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Coal mining accounts for ∼12 % of the total anthropogenic methane (CH4) emissions worldwide. The Upper Silesian Coal Basin (USCB), Poland, where large quantities of CH4 are emitted to the atmosphere via ventilation shafts of underground hard coal (anthracite) mines, is one of the hot spots of methane emissions in Europe. However, coal bed CH4 emissions into the atmosphere are poorly characterized. As part of the carbon dioxide and CH4 mission 1.0 (CoMet 1.0) that took place in May–June 2018, we flew a recently developed active AirCore system aboard an unmanned aerial vehicle (UAV) to obtain CH4 and CO2 mole fractions 150–300 m downwind of five individual ventilation shafts in the USCB. In addition, we also measured δ13C-CH4, δ2H-CH4, ambient temperature, pressure, relative humidity, surface wind speed, and surface wind direction. We used 34 UAV flights and two different approaches (inverse Gaussian approach and mass balance approach) to quantify the emissions from individual shafts. The quantified emissions were compared to both annual and hourly inventory data and were used to derive the estimates of CH4 emissions in the USCB. We found a high correlation (R2=0.7–0.9) between the quantified and hourly inventory data-based shaft-averaged CH4 emissions, which in principle would allow regional estimates of CH4 emissions to be derived by upscaling individual hourly inventory data of all shafts. Currently, such inventory data is available only for the five shafts we quantified. As an alternative, we have developed three upscaling approaches, i.e., by scaling the European Pollutant Release and Transfer Register (E-PRTR) annual inventory, the quantified shaft-averaged emission rate, and the shaft-averaged emission rate, which are derived from the hourly emission inventory. These estimates are in the range of 256–383 kt CH4 yr−1 for the inverse Gaussian (IG) approach and 228–339 kt CH4 yr−1 for the mass balance (MB) approach. We have also estimated the total CO2 emissions from coal mining ventilation shafts based on the observed ratio of CH4/CO2 and found that the estimated regional CO2 emissions are not a major source of CO2 in the USCB. This study shows that the UAV-based active AirCore system can be a useful tool to quantify local to regional point source methane emissions.

We have constructed an atmospheric inversion framework based on TM5-4DVAR to jointly assimilate measurements of methane and δ13C of methane in order to estimate source-specific methane emissions. Here we present global emission estimates from this framework for the period 1999–2016. We assimilate a newly constructed, multi-agency database of CH4 and δ13C measurements. We find that traditional CH4-only atmospheric inversions are unlikely to estimate emissions consistent with atmospheric δ13C data, and assimilating δ13C data is necessary to derive emissions consistent with both measurements. Our framework attributes ca. 85 % of the post-2007 growth in atmospheric methane to microbial sources, with about half of that coming from the tropics between 23.5∘ N and 23.5∘ S. This contradicts the attribution of the recent growth in the methane budget of the Global Carbon Project (GCP). We find that the GCP attribution is only consistent with our top-down estimate in the absence of δ13C data. We find that at global and continental scales, δ13C data can separate microbial from fossil methane emissions much better than CH4 data alone, and at smaller scales this ability is limited by the current δ13C measurement coverage. Finally, we find that the largest uncertainty in using δ13C data to separate different methane source types comes from our knowledge of atmospheric chemistry, specifically the distribution of tropospheric chlorine and the isotopic discrimination of the methane sink.

Intensive coal mining activities in the Upper Silesian Coal Basin (USCB) in southern Poland are resulting in large amounts of methane (CH4) emissions. Annual CH4 emissions reached 448 kt according to the European Pollutant Release and Transfer Register (E-PRTR, 2017). As a CH4 emission hotspot in Europe, it is of importance to investigate its emission sources and make accurate emission estimates. In this study, we use satellite-based total column-averaged dry-air mole fraction of CH4 (XCH4) from the TROPOspheric Monitoring Instrument (TROPOMI) and tropospheric XCH4 (TXCH4) from the Infrared Atmospheric Sounding Interferometer (IASI). In addition, the high-resolution model forecasts, XCH4 and TXCH4, from the Copernicus Atmosphere Monitoring Service (CAMS) are used to estimate the CH4 emission rate averaged over 3 years (November 2017–December 2020) in the USCB region (49.3–50.8∘ N and 18–20∘ E). The wind-assigned anomaly method is first validated using the CAMS forecast data (XCH4 and TXCH4), showing a good agreement with the CAMS GLOBal ANThropogenic emission (CAMS-GLOB-ANT) inventory. It indicates that the wind-assigned method works well. This wind-assigned method is further applied to the TROPOMI XCH4 and TROPOMI + IASI TXCH4 by using the Carbon dioxide and Methane (CoMet) inventory derived for the year 2018. The calculated averaged total CH4 emissions over the USCB region is about 496 kt yr−1 (5.9×1026 molec. s−1) for TROPOMI XCH4 and 437 kt yr−1 (5.2×1026 molec. s−1) for TROPOMI + IASI TXCH4. These values are very close to the ones given in the E-PRTR inventory (448 kt yr−1) and the ones in the CoMet inventory (555 kt yr−1), and are thus in agreement with these inventories. The similar estimates of XCH4 and TXCH4 also imply that for a strong source, the dynamically induced variations of the CH4 mixing ratio in the upper troposphere and lower stratosphere region are of secondary importance. Uncertainties from different error sources (background removal and noise in the data, vertical wind shear, wind field segmentation, and angle of the emission cone) are approximately 14.8 % for TROPOMI XCH4 and 11.4 % for TROPOMI + IASI TXCH4. These results suggest that our wind-assigned method is quite robust and might also serve as a simple method to estimate CH4 or CO2 emissions for other regions.

Methane (CH4) is the second most important anthropogenic greenhouse gas, whose atmospheric concentration is modulated by human-induced activities, and it has a larger global warming potential than carbon dioxide (CO2). Because of its short atmospheric lifetime relative to that of CO2, the reduction of the atmospheric abundance of CH4 is an attractive target for short-term climate mitigation strategies. However, reducing the atmospheric CH4 concentration requires a reduction of its emissions and, therefore, knowledge of its sources. For this reason, the CO2 and Methane (CoMet) campaign in May and June 2018 assessed emissions of one of the largest CH4 emission hot spots in Europe, the Upper Silesian Coal Basin (USCB) in southern Poland, using top-down approaches and inventory data. In this study, we will focus on CH4 column anomalies retrieved from spectral radiance observations, which were acquired by the 1D nadir-looking passive remote sensing Methane Airborne MAPper (MAMAP) instrument, using the weighting-function-modified differential optical absorption spectroscopy (WFM-DOAS) method. The column anomalies, combined with wind lidar measurements, are inverted to cross-sectional fluxes using a mass balance approach. With the help of these fluxes, reported emissions of small clusters of coal mine ventilation shafts are then assessed. The MAMAP CH4 column observations enable an accurate assignment of observed fluxes to small clusters of ventilation shafts. CH4 fluxes are estimated for four clusters with a total of 23 ventilation shafts, which are responsible for about 40 % of the total CH4 mining emissions in the target area. The observations were made during several overflights on different days. The final average CH4 fluxes for the single clusters (or sub-clusters) range from about 1 to 9 t CH4 h−1 at the time of the campaign. The fluxes observed at one cluster during different overflights vary by as much as 50 % of the average value. Associated errors (1σ) are usually between 15 % and 59 % of the average flux, depending mainly on the prevailing wind conditions, the number of flight tracks, and the magnitude of the flux itself. Comparison to known hourly emissions, where available, shows good agreement within the uncertainties. If only emissions reported annually are available for comparison with the observations, caution is advised due to possible fluctuations in emissions during a year or even within hours. To measure emissions even more precisely and to break them down further for allocation to individual shafts in a complex source region such as the USCB, imaging remote sensing instruments are recommended.

Methane (CH4) emissions from human activities are a threat to the resilience of our current climate system. The stable isotopic composition of methane (δ13C and δ2H) allows us to distinguish between the different CH4 origins. A significant part of the European CH4 emissions, 3.6 % in 2018, comes from coal extraction in Poland, the Upper Silesian Coal Basin (USCB) being the main hotspot. Measurements of CH4 mole fraction (χ(CH4)), δ13C, and δ2H in CH4 in ambient air were performed continuously during 6 months in 2018 and 2019 at Krakow, Poland, in the east of the USCB. In addition, air samples were collected during parallel mobile campaigns, from multiple CH4 sources in the footprint area of the continuous measurements. The resulting isotopic signatures from sampled plumes allowed us to distinguish between natural gas leaks, coal mine fugitive emissions, landfill and sewage, and ruminants. The use of δ2H in CH4 is crucial to distinguish the fossil fuel emissions in the case of Krakow because their relatively depleted δ13C values overlap with the ones of microbial sources. The observed χ(CH4) time series showed regular daily night-time accumulations, sometimes combined with irregular pollution events during the day. The isotopic signatures of each peak were obtained using the Keeling plot method and generally fall in the range of thermogenic CH4 formation – with δ13C between −59.3 ‰ and −37.4 ‰ Vienna Pee Dee Belemnite (V-PDB) and δ2H between −291 ‰ and −137 ‰ Vienna Standard Mean Ocean Water (V-SMOW). They compare well with the signatures measured for gas leaks in Krakow and USCB mines. The CHIMERE transport model was used to compute the CH4 and isotopic composition time series in Krakow, based on two emission inventories. The magnitude of the pollution events is generally underestimated in the model, which suggests that emission rates in the inventories are too low. The simulated isotopic source signatures, obtained with Keeling plots on each simulated peak, indicate that a higher contribution from fuel combustion sources in the EDGAR v5.0 inventory would lead to a better agreement than when using CAMS-REG-GHG v4.2 (Copernicus Atmosphere Monitoring Service REGional inventory for Air Pollutants and GreenHouse Gases). The isotopic mismatches between model and observations are mainly caused by uncertainties in the assigned isotopic signatures for each source category and the way they are classified in the inventory. These uncertainties are larger for emissions close to the study site, which are more heterogenous than the ones advected from the USCB coal mines. Our isotope approach proves to be very sensitive in this region, thus helping to evaluate emission estimates.

We present highly time-resolved (30 to 120 min) measurements of size-fractionated (PM10 and PM2.5) elements in two cities in Asia (Delhi and Beijing) and Europe (Krakow and London). For most elements, the mean concentrations in PM10 and PM2.5 are higher in the Asian cities (up to 24 and 28 times, respectively) than in Krakow and often higher in Delhi than in Beijing. Among European cities, Krakow shows higher elemental concentrations (up to 20 and 27 times, respectively) than London. Hourly maximum concentrations of Pb and Zn reach up to 1 µg m−3 in Delhi, substantially higher than at the other sites. The enrichment factor of an element together with the size distribution allows for a rough classification of elements by major source. We define five groups: (1) dust emissions, (2) non-exhaust traffic emissions, (3) solid fuel combustion, (4) mixed traffic/industrial emissions, and (5) industrial/coal/waste burning emissions, with the last group exhibiting the most site-to-site variability. We demonstrate that the high time resolution and size-segregated elemental dataset can be a powerful tool to assess aerosol composition and sources in urban environments. Our results highlight the need to consider the size distributions of toxic elements, diurnal patterns of targeted emissions, and local vs. regional effects in formulating effective environmental policies to protect public health.

We present inverse modelling (top down) estimates of European methane (CH4) emissions for 2006–2012 based on a new quality-controlled and harmonised in situ data set from 18 European atmospheric monitoring stations. We applied an ensemble of seven inverse models and performed four inversion experiments, investigating the impact of different sets of stations and the use of a priori information on emissions. The inverse models infer total CH4 emissions of 26.8 (20.2–29.7) Tg CH4 yr−1 (mean, 10th and 90th percentiles from all inversions) for the EU-28 for 2006–2012 from the four inversion experiments. For comparison, total anthropogenic CH4 emissions reported to UNFCCC (bottom up, based on statistical data and emissions factors) amount to only 21.3 Tg CH4 yr−1 (2006) to 18.8 Tg CH4 yr−1 (2012). A potential explanation for the higher range of top-down estimates compared to bottom-up inventories could be the contribution from natural sources, such as peatlands, wetlands, and wet soils. Based on seven different wetland inventories from the Wetland and Wetland CH4 Inter-comparison of Models Project (WETCHIMP), total wetland emissions of 4.3 (2.3–8.2) Tg CH4 yr−1 from the EU-28 are estimated. The hypothesis of significant natural emissions is supported by the finding that several inverse models yield significant seasonal cycles of derived CH4 emissions with maxima in summer, while anthropogenic CH4 emissions are assumed to have much lower seasonal variability. Taking into account the wetland emissions from the WETCHIMP ensemble, the top-down estimates are broadly consistent with the sum of anthropogenic and natural bottom-up inventories. However, the contribution of natural sources and their regional distribution remain rather uncertain. Furthermore, we investigate potential biases in the inverse models by comparison with regular aircraft profiles at four European sites and with vertical profiles obtained during the Infrastructure for Measurement of the European Carbon Cycle (IMECC) aircraft campaign. We present a novel approach to estimate the biases in the derived emissions, based on the comparison of simulated and measured enhancements of CH4 compared to the background, integrated over the entire boundary layer and over the lower troposphere. The estimated average regional biases range between −40 and 20 % at the aircraft profile sites in France, Hungary and Poland.

We investigate the sensitivity of future spaceborne lidar measurements to changes in surface methane emissions. We use surface methane observations from nine European ground stations and a Lagrangian transport model to infer surface methane emissions for 2010. Our inversion shows the strongest emissions from the Netherlands, the coal mines in Upper Silesia, Poland, and wetlands in southern Finland. The simulated methane surface concentrations capture at least half of the daily variability in the observations, suggesting that the transport model is correctly simulating the regional transport pathways over Europe. With this tool we can test whether proposed methane lidar instruments will be sensitive to changes in surface emissions. We show that future lidar instruments should be able to detect a 50% reduction in methane emissions from the Netherlands and Germany, at least during summer.

The Bayesian framework of CO2 flux inversions permits estimates of the retrieved flux uncertainties. Here, the reliability of these theoretical estimates is studied through a comparison against the misfits between the inverted fluxes and independent measurements of the CO2 Net Ecosystem Exchange (NEE) made by the eddy covariance technique at local (few hectares) scale. Regional inversions at 0.5° resolution are applied for the western European domain where ~ 50 eddy covariance sites are operated. These inversions are conducted for the period 2002–2007. They use a mesoscale atmospheric transport model, a prior estimate of the NEE from a terrestrial ecosystem model and rely on the variational assimilation of in situ continuous measurements of CO2 atmospheric mole fractions. Averaged over monthly periods and over the whole domain, the misfits are in good agreement with the theoretical uncertainties for prior and inverted NEE, and pass the chi-square test for the variance at the 30% and 5% significance levels respectively, despite the scale mismatch and the independence between the prior (respectively inverted) NEE and the flux measurements. The theoretical uncertainty reduction for the monthly NEE at the measurement sites is 53% while the inversion decreases the standard deviation of the misfits by 38%. These results build confidence in the NEE estimates at the European/monthly scales and in their theoretical uncertainty from the regional inverse modelling system. However, the uncertainties at the monthly (respectively annual) scale remain larger than the amplitude of the inter-annual variability of monthly (respectively annual) fluxes, so that this study does not engender confidence in the inter-annual variations. The uncertainties at the monthly scale are significantly smaller than the seasonal variations. The seasonal cycle of the inverted fluxes is thus reliable. In particular, the CO2 sink period over the European continent likely ends later than represented by the prior ecosystem model.

We adapt general statistical methods to estimate the optimal error covariance matrices in a regional inversion system inferring methane surface emissions from atmospheric concentrations. Using a minimal set of physical hypotheses on the patterns of errors, we compute a guess of the error statistics that is optimal in regard to objective statistical criteria for the specific inversion system. With this very general approach applied to a real-data case, we recover sources of errors in the observations and in the prior state of the system that are consistent with expert knowledge while inferred from objective criteria and with affordable computation costs. By not assuming any specific error patterns, our results depict the variability and the inter-dependency of errors induced by complex factors such as the misrepresentation of the observations in the transport model or the inability of the model to reproduce well the situations of steep gradients of concentrations. Situations with probable significant biases (e.g., during the night when vertical mixing is ill-represented by the transport model) can also be diagnosed by our methods in order to point at necessary improvement in a model. By additionally analysing the sensitivity of the inversion to each observation, guidelines to enhance data selection in regional inversions are also proposed. We applied our method to a recent significant accidental methane release from an offshore platform in the North Sea and found methane fluxes of the same magnitude than what was officially declared.

This paper presents an analysis of the recent tropospheric molecular hydrogen (H2) budget with a particular focus on soil uptake and European surface emissions. A variational inversion scheme is combined with observations from the RAMCES and EUROHYDROS atmospheric networks, which include continuous measurements performed between mid-2006 and mid-2009. Net H2 surface flux, then deposition velocity and surface emissions and finally, deposition velocity, biomass burning, anthropogenic and N2 fixation-related emissions were simultaneously inverted in several scenarios. These scenarios have focused on the sensibility of the soil uptake value to different spatio-temporal distributions. The range of variations of these diverse inversion sets generate an estimate of the uncertainty for each term of the H2 budget. The net H2 flux per region (High Northern Hemisphere, Tropics and High Southern Hemisphere) varies between −8 and +8 Tg yr−1. The best inversion in terms of fit to the observations combines updated prior surface emissions and a soil deposition velocity map that is based on bottom-up and top-down estimations. Our estimate of global H2 soil uptake is −59±9 Tg yr−1. Forty per cent of this uptake is located in the High Northern Hemisphere and 55% is located in the Tropics. In terms of surface emissions, seasonality is mainly driven by biomass burning emissions. The inferred European anthropogenic emissions are consistent with independent H2 emissions estimated using a H2/CO mass ratio of 0.034 and CO emissions within the range of their respective uncertainties. Additional constraints, such as isotopic measurements would be needed to infer a more robust partition of H2 sources and sinks.

Anthropogenic emissions are the primary source of the increase in atmospheric methane (CH4) levels. However, estimates of anthropogenic CH4 emissions still show large uncertainties at global and regional scales. Differences in CH4 isotopic source signatures δ13C and δ2H can help to constrain different source contributions (e.g., fossil, waste, agriculture). The Upper Silesian Coal Basin (USCB) represents one of the largest European CH4 emission regions, with more than 500 Gg CH4 yr−1 released from more than 50 coal mine ventilation shafts, landfills, and wastewater treatment plants. During the CoMet (Carbon Dioxide and Methane Mission) campaign in June 2018 methane observations were conducted from a variety of platforms including aircraft and cars to quantify these emissions. Besides the continuous sampling of atmospheric methane concentration, numerous air samples were taken from inside and around the ventilation shafts (1–2 km distance) and aboard the High Altitude and Long Range Research Aircraft (HALO) and DLR Cessna Caravan aircraft, and they were analyzed in the laboratory for the isotopic composition of CH4. The airborne samples downwind of the USCB contained methane from the entire region and thus enabled determining the mean signature of the USCB accurately. This mean isotopic signature of methane emissions was -50.9±0.7 ‰ for δ13C and -226±9 ‰ for δ2H. This is in the range of previous USCB studies based on samples taken within the mines for δ13C but more depleted in δ2H than reported before. Signatures of methane enhancements sampled upwind of the mines and in the free troposphere clearly showed the influence of biogenic sources. We determined the source signatures of individual coal mine ventilation shafts using ground-based samples. These signatures displayed a considerable range between different mines and also varied for individual shafts from day to day. Different layers of the USCB coal contain thermogenic methane, isotopically similar to natural gas, and methane formed through biogenic carbonate reduction. The signatures vary depending on what layer of coal is mined at the time of sampling. Mean shaft signatures range from −60 ‰ to −42 ‰ for δ13C and from −200 ‰ to −160 ‰ for δ2H. A gradient in the signatures of subregions of the USCB is reflected both in the aircraft data and in the ground samples, with emissions from the southwest being most depleted in δ2H and emissions from the south being most depleted in δ13C, which is probably associated with the structural and lithostratigraphic history of the USCB and generation and migration processes of methane in the coal. The average signature of -49.8±5.7 ‰ in δ13C and -184±32 ‰ in δ2H from the ventilation shafts clearly differs from the USCB regional signature in δ2H. This makes a source attribution using δ2H signatures possible, which would not be possible with only the δ13C isotopic signatures. We assume that the USCB plume mainly contains fossil coal mine methane and biogenic methane from waste treatment, because the USCB is a highly industrialized region with few other possible methane sources. Assuming a biogenic methane signature between and −320 ‰ and −280 ‰ for δ2H, the biogenic methane emissions from the USCB account for 15 %–50 % of total emissions. The uncertainty range shows the need of comprehensive and extensive sampling from all possible source sectors for source apportionment. The share of anthropogenic–biogenic emissions of 0.4 %–14 % from this densely populated industrial region is underestimated in commonly used emission inventories. Generally, this study demonstrates the importance of δ2H-CH4 observations for methane source apportionment in regions with a mix of thermogenic and biogenic sources and, especially in our case, where the δ13C signature of the coal mine gas has a large variability.

Recent climate change mitigation strategies rely on the reduction of methane (CH4) emissions. Carbon and hydrogen isotope ratio (δ13CCH4 and δ2HCH4) measurements can be used to distinguish sources and thus to understand the CH4 budget better. The CH4 emission estimates by models are sensitive to the isotopic signatures assigned to each source category, so it is important to provide representative estimates of the different CH4 source isotopic signatures worldwide. We present new measurements of isotope signatures of various, mainly anthropogenic, CH4 sources in Europe, which represent a substantial contribution to the global dataset of source isotopic measurements from the literature, especially for δ2HCH4. They improve the definition of δ13CCH4 from waste sources, and demonstrate the use of δ2HCH4 for fossil fuel source attribution. We combined our new measurements with the last published database of CH4 isotopic signatures and with additional literature, and present a new global database. We found that microbial sources are generally well characterised. The large variability in fossil fuel isotopic compositions requires particular care in the choice of weighting criteria for the calculation of a representative global value. The global dataset could be further improved by measurements from African, South American, and Asian countries, and more measurements from pyrogenic sources. We improved the source characterisation of CH4 emissions using stable isotopes and associated uncertainty, to be used in top-down studies. We emphasise that an appropriate use of the database requires the analysis of specific parameters in relation to source type and the region of interest. The final version of the European CH4 isotope database coupled with a global inventory of fossil and non-fossil δ13CCH4 and δ2HCH4 source signature measurements is available at https://doi.org/10.24416/UU01-YP43IN (Menoud et al., 2022a).

Given its abundant coal mining activities, the Upper Silesian Coal Basin (USCB) in southern Poland is one of the largest sources of anthropogenic methane (CH4) emissions in Europe. Here, we report on CH4 emission estimates for coal mine ventilation facilities in the USCB. Our estimates are driven by pairwise upwind–downwind observations of the column-average dry-air mole fractions of CH4 (XCH4) by a network of four portable, ground-based, sun-viewing Fourier transform spectrometers of the type EM27/SUN operated during the CoMet campaign in May–June 2018. The EM27/SUN instruments were deployed in the four cardinal directions around the USCB approximately 50 km from the center of the basin. We report on six case studies for which we inferred emissions by evaluating the mismatch between the observed downwind enhancements and simulations based on trajectory calculations releasing particles out of the ventilation shafts using the Lagrangian particle dispersion model FLEXPART. The latter was driven by wind fields calculated by WRF (Weather Research and Forecasting model) under assimilation of vertical wind profile measurements of three co-deployed wind lidars. For emission estimation, we use a Phillips–Tikhonov regularization scheme with the L-curve criterion. Diagnosed by the emissions averaging kernels, we find that, depending on the catchment area of the downwind measurements, our ad hoc network can resolve individual facilities or groups of ventilation facilities but that inspecting the emissions averaging kernels is essential to detect correlated estimates. Generally, our instantaneous emission estimates range between 80 and 133 kt CH4 a−1 for the southeastern part of the USCB and between 414 and 790 kt CH4 a−1 for various larger parts of the basin, suggesting higher emissions than expected from the annual emissions reported by the E-PRTR (European Pollutant Release and Transfer Register). Uncertainties range between 23 % and 36 %, dominated by the error contribution from uncertain wind fields.

Kraków is routinely affected by very high air pollution levels, especially during the winter months. Although a lot of effort has been made to characterize ambient aerosol, there is a lack of online and long-term measurements of non-refractory aerosol. Our measurements at the AGH University of Science and Technology provide the online long-term chemical composition of ambient submicron particulate matter (PM1) between January 2018 and April 2019. Here we report the chemical characterization of non-refractory submicron aerosol and source apportionment of the organic fraction by positive matrix factorization (PMF). In contrast to other long-term source apportionment studies, we let a small PMF window roll over the dataset instead of performing PMF over the full dataset or on separate seasons. In this way, the seasonal variation in the source profiles can be captured. The uncertainties in the PMF solutions are addressed by the bootstrap resampling strategy and the random a-value approach for constrained factors. We observe clear seasonal patterns in the concentration and composition of PM1, with high concentrations during the winter months and lower concentrations during the summer months. Organics are the dominant species throughout the campaign. Five organic aerosol (OA) factors are resolved, of which three are of a primary nature (hydrocarbon-like OA (HOA), biomass burning OA (BBOA) and coal combustion OA (CCOA)) and two are of a secondary nature (more oxidized oxygenated OA (MO-OOA) and less oxidized oxygenated OA (LO-OOA)). While HOA contributes on average 8.6 % ± 2.3 % throughout the campaign, the solid-fuel-combustion-related BBOA and CCOA show a clear seasonal trend with average contributions of 10.4 % ± 2.7 % and 14.1 %, ±2.1 %, respectively. Not only BBOA but also CCOA is associated with residential heating because of the pronounced yearly cycle where the highest contributions are observed during wintertime. Throughout the campaign, the OOA can be separated into MO-OOA and LO-OOA with average contributions of 38.4 % ± 8.4 % and 28.5 % ± 11.2 %, respectively.

A severe reduction of greenhouse gas emissions is necessary to reach the objectives of the Paris Agreement. The implementation and continuous evaluation of mitigation measures requires regular independent information on emissions of the two main anthropogenic greenhouse gases, carbon dioxide (CO2) and methane (CH4). Our aim is to employ an observation-based method to determine regional-scale greenhouse gas emission estimates with high accuracy. We use aircraft- and ground-based in situ observations of CH4, CO2, carbon monoxide (CO), and wind speed from two research flights over the Upper Silesian Coal Basin (USCB), Poland, in summer 2018. The flights were performed as a part of the Carbon Dioxide and Methane (CoMet) mission above this European CH4 emission hot-spot region. A kriging algorithm interpolates the observed concentrations between the downwind transects of the trace gas plume, and then the mass flux through this plane is calculated. Finally, statistic and systematic uncertainties are calculated from measurement uncertainties and through several sensitivity tests, respectively. For the two selected flights, the in-situ-derived annual CH4 emission estimates are 13.8±4.3 and 15.1±4.0 kg s−1, which are well within the range of emission inventories. The regional emission estimates of CO2, which were determined to be 1.21±0.75 and 1.12±0.38 t s−1, are in the lower range of emission inventories. CO mass balance emissions of 10.1±3.6 and 10.7±4.4 kg s−1 for the USCB are slightly higher than the emission inventory values. The CH4 emission estimate has a relative error of 26 %–31 %, the CO2 estimate of 37 %–62 %, and the CO estimate of 36 %–41 %. These errors mainly result from the uncertainty of atmospheric background mole fractions and the changing planetary boundary layer height during the morning flight. In the case of CO2, biospheric fluxes also add to the uncertainty and hamper the assessment of emission inventories. These emission estimates characterize the USCB and help to verify emission inventories and develop climate mitigation strategies.

Particulate chloride is an important component of fine particulate matter in marine air masses. Recent field studies also report elevated concentrations of gas-phase reactive chlorine species and particulate chloride related to anthropogenic activities. This work focuses on particulate chloride detection and quantification issues observed for some quadrupole aerosol chemical speciation monitors (Q-ACSMs) which are designed for the long-term measurement of ambient aerosol composition. The ACSM reports particle concentrations based on the difference between measurements of ambient air (sample mode) and particle-free ambient air (filter mode). For our long-term campaign in Krakow, Poland, the Q-ACSM reports apparent negative total chloride concentration for most of the campaign when analyzed with the default fragmentation table. This is the result of the difference signal from m∕z 35 (35Cl+) being negative, which dominates over the positive difference signal from m∕z 36 (H35Cl+). Highly time-resolved experiments with NH4Cl, NaCl and KCl particles show that the signal response of m∕z 35 is non-ideal when the signal builds up and decreases slowly for all three salts, leading to a negative difference measurement. In contrast, the m∕z 36 signal exhibits a near step-change response for NH4Cl during the sampling and filter period, resulting in a positive difference signal. The response of m∕z 36 for NaCl and KCl is not as prompt as for NH4Cl but still fast enough to have a positive difference signal. Furthermore, it is shown that this behavior is mostly independent of vaporizer temperature. Based on these observations, this work presents an approach to correct the chloride concentration time series by adapting the standard fragmentation table coupled with a calibration of NH4Cl to obtain a relative ionization efficiency (RIE) based on the signal at m∕z 36 (H35Cl+). This correction can be applied to measurements in environments where chloride is dominated by NH4Cl. Caution should be exercised when other chloride salts dominate the ambient particulate chloride.

Methane (CH4) emissions from coal production amount to roughly one-third of European anthropogenic CH4 emissions in the atmosphere. Poland is the largest hard coal producer in the European Union with the Polish side of the Upper Silesian Coal Basin (USCB) as the main part of it. Emission estimates for CH4 from the USCB for individual coal mine ventilation shafts range between 0.03 and 20 kt a−1, amounting to a basin total of roughly 440 kt a−1 according to the European Pollutant Release and Transfer Register (E-PRTR, http://prtr.ec.europa.eu/, 2014). We mounted a ground-based, portable, sun-viewing FTS (Fourier transform spectrometer) on a truck for sampling coal mine ventilation plumes by driving cross-sectional stop-and-go patterns at 1 to 3 km from the exhaust shafts. Several of these transects allowed for estimation of CH4 emissions based on the observed enhancements of the column-averaged dry-air mole fractions of methane (XCH4) using a mass balance approach. Our resulting emission estimates range from 6±1 kt a−1 for a single shaft up to 109±33 kt a−1 for a subregion of the USCB, which is in broad agreement with the E-PRTR reports. Three wind lidars were deployed in the larger USCB region providing ancillary information about spatial and temporal variability of wind and turbulence in the atmospheric boundary layer. Sensitivity studies show that, despite drawing from the three wind lidars, the uncertainty of the local wind dominates the uncertainty of the emission estimates, by far exceeding errors related to the XCH4 measurements themselves. Wind-related relative errors on the emission estimates typically amount to 20 %.

Competing Interests: Declaration of competing interest Francesco Canonaco and Anna Tobler work for Datalystica Ltd., which provides the SoFi software used in this paper. Otherwise, the authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Winter smog episodes are a severe problem in many cities around the world. The following two mechanisms are responsible for influencing the level of pollutant concentrations: emission of pollutants from different sources and associated processes leading to formation of secondary aerosols in the atmosphere and meteorology, including advection, which is stimulated by horizontal wind, and convection, which depends on vertical air mass movements associated with boundary layer stability that are determined by vertical temperature and humidity gradients. The aim of the present study was to evaluate the performance of an unmanned aerial vehicle (UAV)-based measurement system developed for investigation of urban boundary layer dynamics. The evaluation was done by comparing the results of temperature, relative humidity, wind speed and particulate matter fraction with aerodynamic diameter below 10 μm (PM 10 ) concentration vertical profiles obtained using this system with two reference meteorological stations: Jagiellonian University Campus (JUC) and radio transmission tower (RTCN), located in the urban area of Krakow city, Southern Poland. The secondary aim of the study was to optimize data processing algorithms improving the response time of UAV sensor measurements during the ascent and descent parts of the flight mission.

During the summer of 2018, a widespread drought developed over Northern and Central Europe. The increase in temperature and the reduction of soil moisture have influenced carbon dioxide (CO 2 ) exchange between the atmosphere and terrestrial ecosystems in various ways, such as a reduction of photosynthesis, changes in ecosystem respiration, or allowing more frequent fires. In this study, we characterize the resulting perturbation of the atmospheric CO 2 seasonal cycles. 2018 has a good coverage of European regions affected by drought, allowing the investigation of how ecosystem flux anomalies impacted spatial CO 2 gradients between stations. This density of stations is unprecedented compared to previous drought events in 2003 and 2015, particularly thanks to the deployment of the Integrated Carbon Observation System (ICOS) network of atmospheric greenhouse gas monitoring stations in recent years. Seasonal CO 2 cycles from 48 European stations were available for 2017 and 2018. Earlier data were retrieved for comparison from international databases or national networks. Here, we show that the usual summer minimum in CO 2 due to the surface carbon uptake was reduced by 1.4 ppm in 2018 for the 10 stations located in the area most affected by the temperature anomaly, mostly in Northern Europe. Notwithstanding, the CO 2 transition phases before and after July were slower in 2018 compared to 2017, suggesting an extension of the growing season, with either continued CO 2 uptake by photosynthesis and/or a reduction in respiration driven by the depletion of substrate for respiration inherited from the previous months due to the drought. For stations with sufficiently long time series, the CO 2 anomaly observed in 2018 was compared to previous European droughts in 2003 and 2015. Considering the areas most affected by the temperature anomalies, we found a higher CO 2 anomaly in 2003 (+3 ppm averaged over 4 sites), and a smaller anomaly in 2015 (+1 ppm averaged over 11 sites) compared to 2018. This article is part of the theme issue 'Impacts of the 2018 severe drought and heatwave in Europe: from site to continental scale'.

Regular measurements of atmospheric CO (2) mixing ratios and their carbon isotope composition ((13)C/(12)C and (14)C/(12)C ratios) performed between 2005 and 2009 at two sites of contrasting characteristics (Krakow and the remote mountain site Kasprowy Wierch) located in southern Poland were used to derive fossil fuel-related and biogenic contributions to the total CO (2) load measured at both sites. Carbon dioxide present in the atmosphere, not coming from fossil fuel and biogenic sources, was considered 'background' CO (2). In Krakow, the average contribution of fossil fuel CO (2) was approximately 3.4%. The biogenic component was of the same magnitude. Both components revealed a distinct seasonality, with the fossil fuel component reaching maximum values during winter months and the biogenic component shifted in phase by approximately 6 months. The partitioning of the local CO (2) budget for the Kasprowy Wierch site revealed large differences in the derived components: the fossil fuel component was approximately five times lower than that derived for Krakow, whereas the biogenic component was negative in summer, pointing to the importance of photosynthetic sink associated with extensive forests in the neighbourhood of the station. While the presented study has demonstrated the strength of combined measurements of CO (2) mixing ratios and their carbon isotope signature as efficient tools for elucidating the partitioning of local atmospheric CO (2) loads, it also showed the important role of the land cover and the presence of the soil in the footprint of the measurement location, which control the net biogenic surface CO (2) fluxes.

This article presents the results of measurements of the isotopic composition and concentration of atmospheric carbon dioxide, performed on air samples from Kraków (Southern Poland) in different seasons of the year. A simple isotope mass balance model has been applied to determine the contributions of different sources of CO2 to the urban atmosphere of Kraków city: the latitudinal/regional background, biospheric contributions and anthropogenic emissions. The calculations show that during the summer and early autumn the dominant contribution to local CO2 peaks is the biosphere, making up to 20% of atmospheric CO2 during the nocturnal temperature inversion in the lower troposphere. During early spring and winter, anthropogenic emissions are the main local source., (Copyright 2004 Taylor and Francis Ltd.)