Abstract. Among the more than 20 ground-based FTIR (Fourier transform infrared) stations currently operating around the globe, only a few have provided formaldehyde (HCHO) total column time series until now. Although several independent studies have shown that the FTIR measurements can provide formaldehyde total columns with good precision, the spatial coverage has not been optimal for providing good diagnostics for satellite or model validation. Furthermore, these past studies used different retrieval settings, and biases as large as 50 % can be observed in the HCHO total columns depending on these retrieval choices, which is also a weakness for validation studies combining data from different ground-based stations.For the present work, the HCHO retrieval settings have been optimized based on experience gained from past studies and have been applied consistently at the 21 participating stations. Most of them are either part of the Network for the Detection of Atmospheric Composition Change (NDACC) or under consideration for membership. We provide the harmonized settings and a characterization of the HCHO FTIR products. Depending on the station, the total systematic and random uncertainties of an individual HCHO total column measurement lie between 12 % and 27 % and between 1 and 11×1014 molec cm−2, respectively. The median values among all stations are 13 % and 2.9×1014 molec cm−2 for the total systematic and random uncertainties.This unprecedented harmonized formaldehyde data set from 21 ground-based FTIR stations is presented and its comparison with a global chemistry transport model shows consistency in absolute values as well as in seasonal cycles. The network covers very different concentration levels of formaldehyde, from very clean levels at the limit of detection (few 1013 molec cm−2) to highly polluted levels (7×1016 molec cm−2). Because the measurements can be made at any time during daylight, the diurnal cycle can be observed and is found to be significant at many stations. These HCHO time series, some of them starting in the 1990s, are crucial for past and present satellite validation and will be extended in the coming years for the next generation of satellite missions.

Abstract. Global climate change is one of the most important scientific, societal and economic contemporary challenges. Fundamental understanding of the major processes driving climate change is the key problem which is to be solved not only on a global but also on a regional scale. The accuracy of regional climate modelling depends on a number of factors. One of these factors is the adequate and comprehensive information on the anthropogenic impact which is highest in industrial regions and areas with dense population – modern megacities. Megacities are not only “heat islands”, but also significant sources of emissions of various substances into the atmosphere, including greenhouse and reactive gases. In 2019, the mobile experiment EMME (Emission Monitoring Mobile Experiment) was conducted within the St. Petersburg agglomeration (Russia) aiming to estimate the emission intensity of greenhouse (CO2, CH4) and reactive (CO, NOx) gases for St. Petersburg, which is the largest northern megacity. St. Petersburg State University (Russia), Karlsruhe Institute of Technology (Germany) and the University of Bremen (Germany) jointly ran this experiment. The core instruments of the campaign were two portable Bruker EM27/SUN Fourier transform infrared (FTIR) spectrometers which were used for ground-based remote sensing measurements of the total column amount of CO2, CH4 and CO at upwind and downwind locations on opposite sides of the city. The NO2 tropospheric column amount was observed along a circular highway around the city by continuous mobile measurements of scattered solar visible radiation with an OceanOptics HR4000 spectrometer using the differential optical absorption spectroscopy (DOAS) technique. Simultaneously, air samples were collected in air bags for subsequent laboratory analysis. The air samples were taken at the locations of FTIR observations at the ground level and also at altitudes of about 100 m when air bags were lifted by a kite (in case of suitable landscape and favourable wind conditions). The entire campaign consisted of 11 mostly cloudless days of measurements in March–April 2019. Planning of measurements for each day included the determination of optimal location for FTIR spectrometers based on weather forecasts, combined with the numerical modelling of the pollution transport in the megacity area. The real-time corrections of the FTIR operation sites were performed depending on the actual evolution of the megacity NOx plume as detected by the mobile DOAS observations. The estimates of the St. Petersburg emission intensities for the considered greenhouse and reactive gases were obtained by coupling a box model and the results of the EMME observational campaign using the mass balance approach. The CO2 emission flux for St. Petersburg as an area source was estimated to be 89 ± 28 ktkm-2yr-1, which is 2 times higher than the corresponding value in the EDGAR database. The experiment revealed the CH4 emission flux of 135 ± 68 tkm-2yr-1, which is about 1 order of magnitude greater than the value reported by the official inventories of St. Petersburg emissions (∼ 25 tkm-2yr-1 for 2017). At the same time, for the urban territory of St. Petersburg, both the EMME experiment and the official inventories for 2017 give similar results for the CO anthropogenic flux (251 ± 104 tkm-2yr-1 vs. 410 tkm-2yr-1) and for the NOx anthropogenic flux (66 ± 28 tkm-2yr-1 vs. 69 tkm-2yr-1).

Carbonyl sulfide (OCS) is a non-hygroscopic trace species in the free troposphere and a large sulfur reservoir maintained by both direct oceanic, geologic, biogenic, and anthropogenic emissions and the oxidation of other sulfur-containing source species. It is the largest source of sulfur transported to the stratosphere during volcanically quiescent periods. Data from 22 ground-based globally dispersed stations are used to derive trends in total and partial column OCS. Middle infrared spectral data are recorded by solar-viewing Fourier transform interferometers that are operated as part of the Network for the Detection of Atmospheric Composition Change between 1986 and 2020. Vertical information in the retrieved profiles provides analysis of discreet altitudinal regions. Trends are found to have well-defined inflection points. In two linear trend time periods ∼2002 to 2008 and ∼2008 to 2016 tropospheric trends range from ∼0.0 to (1.55 ± 0.30%/yr) in contrast to the prior period where all tropospheric trends are negative. Regression analyses show strongest correlation in the free troposphere with anthropogenic emissions. Stratospheric trends in the period ∼2008 to 2016 are positive up to (1.93 ± 0.26%/yr) except notably low latitude stations that have negative stratospheric trends. Since ∼2016, all stations show a free tropospheric decrease to 2020. Stratospheric OCS is regressed with simultaneously measured N 2 O to derive a trend accounting for dynamical variability. Stratospheric lifetimes are derived and range from (54.1 ± 9.7)yr in the sub-tropics to (103.4 ± 18.3)yr in Antarctica. These unique long-term measurements provide new and critical constraints on the global OCS budget.Plain Language Summary Carbonyl sulfide (OCS) is the most abundant sulfur containing gas in the atmosphere. There are many sources and sinks of OCS and other sulfur species in the atmosphere but most other short lived sulfur species eventually are converted to OCS. It is important to quantify and understand OCS as it can be used to understand CO 2 and the carbon cycle and also since it eventually is transported into the stratosphere where it maintains the sulfate aerosol layer at about 20 km into the atmosphere. This layer is very important for earth's energy balance and climate change. In contrast with earlier and less comprehensive reports, this global study from 22 observation stations worldwide, shows stratospheric OCS to be increasing HANNIGAN ET AL.

Abstract. We present a multiyear time series of column abundances of carbon monoxide (CO), hydrogen cyanide (HCN), and ethane (C2H6) measured using Fourier-transform infrared (FTIR) spectrometers at 10 sites affiliated with the Network for the Detection of Atmospheric Composition Change (NDACC). Six are high-latitude sites: Eureka, Ny-Ålesund, Thule, Kiruna, Poker Flat, and St. Petersburg, and four are midlatitude sites: Zugspitze, Jungfraujoch, Toronto, and Rikubetsu. For each site, the interannual trends and seasonal variabilities of the CO time series are accounted for, allowing background column amounts to be determined. Enhancements above the seasonal background were used to identify possible wildfire pollution events. Since the abundance of each trace gas emitted in a wildfire event is specific to the type of vegetation burned and the burning phase, correlations of CO to the long-lived wildfire tracers HCN and C2H6 allow for further confirmation of the detection of wildfire pollution. A GEOS-Chem tagged CO simulation with Global Fire Assimilation System (GFASv1.2) biomass burning emissions was used to determine the source attribution of CO concentrations at each site from 2003 to 2018. For each detected wildfire pollution event, FLEXPART back-trajectory simulations were performed to determine the transport times of the smoke plume. Accounting for the loss of each species during transport, the enhancement ratios of HCN and C2H6 with respect to CO were converted to emission ratios. We report mean emission ratios with respect to CO for HCN and C2H6 of 0.0047 and 0.0092, respectively, with a standard deviation of 0.0014 and 0.0046, respectively, determined from 23 boreal North American wildfire events. Similarly, we report mean emission ratios for HCN and C2H6 of 0.0049 and 0.0100, respectively, with a standard deviation of 0.0025 and 0.0042, respectively, determined from 39 boreal Asian wildfire events. The agreement of our emission ratios with literature values illustrates the capability of ground-based FTIR measurements to quantify biomass burning emissions. We provide a comprehensive dataset that quantifies HCN and C2H6 emission ratios from 62 wildfire pollution events. Our dataset provides novel emission ratio estimates, which are sparsely available in the published literature, particularly for boreal Asian sources.

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