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Concentration of radon (222Rn) in the near-ground atmosphere has been measured quasi-continuously from January 2005 to December 2009 at two continental sites in Europe: Heidelberg (south-west Germany) and Krakow (southern Poland). The atmosphere was sampled at ca. 30 and 20 m above the local ground. Both stations were equipped with identical instruments. Regular observations of 222Rn were supplemented by measurements of surface fluxes of this gas in the Krakow urban area, using two different approaches. The measured concentrations of 222Rn varied at both sites in a wide range, from less than 2.0 Bq m−3 to approximately 40 Bq m−3 in Krakow and 35 Bq m−3 in Heidelberg. The mean 222Rn content in Krakow, when averaged over the entire observation period, was 30% higher than in Heidelberg (5.86 ± 0.09 and 4.50 ± 0.07 Bq m−3, respectively). Distinct seasonality of 222Rn signal is visible in the obtained time series of 222Rn concentration, with higher values recorded generally during late summer and autumn. The surface 222Rn fluxes measured in Krakow also revealed a distinct seasonality, with broad maximum observed during summer and early autumn and minimum during the winter. When averaged over a 5-year observation period, the night-time surface 222Rn flux was equal to 46.8 ± 2.4 Bq m−2 h−1. Although the atmospheric 222Rn levels at Heidelberg and Krakow appeared to be controlled primarily by local factors, it was possible to evaluate the "continental effect" in atmospheric 222Rn content between both sites, related to gradual build-up of 222Rn concentration in the air masses travelling between Heidelberg and Krakow. The mean value of this build-up was equal to 0.78 ± 0.12 Bq m−3. The measured minimum 222Rn concentrations at both sites and the difference between them was interpreted in the framework of a simple box model coupled with HYSPLIT (Hybrid Single Particle Lagrangian Integrated Trajectory) analysis of air mass trajectories. The best fit of experimental data was obtained for the mean 222Rn flux over the European continent equal to 52 Bq m−2 h−1, the mean transport velocity of the air masses within the convective mixed layer of the planetary boundary layer (PBL) on their route from the Atlantic coast to Heidelberg and Krakow equal to 3.5 m s−1, the mean rate constant of 222Rn removal across the top of the PBL equal to the 222Rn decay constant and the mean height of the convective mixed layer equal to 1600 m.

Air quality is of large concern in the city of Krakow, southern Poland. A comprehensive study was launched by us in which two PM fractions (PM 1 and PM 10 ) were sampled during 1-year campaign, lasting from April 21, 2018 to March 19, 2019. A suite of modern analytical methods was used to characterize the chemical composition of the collected samples. The contents of 14 sugars, sugar alcohols and anhydrosugars, 16 polycyclic aromatic hydrocarbons, selected metals and non-metals and ions were analyzed, in addition to organic and elemental carbon content. The carbon isotope composition in both analysed PM fractions, combined with an isotope-mass balance method, allowed to distinguish three main components of carbonaceous emissions in the city: (1) emissions related to combustion of hard coal, (2) emissions related to road transport, and (3) biogenic emissions. The heating season emissions from coal combustion had the biggest contribution to the reservoir of carbonaceous aerosols in the PM 10 fraction (44%) and, together with the biogenic emission, they were the biggest contributors to the PM 1 fraction (41% and 44%, respectively). In the non-heating season, the dominant source of carbon in PM 10 and PM 1 fraction were the biogenic emissions (48 and 54%, respectively)., (© 2024. The Author(s).)

Rationale: The presence of substantial amounts of dissolved salts creates serious difficulties in isotope analyses of water samples using conventional isotope ratio mass spectrometry. Although nowadays laser-based instruments are increasingly used for this purpose, a comprehensive assessment of isotope effects associated with direct analyses of aqueous saline solutions using this technology is lacking., Methods: Here we report the results of laboratory experiments aimed at quantifying isotope effects associated with direct, δ 2 H, δ 18 O and δ 17 O analyses of single-salt solutions and double-salt mixtures prepared with a water of known isotopic composition. Three single-salt solutions (NaCl, CaCl 2 and MgSO 4 ) and two double-salt mixtures (NaCl + CaCl 2 and NaCl + MgSO 4 ) were prepared and investigated for a wide range of molalities. The triple-isotope composition of the prepared solutions was analysed with the aid of a Picarro L2140-i Cavity Ring-Down Spectroscopy analyser., Results: The NaCl and CaCl 2 solutions revealed small negative salt effects, independent of molality and comparable with measurement uncertainty. The MgCl 2 solution showed the highest salt effects, reaching saturated solution ca. +2.7‰ ( 2 H), -3.5‰ ( 18 O) and -1.7‰ ( 17 O). Salt effects for the double-salt mixtures generally mirrored the effects observed for the single-salt solutions. The observed salt effects are discussed in the context of processes occurring during the injection of the salt solutions into the vaporizer unit of the CRDS analyser., Conclusions: The presented study has demonstrated feasibility of direct, triple-isotope analyses of aqueous salt solutions using a Picarro L2140-i CRDS analyser for a broad range of salinities up to saturated conditions. Large uncertainties of 17 O-excess determinations for solutions forming hydrated salts preclude the use of this parameter for interpretation purposes., (© 2023 The Authors. Rapid Communications in Mass Spectrometry published by John Wiley & Sons Ltd.)

Here, we present the results of a comprehensive study of air quality in two tunnels located in the city of Krakow, southern Poland. The study comprised three PM fractions of suspended particulate matter (PM 1 , PM 2.5 and PM 10 ) sampled during campaigns lasting from March 14 to April 24, 2016 and from June 28 to July 18, 2016, in the road tunnel and the tram tunnel, respectively. The collected samples had undergone comprehensive chemical, elemental and carbon isotope analyses. The results of these analyses gave the basis for better characterization of urban transport as a source of air pollution in the city. The concentrations of particulate matter varied, depending on the analysed PM fraction and the place of sampling. For the tram tunnel, the average concentrations were 53.2 µg·m -3 (PM 1 ), 73.8 µg·m -3 (PM 2.5 ), 96.5 µg·m -3 (PM 10 ), to be compared with 44.2 µg·m -3 , 137.7 µg·m -3 , 221.5 µg·m -3 , respectively, recorded in the road tunnel. The isotope-mass balance calculations carried out separately for the road and tram tunnel and for each PM fraction, revealed that 60 to 79% of carbon present in the samples collected in the road tunnel was associated with road transport, to be compared with 15-33% obtained in the tram tunnel. The second in importance were biogenic emissions (17-21% and 41-49% in the road and tram tunnel, respectively. Sixteen different polycyclic aromatic hydrocarbons (PAHs) have been identified in the analysed samples. As expected, much higher concentrations of PAHs were detected in the road tunnel when compared to the tram tunnel. Based on the analysed PAHs concentrations, health risk assessment was determined using 3 different types of indicators: carcinogenic equivalent (CEQ), mutagenic equivalent (MEQ) and toxic equivalent (TEQ)., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Competing Interests: Declaration of competing interest The authors declare no competing financial interests or personal relationships which could influence the reported work.

The procedure of calibrating in-house water standards suitable for routine analyses of triple-isotope composition of water samples using Picarro L2140- i CRDS analyser is presented and discussed. Such standards are indispensable for achieving and maintaining high quality of isotope analyses of water in terms of their precision and accuracy. A set of seven different water standards consisting of three in-house standards and four secondary standards commercially available was calibrated against VSMOW2/SLAP2 primary reference materials. The calibrated standards cover a wide range of isotopic composition, with δ values ranging from close to zero to the values comparable with SLAP2. The apparent consistency of the calibrated values of δ 2 H, δ 18 O and d -excess with corresponding certified values for commercially available USGS47-50 standards and the consistency of the calibrated values of δ 17 O and Δ 17 O with its literature values for USGS47-48 standards confirm the high quality of the performed calibration. Moreover, the calibration exercise allowed to obtain δ 17 O and Δ 17 O values for USGS49 and USGS50 standards, not reported so far.

A thorough evaluation of measurement uncertainty together with control of short-term and long-term precision of measurements should be a basis of any successful quality assurance/quality control (QA/QC) strategy aimed at maintaining a high quality of the analytical process. Here we present the results of a comprehensive assessment of the analytical performance of a Picarro L2140-i CRDS laser spectrometer analysing δ 2 H, δ 18 O and δ 17 O in water. The assessment is based on results obtained during 15 months of continuous operation of this instrument (February 2017 to May 2018). The short-term precision of measured and derived quantities was 0.11, 0.036, 0.028, 0.23 ‰ and 11 per meg, for δ 2 H, δ 18 O, δ 17 O, d-excess and Δ 17 O, respectively, and is comparable to the precision reported by the manufacturer. The long-term precision of the L2140-i, defined as standard uncertainty of the time series of 153 analyses of a laboratory standard conducted throughout 15 months, was roughly two times lower (0.24, 0.053, 0.038, 0.37 ‰ and 21 per meg, for δ 2 H, δ 18 O, δ 17 O, d-excess and Δ 17 O). In-depth assessment of the measurement uncertainty of a single analysis revealed that assigned uncertainty of the calibration standards is an important component of the uncertainty budget, especially in case of δ 2 H analysis.

As urban atmosphere is depleted of (13)CO2, its imprint should be detectable in the local vegetation and therefore in its CO2 respiratory emissions. This work was aimed at characterising strength and isotope signature of CO2 fluxes from soil in urban areas with varying distances from anthropogenic CO2 emissions. The soil CO2 flux and its δ(13)C isotope signature were measured using a chamber method on a monthly basis from July 2009 to May 2012 within the metropolitan area of Krakow, Southern Poland, at two locations representing different levels of anthropogenic influence: a lawn adjacent to a busy street (A) and an urban meadow (B). The small-scale spatial variability of the soil CO2 flux was also investigated at site B. Site B revealed significantly higher summer CO2 fluxes (by approximately 46 %) than site A, but no significant differences were found between their δ(13)CO2 signatures.

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.