and -0.2 +/- 0.1% for v2.2 minus v3.0 ozone and NO2, respectively. Ozone columns were constructed from 14-52 km satellite and 0-14 km ozonesonde partial columns and compared with the ground-based total column measurements. The satellite-plus-sonde measurements agree with the ground-based ozone total columns with mean relative differences of 0.1-7.3%. For NO2, partial columns from 17 km upward were scaled to noon using a photochemical model. Mean relative differences between OSIRIS, ACE-FTS and ground-based NO2 measurements do not exceed 20%. ACE-MAESTRO measures more NO2 than the other instruments, with mean relative differences of 25-52%. Seasonal variation in the differences between NO2 partial columns is observed, suggesting that there are systematic errors in the measurements and/or the photochemical model corrections. For ozone spring-time measurements, additional coincidence criteria based on stratospheric temperature and the location of the polar vortex were found to improve agreement between some of the instruments. For ACE-FTS v2.2 minus Bruker FTIR, the 2007-2009 spring-time mean relative difference improved from -5.0 +/- 0.4% to -3.1 +/- 0.8% with the dynamical selection criteria. This was the largest improvement, likely because both instruments measure direct sunlight and therefore have well-characterized lines-of-sight compared with scattered sunlight measurements. For NO2, the addition of a +/- 1A degrees latitude coincidence criterion improved spring-time intercomparison results, likely due to the sharp latitudinal gradient of NO2 during polar sunrise. The differences between satellite and ground-based measurements do not show any obvious trends over the missions, indicating that both the ACE and OSIRIS instruments continue to perform well

Can forest management based on natural disturbances maintain ecological resilience?

Given the increasingly global stresses on forests, many ecologists argue that managers must maintain ecological resilience: the capacity of ecosystems to absorb disturbances without undergoing fundamental change. In this review we ask: Can the emerging paradigm of natural-disturbance-based management (NDBM) maintain ecological resilience in managed forests? Applying resilience theory requires careful articulation of the ecosystem state under consideration, the disturbances and stresses that affect the persistence of possible alternative states, and the spatial and temporal scales of management relevance. Implementing NDBM while maintaining resilience means recognizing that (i) biodiversity is important for long-term ecosystem persistence, (ii) natural disturbances play a critical role as a generator of structural and compositional heterogeneity at multiple scales, and (iii) traditional management tends to produce forests more homogeneous than those disturbed naturally and increases the likelihood of unexpected catastrophic change by constraining variation of key environmental processes. NDBM may maintain resilience if silvicultural strategies retain the structures and processes that perpetuate desired states while reducing those that enhance resilience of undesirable states. Such strategies require an understanding of harvesting impacts on slow ecosystem processes, such as seed-bank or nutrient dynamics, which in the long term can lead to ecological surprises by altering the forest's capacity to reorganize after disturbance

Validation of Sentinel-5P TROPOMI tropospheric NO2 products by comparison with NO2 measurements from airborne imaging, ground-based stationary, and mobile car DOAS measurements during the S5P-VAL-DE-Ruhr campaign

Airborne imaging differential optical absorption spectroscopy (DOAS), ground-based stationary and car DOAS measurements were conducted during the S5P-VAL-DE-Ruhr campaign in September 2020. The campaign area is located in the Rhine-Ruhr region of North Rhine-Westphalia, Western Germany, which is a pollution hotspot in Europe comprising urban and large industrial emitters. The measurements are used to validate space-borne NO2 tropospheric vertical column density data products from the Sentinel-5 Precursor (S5P) TROPOspheric Monitoring Instrument (TROPOMI). Seven flights were performed with the airborne imaging DOAS instrument for measurements of atmospheric pollution (AirMAP), providing measurements which were used to create continuous maps of NO2 in the layer below the aircraft. These flights cover many S5P ground pixels within an area of 30 km x 35 km and were accompanied by ground-based stationary measurements and three mobile car DOAS instruments. Stationary measurements were conducted by two Pandora, two zenith-sky and two MAX-DOAS instruments distributed over three target areas. Ground-based stationary and car DOAS measurements are used to evaluate the AirMAP tropospheric NO2 vertical column densities and show high Pearson correlation coefficients of 0.87 and 0.89 and slopes of 0.93 &plusmn; 0.09 and 0.98 &plusmn; 0.02 for the stationary and car DOAS, respectively. Having a spatial resolution of about 100 m x 30 m, the AirMAP tropospheric NO2 vertical column density (VCD) data creates a link between the ground-based and the TROPOMI measurements with a resolution of 3.5 km x 5.5 km and is therefore well suited to validate the TROPOMI tropospheric NO2 VCD. The measurements on the seven flight days show strong NO2 variability, which is dependent on the different target areas, the weekday, and the meteorological conditions. The AirMAP campaign dataset is compared to the TROPOMI NO2 operational off-line (OFFL) V01.03.02 data product, the reprocessed NO2 data, using the V02.03.01 of the official L2 processor, provided by the Product Algorithm Laboratory (PAL), and several scientific TROPOMI NO2 data products. The TROPOMI data products and the AirMAP data are highly correlated with correlation coefficients between 0.72 and 0.87, and slopes of 0.38 &plusmn; 0.02 to 1.02 &plusmn; 0.07. On average, TROPOMI tropospheric NO2 VCDs are lower than the AirMAP NO2 results. The slope increased from 0.38 &plusmn; 0.02 for the operational OFFL V01.03.02 product to 0.83 &plusmn; 0.06 after the improvements in the retrieval of the PAL V02.03.01 product were implemented. Different auxiliary data, such as spatially higher resolved a priori NO2 vertical profiles, surface reflectivity and the cloud treatment, are investigated using scientific TROPOMI tropospheric NO2 VCD data products to evaluate their impact on the operational TROPOMI NO2 VCD data product. The comparison of the AirMAP campaign dataset to the scientific data products shows that the choice of surface reflectivity data base has a minor impact on the tropospheric NO2 VCD retrieval in the campaign region and season. In comparison, the replacement of the a priori NO2 profile in combination with the improvements in the retrieval of the PAL V02.03.01 product regarding cloud heights has a major impact on the tropospheric NO2 VCD retrieval and increases the slope from 0.88 &plusmn; 0.06 to 1.00 &plusmn; 0.07. This study demonstrates that the underestimation of the TROPOMI tropospheric NO2 VCD product with respect to the validation dataset has been and can be further significantly improved.</p

The 2015 edition of the GEISA spectroscopic database

The GEISA database (Gestion et Etude des Informations Spectroscopiques Atmosphériques: Management and Study of Atmospheric Spectroscopic Information) has been developed and maintained by the ARA/ABC(t) group at LMD since 1974. GEISA is constantly evolving, taking into account the best available spectroscopic data. This paper presents the 2015 release of GEISA (GEISA-2015), which updates the last edition of 2011 and celebrates the 40th anniversary of the database. Significant updates and additions have been implemented in the three following independent databases of GEISA. The “line parameters database” contains 52 molecular species (118 isotopologues) and transitions in the spectral range from 10−6 to 35,877.031 cm−1, representing 5,067,351 entries, against 3,794,297 in GEISA-2011. Among the previously existing molecules, 20 molecular species have been updated. A new molecule (SO3) has been added. HDO, isotopologue of H2O, is now identified as an independent molecular species. Seven new isotopologues have been added to the GEISA-2015 database. The “cross section sub-database” has been enriched by the addition of 43 new molecular species in its infrared part, 4 molecules (ethane, propane, acetone, acetonitrile) are also updated; they represent 3% of the update. A new section is added, in the near-infrared spectral region, involving 7 molecular species: CH3CN, CH3I, CH3O2, H2CO, HO2, HONO, NH3. The “microphysical and optical properties of atmospheric aerosols sub-database” has been updated for the first time since 2003. It contains more than 40 species originating from NCAR and 20 from the ARIA archive of Oxford University. As for the previous versions, this new release of GEISA and associated management software facilities are implemented and freely accessible on the AERIS/ESPRI atmospheric chemistry data center website

The 2009 edition of the GEISA spectroscopic database

The updated 2009 edition of the spectroscopic database GEISA (Gestionet Etudedes Informations Spectroscopiques Atmospheriques ; Management and Study of Atmospheric Spectroscopic Information) is described in this paper. GEISA is a computer-accessible system comprising three independent sub-databases devoted, respectively, to: line parameters, infrared and ultraviolet/visible absorption cross-sections, microphysical and optical properties of atmospheric aerosols. In this edition, 50 molecules are involved in the line parameters sub-database, including 111 isotopologues, for a total of 3,807,997 entries, in the spectral range from 10-6 to 35,877.031cm-1. GEISA, continuously developed and maintained at LMD (Laboratoirede Meteorologie Dynamique, France) since 1976, is implemented on the IPSL/CNRS(France) ‘‘Ether’’ Products and Services Centre WEB site (http://ether.ipsl.jussieu.fr), where all archived spectroscopic data can be handled through general and user friendly associated managements of software facilities. More than 350 researchers are registered for online use of GEISA