Mixing of endogenous CO2 and meteoric H2O causes extremely efficient carbonate dissolution.

Karst corrosion of carbonate rocks by water with dissolved gases proceeds in most cases along two major scenarios: (i) meteoric water absorbs CO2 from soil and atmosphere, or (ii) ascending water of deep circulation carries with it dissolved endogenous gases, mainly CO2 and H2S. We have observed a peculiar variant where meteoric water absorbs ascending endogenous gases at a natural gas vent on a travertine mound in Slovakia. Carbonate dissolution's extreme effectiveness is demonstrated by mineralization of rainwater ponded at a gas vent, rising to 3.2 g/L of dissolved solids shortly after the rainfall. One liter of water ponded at the vent and mixing with the venting gas, dissolved up to 800 mg of calcium at a rate exceeding 5.8 mg/L·min. Limestone tablets placed at the vent show signs of significant corrosion, at rates up to 126 mm/ka. The rate is comparable to those in coastal karst, where freshwater is mixing with seawater and to those in sulfuric acid speleogenesis (SAS), both the highest hitherto known rates of karst corrosion in carbonates. The geomorphic effects of the process described are depressions on the surface of travertine near the vents of endogenous CO2. This type of corrosion seems to be universal and probably occurs everywhere where endogenous CO2 is exhaled to the surface from carbonate rocks.

Temporal dynamics and controlling factors of CO2 and CH4 variability in the urban atmosphere of Wroclaw, Poland.

Temporal and spatial distribution of both biogenic and anthropogenic components of atmospheric carbon dioxide (CO2) and methane (CH4) is crucial for understanding the environmental impacts of climate change over urban areas. This research focuses on applying stable isotope source-partitioning studies to determine the interactions between biogenic and anthropogenic CO2 and CH4 emissions in an average-sized city environment. Study signifies the weight of instantaneous variability and diurnal averaging as compared with seasonal records of variations of the atmospheric CO2 and CH4 at a variety of typical urban sites in the city of Wroclaw, conducted during a one-year period from June 2017 to August 2018. The findings reveal distinct temporal variations in atmospheric CO2 and CH4 mole fractions and their isotopic composition. The average atmospheric CO2 and CH4 mole fractions during the study period were 416.4 ± 20.5 ppm, and 1.95 ± 0.09 ppm, respectively. The study highlights the high variability of driving forces, including current energy use patterns, natural carbon reservoirs, planetary boundary layer dynamics, and atmospheric transport. Additionally, the relationship between the evolution of the convective boundary layer depth and the CO2 budget was analyzed using the CLASS model with input parameters based on field observations, resulting in insights such as an increase in the range of 25-65 ppm of CO2 during stable nocturnal boundary layers. The observed changes in stable isotopic signatures of air samples allowed for the identification of two main source categories in the city area: fuel combustion and biogenic processes. The δ13C-CO2 values of collected samples suggest that biogenic emissions dominate (up to 60 % of CO2 excess mole fraction) during the growing season, but are reduced by plant photosynthesis during summer afternoons. In contrast, local fossil-fuel CO2 contribution (up to 90 % of excess CO2 mole fraction) from domestic heating, vehicle emissions, and heat and power plants predominantly influence the urban GHG budget during winter. The δ13C-CH4 values indicate anthropogenic sources related to fossil fuel combustion during winter, with values ranging from -44.2 ‰ to -51.4 ‰, while slightly more depleted values, between -47.1 ‰ and -54.2 ‰, reflect a larger input of biological processes in the methane urban budget during summer. Overall, instantaneous and hourly variability of the above-mentioned readings of gas mole fraction and isotopic composition, have shown higher variability than seasonal amplitudes. Hence, respecting this granularity is the key to alignment and understanding significance of such localized atmospheric pollution studies. Additionally, the changing overprint of the system's framework, such as variability of wind and atmospheric layering patterns, weather events, provides context of sampling and data analysis at different frequencies.

European aerosol phenomenology - 8: Harmonised source apportionment of organic aerosol using 22 Year-long ACSM/AMS datasets.

Organic aerosol (OA) is a key component of total submicron particulate matter (PM1), and comprehensive knowledge of OA sources across Europe is crucial to mitigate PM1 levels. Europe has a well-established air quality research infrastructure from which yearlong datasets using 21 aerosol chemical speciation monitors (ACSMs) and 1 aerosol mass spectrometer (AMS) were gathered during 2013-2019. It includes 9 non-urban and 13 urban sites. This study developed a state-of-the-art source apportionment protocol to analyse long-term OA mass spectrum data by applying the most advanced source apportionment strategies (i.e., rolling PMF, ME-2, and bootstrap). This harmonised protocol was followed strictly for all 22 datasets, making the source apportionment results more comparable. In addition, it enables quantification of the most common OA components such as hydrocarbon-like OA (HOA), biomass burning OA (BBOA), cooking-like OA (COA), more oxidised-oxygenated OA (MO-OOA), and less oxidised-oxygenated OA (LO-OOA). Other components such as coal combustion OA (CCOA), solid fuel OA (SFOA: mainly mixture of coal and peat combustion), cigarette smoke OA (CSOA), sea salt (mostly inorganic but part of the OA mass spectrum), coffee OA, and ship industry OA could also be separated at a few specific sites. Oxygenated OA (OOA) components make up most of the submicron OA mass (average = 71.1%, range from 43.7 to 100%). Solid fuel combustion-related OA components (i.e., BBOA, CCOA, and SFOA) are still considerable with in total 16.0% yearly contribution to the OA, yet mainly during winter months (21.4%). Overall, this comprehensive protocol works effectively across all sites governed by different sources and generates robust and consistent source apportionment results. Our work presents a comprehensive overview of OA sources in Europe with a unique combination of high time resolution (30-240 min) and long-term data coverage (9-36 months), providing essential information to improve/validate air quality, health impact, and climate models.

Ultra-Light Airborne Measurement System for Investigation of Urban Boundary Layer Dynamics.

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 (PM10) 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.

Partitioning of atmospheric carbon dioxide over Central Europe: insights from combined measurements of CO2 mixing ratios and their carbon isotope composition.

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.

Diurnal variability of delta13C and delta18O of atmospheric CO2 in the urban atmosphere of Kraków, Poland.

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.