Using ground-based solar and lunar infrared spectroscopy to study the diurnal trend of carbon monoxide in the Mexico City boundary layer

Carbon monoxide (CO) is an important pollutant in urban agglomerations. Quantifying the total burden of this pollutant in a megacity is challenging because not only its surface concentration but also its vertical dispersion present different behaviours and high variability. The diurnal trend of columnar CO in the boundary layer of Mexico City has been measured during various days with ground-based infrared absorption spectroscopy. Daytime CO total columns are retrieved from solar spectra and for the first time, nocturnal CO total columns using moonlight have been retrieved within a megacity. The measurements were taken at the Universidad Nacional Autónoma de México (UNAM) campus located in Mexico City (19.33° N, 99.18° W, 2260 m a.s.l.) from October 2007 until February 2008 with a Fourier-transform infrared spectrometer at 0.5 cm<sup>−1</sup> resolution. The atmospheric CO background column was measured from the high altitude site Altzomoni (19.12° N, 98.65° W, 4010 m a.s.l.) located 60 km southeast of Mexico City. The total CO column within the city presents large variations. Fresh CO emissions at the surface, the transport of cleaner or more polluted air masses within the field-of-view of the instrument and other processes contribute to this variability. The mean background value above the boundary mixing layer was found to be (8.4±0.5)×10<sup>17</sup> molecules/cm<sup>2</sup>, while inside the city, the late morning mean on weekdays and Sundays was found to be (2.73±0.41)×10<sup>18</sup> molecules/cm<sup>2</sup> and (2.04±0.57)×10<sup>18</sup> molecules/cm<sup>2</sup>, respectively. Continuous CO column retrieval during the day and night (when available), in conjunction with surface CO measurements, allow for a reconstruction of the effective mixing layer height. The limitations from this simplified approach, as well as the potential of using continuous column measurements in order to derive top-down CO emissions from a large urban area, are discussed. Also, further monitoring will provide more insight in daily and weekly emission patterns and a usable database for the quantitative validation of CO from satellite observations in a megacity

Stratospheric and tropospheric NO₂ variability on the diurnal and annual scale: a combined retrieval from ENVISAT/SCIAMACHY and solar FTIR at the Permanent Ground-Truthing Facility Zugspitze/Garmisch

International audienceColumnar NO2 retrievals from solar FTIR measurements at the Zugspitze (47.42° N, 10.98° E, 2964 m a.s.l.), Germany were investigated synergistically with columnar NO2 retrieved from SCIAMACHY data by the University of Bremen scientific algorithm UB1.5 for the time span July 2002-October 2004. A new concept to match FTIR data to the time of satellite overpass makes use of the NO2 daytime increasing rate retrieved from the FTIR data set itself [+1.02(6)E+14 cm-2/h]. This measured increasing rate shows no significant seasonal variation. SCIAMACHY data within a 200-km radius around Zugspitze were considered, and a pollution-clearing scheme was developed to select only pixels corresponding to clean background (free) tropospheric conditions, and exclude local pollution hot spots. The resulting difference between SCIAMACHY and FTIR columns (without correcting for the different sensitivities of the instruments) varies between 0.60-1.24E+15 cm-2 with an average of 0.83E+15 cm-2. A day-to-day scatter of daily means of ?7-10% could be retrieved in mutual agreement from FTIR and SCIAMACHY. Both data sets are showing sufficient precisions to make this assessment. Analysis of the averaging kernels gives proof that at high-mountain-site FTIR is a highly accurate measure for the pure stratospheric column, while SCIAMACHY shows significant tropospheric sensitivity. Based on this finding, we set up a combined a posteriori FTIR-SCIAMACHY retrieval for tropospheric NO2, based upon the averaging kernels. It yields an annual cycle of the clean background (free) tropospheric column (-2, an average of 1.09E+15 cm-2, and an intermediate phase between that of the well known boundary layer and stratospheric annual cycles. The outcome is a concept for an integrated global observing system for tropospheric NO2 that comprises DOAS nadir satellite measurements and a set of latitudinally distributed mountain-site or clean-air FTIR stations

Combined direct-sun ultraviolet and infrared spectroscopies at Popocatépetl volcano (Mexico)

Volcanic plume composition is strongly influenced by both changes in magmatic systems and plume-atmosphere interactions. Understanding the degassing mechanisms controlling the type of volcanic activity implies deciphering the contributions of magmatic gases reaching the surface and their posterior chemical transformations in contact with the atmosphere. Remote sensing techniques based on direct solar absorption spectroscopy provide valuable information about most of the emitted magmatic gases but also on gas species formed and converted within the plumes. In this study, we explore the procedures, performances and benefits of combining two direct solar absorption techniques, high resolution Fourier Transform Infrared Spectroscopy (FTIR) and Ultraviolet Differential Optical Absorption Spectroscopy (UV-DOAS), to observe the composition changes in the Popocatépetl’s plume with high temporal resolution. The SO2 vertical columns obtained from three instruments (DOAS, high resolution FTIR and Pandora) were found similar (median difference <12%) after their intercalibration. We combined them to determine with high temporal resolution the different hydrogen halide and halogen species to sulfur ratios (HF/SO$_{2}$, BrO/SO$_{2}$, HCl/SO$_{2}$, SiF$_{4}$/SO$_{2}$, detection limit of HBr/SO$_{2}$) and HCl/BrO in the Popocatépetl’s plume over a 2.5-years period (2017 to mid-2019). BrO/SO$_{2}$, BrO/HCl, and HCl/SO$_{2}$ ratios were found in the range of (0.63 ± 0.06 to 1.14 ± 0.20) × 10$^{–4}$, (2.6 ± 0.5 to 6.9 ± 2.6) × 10$^{–4}$, and 0.08 ± 0.01 to 0.21 ± 0.01 respectively, while the SiF4/SO$_{2}$ and HF/SO$_{2}$ ratios were found fairly constant at (1.56 ± 0.25) × 10$^{–3}$ and 0.049 ± 0.001. We especially focused on the full growth/destruction cycle of the most voluminous lava dome of the period that took place between February and April 2019. A decrease of the HCl/SO$_{2}$ ratio was observed with the decrease of the extrusive activity. Furthermore, the short-term variability of BrO/SO$_{2}$ is measured for the first time at Popocatépetl volcano together with HCl/SO$_{2}$, revealing different behaviors with respect to the volcanic activity. More generally, providing such temporally resolved and near-real-time time series of both primary and secondary volcanic gaseous species is critical for the management of volcanic emergencies, as well as for the understanding of the volcanic degassing processes and their impact on the atmospheric chemistry

Ground-based FTIR measurements of O3- and climate-related gases in the free troposphere and lower stratosphere

In the frame of the EC project UFTIR (Time series of Upper Free Troposphere observations from a European ground-based FTIR network), a common strategy for an optimal determination of the chemical composition in the free troposphere and lower stratosphere with ground-based Fourier-transform infrared (FTIR) spectrometers is being developed. The project focuses on 6 target species that are O3, CO, CH4, N2O, C2H6 and CHClF2 (HCFC-22). The strategy consists in selecting the most appropriate parameters to retrieve vertical concentration profiles from solar FTIR spectra. Among the important parameters are the spectral microwindows: they have been optimised to maximise the information content and to minimize the influence of poorly known spectroscopic data and interfering species