Abstract. TROPOMI (the TROPOspheric Monitoring Instrument), on board the Sentinel-5 Precursor (S5P) satellite, has been monitoring the Earth's atmosphere since October 2017 with an unprecedented horizontal resolution (initially 7 km2×3.5 km2, upgraded to 5.5 km2×3.5 km2 in August 2019). Monitoring air quality is one of the main objectives of TROPOMI; it obtains measurements of important pollutants such as nitrogen dioxide, carbon monoxide, and formaldehyde (HCHO). In this paper we assess the quality of the latest HCHO TROPOMI products versions 1.1.(5-7), using ground-based solar-absorption FTIR (Fourier-transform infrared) measurements of HCHO from 25 stations around the world, including high-, mid-, and low-latitude sites. Most of these stations are part of the Network for the Detection of Atmospheric Composition Change (NDACC), and they provide a wide range of observation conditions, from very clean remote sites to those with high HCHO levels from anthropogenic or biogenic emissions. The ground-based HCHO retrieval settings have been optimized and harmonized at all the stations, ensuring a consistent validation among the sites. In this validation work, we first assess the accuracy of TROPOMI HCHO tropospheric columns using the median of the relative differences between TROPOMI and FTIR ground-based data (BIAS). The pre-launch accuracy requirements of TROPOMI HCHO are 40 %–80 %. We observe that these requirements are well reached, with the BIAS found below 80 % at all the sites and below 40 % at 20 of the 25 sites. The provided TROPOMI systematic uncertainties are well in agreement with the observed biases at most of the stations except for the highest-HCHO-level site, where it is found to be underestimated. We find that while the BIAS has no latitudinal dependence, it is dependent on the HCHO concentration levels: an overestimation (+26±5 %) of TROPOMI is observed for very low HCHO levels (<2.5×1015 molec. cm−2), while an underestimation (-30.8%±1.4 %) is found for high HCHO levels (>8.0×1015 molec. cm−2). This demonstrates the great value of such a harmonized network covering a wide range of concentration levels, the sites with high HCHO concentrations being crucial for the determination of the satellite bias in the regions of emissions and the clean sites allowing a small TROPOMI offset to be determined. The wide range of sampled HCHO levels within the network allows the robust determination of the significant constant and proportional TROPOMI HCHO biases (TROPOMI =+1.10±0.05 ×1015+0.64±0.03 × FTIR; in molecules per square centimetre). Second, the precision of TROPOMI HCHO data is estimated by the median absolute deviation (MAD) of the relative differences between TROPOMI and FTIR ground-based data. The clean sites are especially useful for minimizing a possible additional collocation error. The precision requirement of 1.2×1016 molec. cm−2 for a single pixel is reached at most of the clean sites, where it is found that the TROPOMI precision can even be 2 times better (0.5–0.8×1015 molec. cm−2 for a single pixel). However, we find that the provided TROPOMI random uncertainties may be underestimated by a factor of 1.6 (for clean sites) to 2.3 (for high HCHO levels). The correlation is very good between TROPOMI and FTIR data (R=0.88 for 3 h mean coincidences; R=0.91 for monthly means coincidences). Using about 17 months of data (from May 2018 to September 2019), we show that the TROPOMI seasonal variability is in very good agreement at all of the FTIR sites. The FTIR network demonstrates the very good quality of the TROPOMI HCHO products, which is well within the pre-launch requirements for both accuracy and precision. This paper makes suggestions for the refinement of the TROPOMI random uncertainty budget and TROPOMI quality assurance values for a better filtering of the remaining outliers.

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.

We present new δ13C and δ18O records of surface (Morozovella and Acarinina) and thermocline dwelling (Subbotina) planktonic foraminifera and benthic foraminifera (Gavelinella, Cibicidoides, and Anomalinoides) during the Paleocene‐Eocene Thermal Maximum (PETM) from Millville, New Jersey, and compare them with three other sites located along a paleoshelf transect from the U.S. mid‐Atlantic coastal plain. Our analyses show different isotopic responses during the PETM in surface versus thermocline and benthic species. Whereas all taxa record a 3.6–4.0‰ δ13C decrease associated with the carbon isotope excursion, thermocline dwellers and benthic foraminifera show larger δ18O decreases compared to surface dwellers. We consider two scenarios that can explain the observed isotopic records: (1) a change in the water column structure and (2) a change in habitat or calcification season of the surface dwellers due to environmental stress (e.g., warming, ocean acidification, surface freshening, and/or eutrophication). In the first scenario, persistent warming during the PETM would have propagated heat into deeper layers and created a more homogenous water column with a thicker warm mixed layer and deeper, more gradual thermocline. We attribute the hydrographic change to decreased meridional thermal gradients, consistent with models that predict polar amplification. The second scenario assumes that environmental change was greater in the mixed layer forcing surface dwellers to descend into thermocline waters as a refuge or restrict their calcification to the colder seasons. Although both scenarios are plausible, similar δ13C responses recorded in surface, thermocline, and benthic foraminifera challenge mixed layer taxa migration.

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).

This paper presents a validation study of SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) carbon monoxide (CO) total column measurements from the Iterative Maximum Likelihood Method (IMLM) algorithm using ground-based spectrometer observations from twenty surface stations for the five year time period of 2003–2007.

Overall we find a good agreement between SCIAMACHY and ground-based observations for both mean values as well as seasonal variations.

For high-latitude Northern Hemisphere stations absolute differences between SCIAMACHY and ground-based measurements are close to or fall within the SCIAMACHY CO 2σ precision of 0.2 × 10¹⁸ molecules/cm² (∼10%) indicating that SCIAMACHY can observe CO accurately at high Northern Hemisphere latitudes.

For Northern Hemisphere mid-latitude stations the validation is complicated due to the vicinity of emission sources for almost all stations, leading to higher ground-based measurements compared to SCIAMACHY CO within its typical sampling area of 8° × 8°.

Comparisons with Northern Hemisphere mountain stations are hampered by elevation effects. After accounting for these effects, the validation provides satisfactory results.

At Southern Hemisphere mid- to high latitudes SCIAMACHY is systematically lower than the ground-based measurements for 2003 and 2004, but for 2005 and later years the differences between SCIAMACHY and ground-based measurements fall within the SCIAMACHY precision. The 2003–2004 bias is consistent with previously reported results although its origin remains under investigation.

No other systematic spatial or temporal biases could be identified based on the validation presented in this paper.

Validation results are robust with regard to the choices of the instrument-noise error filter, sampling area, and time averaging required for the validation of SCIAMACHY CO total column measurements.

Finally, our results show that the spatial coverage of the ground-based measurements available for the validation of the 2003–2007 SCIAMACHY CO columns is sub-optimal for validation purposes, and that the recent and ongoing expansion of the ground-based network by carefully selecting new locations may be very beneficial for SCIAMACHY CO and other satellite trace gas measurements validation efforts

Abstract. The Sentinel-5 Precursor (S5P) mission with the TROPOspheric Monitoring Instrument (TROPOMI) on board has been measuring solar radiation backscattered by the Earth's atmosphere and surface since its launch on 13 October 2017. In this paper, we present for the first time the S5P operational methane (CH4) and carbon monoxide (CO) products' validation results covering a period of about 3 years using global Total Carbon Column Observing Network (TCCON) and Infrared Working Group of the Network for the Detection of Atmospheric Composition Change (NDACC-IRWG) network data, accounting for a priori alignment and smoothing uncertainties in the validation, and testing the sensitivity of validation results towards the application of advanced co-location criteria. We found that the S5P standard and bias-corrected CH4 data over land surface for the recommended quality filtering fulfil the mission requirements. The systematic difference of the bias-corrected total column-averaged dry air mole fraction of methane (XCH4) data with respect to TCCON data is -0.26±0.56 % in comparison to -0.68±0.74 % for the standard XCH4 data, with a correlation of 0.6 for most stations. The bias shows a seasonal dependence. We found that the S5P CO data over all surfaces for the recommended quality filtering generally fulfil the missions requirements, with a few exceptions, which are mostly due to co-location mismatches and limited availability of data. The systematic difference between the S5P total column-averaged dry air mole fraction of carbon monoxide (XCO) and the TCCON data is on average 9.22±3.45 % (standard TCCON XCO) and 2.45±3.38 % (unscaled TCCON XCO). We found that the systematic difference between the S5P CO column and NDACC CO column (excluding two outlier stations) is on average 6.5±3.54 %. We found a correlation of above 0.9 for most TCCON and NDACC stations. The study shows the high quality of S5P CH4 and CO data by validating the products against reference global TCCON and NDACC stations covering a wide range of latitudinal bands, atmospheric conditions and surface conditions.

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.