δ(34)S values and S concentrations in native and transplanted Pleurozium schreberi in a heavily industrialised area.

Sulphur is an element found in surplus in anthropogenic areas and one of the minerals responsible for the development of acid rains. The analysis of stable S isotopes provides a powerful tool for studying various aspects of the biogeochemical circulation of sulphur. δ(34)S values and S concentrations were determined in a 90-day experiment with the native moss Pleurozium schreberi from rural, urban and industrial sites in Upper Silesia in southern Poland. At the same time P. schreberi from a control site was transplanted to the same rural, urban and industrial sites and the δ(34)S values and S concentrations were determined in the same 90-day experiment. (34)S enrichment (up to 4.7‰) in the mosses tested indicates that these plants responded to environmental pollution stress. Sulphur isotopic composition in the transplanted P. schreberi was related to S concentrations in this species after 90 days of the experiment. Higher δ(34)S values and S concentrations were noted in native mosses than in those transplanted from rural and urban sites while an opposite situation was reported in industrial sites. The transplanted P. schreberi was a better sulphur bioindicator than the native moss in more polluted industrial sites and worse in less polluted rural and urban sites.

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.

Comparison of active and passive methods for atmospheric particulate matter collection: From case study to a useful biomonitoring tool.

In this study we conducted air pollution monitoring using three different methods: active monitoring with the use of high volume aerosol sampler and biomonitoring with the use of lichens and spider webs. All of these monitoring tools were exposed to air pollution in Legnica city, a region of Cu-smelting in the SW Poland, which is well known for exceeding the environmental guidelines. Quantitative analysis was carried out for the particles collected by the three selected methods and concentrations of seven selected elements (Zn, Pb, Cu, Cd, Ni, As, Fe) were obtained. Concentrations found in lichens and in spider webs were directly compared and indicated significant differences between them, with higher amounts noted for spider webs. Then, in order to recognize the main pollution sources the principal component analysis was conducted and obtained results were compared. It resulted that spider webs and aerosol sampler, despite different mechanisms of accumulation, show similar sources of pollution - in this case - copper smelter. Additionally, the HYSPLIT trajectories and the correlations between metals in the aerosol samples also confirmed that this is the most probable source of pollution. This study can be considered innovative as these three air pollution monitoring methods were compared, which has never been conducted before, and their comparison gave satisfying results.

The multi-isotope biogeochemistry (S, C, N and Pb) of Hypogymnia physodes lichens: air quality approach in the Swietokrzyski National Park, Poland.

The isotope biogeochemistry of bioindicators has widely demonstrated its added value in environmental issues by allowing to precisely identify sources of contamination. Most of the studies are based on studying one or two isotope systematics. Here, we are presenting an innovative multi-proxy approach that combines chemistry with both stable (C, S, N) and radiogenic (Pb) isotope systematics. Using Hypogymnia physodes bioindicators, we evaluated air quality in the complex environment of the Swietokrzyski National Park (SNP, Poland) with the ultimate objective of isotopically identifying the sources responsible for the observed contamination. Combining the isotope systematics showed that home heating is a major source of contamination in winter, whereas the contribution of road traffic increases during the summer. Pb isotope ratios identified industrial activities as the major source of this metal in the atmosphere.

The assessment of effectiveness of SEM- EDX and ICP-MS methods in the process of determining the mineralogical and geochemical composition of particulate matter deposited on spider webs.

Air pollution can be monitored using many different methods. In this paper, we aimed to test and validate two analytical techniques based on complex mineralogical and geochemical analyses with the use of spider webs as a passive sampler. The samples of spider webs were collected in 2018 in polluted areas in the vicinity of the copper smelter Glogów (Poland). Samples were analysed using scanning electron microscopy with energy dispersive x-ray analysis (SEM-EDX) to obtain not only the information about the form and size of studied particles but also their origin (anthropogenic or terrigenous). Geochemical analysis was performed using inductively coupled plasma mass spectrometry (ICP-MS), providing the total amount of chosen and potentially toxic elements. The frequency of metal occurrence in atmospheric particles identified with the use of SEM-EDX was compared with the results from ICP-MS and recalculated into the percentage of contribution. A significant correlation between chemical and mineralogical composition was found demonstrating that the phases and minerals were correctly recognised and properly divided into groups. For elements such as Pb, Zn, and Cu, which are the major contaminants in the study area, the validation of the method gave good results, revealing the convergence of results for most sampling points. Finally, our study showed that the results obtained by SEM-EDX analysis can be comparable to quantitative results (ICP-MS analysis).

Isotopic composition of sulphates from meteoric precipitation as an indicator of pollutant origin in Wroclaw (SW Poland).

This paper describes the results of isotopic analyses of (i) hydrogen and oxygen in water (delta DH2O and delta18OH2O ) and (ii) sulphur and oxygen in sulphates (delta34Ssulphate and delta18Osulphate) from atmospheric precipitation collected within a one-year period between 25 May 2004 and 25 May 2005 in Wroclaw (SW Poland). The resulting equation of Local Meteoric Water Line for Wroclaw is delta D=6.373xdelta18O-0.047, (r2=0.97, n=32). The delta34Ssulphate varies from 1.1 to 4.2 per thousand (with an average of 2.5 per thousand), delta18Osulphate varies from 9.0 to 16.7 per thousand (with an average of 13.8 per thousand) and delta18OH2O varies from-0.8 to-16.3 per thousand (with an average of-8.2 per thousand). The above results indicate two main sources of sulphates in Wroclaw precipitation: (i) low-temperature secondary sulphates forming in situ in Wroclaw from the atmospheric SO2 as well as precipitation water (heterogeneous and homogeneous pathways oxidation) and (ii) high-temperature primary sulphates forming in rapid high-temperature hydratation of SO3- in an immediate proximity of industrial chimneys. We hypothesise that the secondary low-temperature type of sulphates is probably formed from the local sulphur and oxygen reservoirs, whereas the primary high-temperature type is allochthonous and it is probably transported from industrial areas located outside of Wroclaw.

The coupled study of metal concentrations and electron paramagnetic resonance (EPR) of lichens (Hypogymnia physodes) from the Swietokrzyski National Park-environmental implications.

SO2, NOx, and metals (including Cd, Cu, Pb, Zn, Mn, Mg, Fe) present in airborne particulate matter are a major threat to preserving good air quality. The complicated pathways and transformation processes that can change their physical/chemical state in the atmosphere renders identifying their origin extremely difficult. With the objective of alleviating this difficulty, we identified and characterized potential local and regional sources of atmospheric pollutants using bioindicators (Hypogymnia physodes) from the Swietokrzyski National Park (SE Poland): 20 lichen samples were collected during winter (February; heating period) and summer (June; vegetative period) seasons and analyzed for metal contents and free radicals concentrations. Our results indicate that the highest gaseous pollutant levels were observed during the heating season, along roads (NO2) and at the highest elevation (SO2). The semiquinone/phenoxyl radical concentrations correlated during the heating season with the atmospheric SO2: ln (free radicals concentrations) = 0.025 SO2atmosphere + 39.11. For Mn/Fe ≥ 2, the electron paramagnetic resonance (EPR) spectra presented a hyperfine splitting. Results showed that since 1994 metal concentrations increased for Cd, Mn, and Mg, Fe remained somewhat constant for Zn and Cu but slightly decreased for Pb, in agreement with the phasing out of lead in gasoline. Finally, a principal component analysis (PCA) identified two main factors controlling variability within the analyzed parameters: air pollutants transport over long distances and local fuel combustion by both transport and home heating.

Carbon and nitrogen isotope analyses coupled with palynological data of PM10 in Wroclaw city (SW Poland)--assessment of anthropogenic impact.

We have applied both palynological and carbon and nitrogen isotopic analyses of PM10 (particulate matter with a diameter of 10 µm or less) to trace its origin and to assess the anthropogenic impact for the area under study. The PM10 samples were collected in Wroclaw (SW Poland) by the Regional Inspectorate for Environment Protection during the year 2007. The usefulness of the palynological observations in the case of PM10 is much lower than that for total suspended particles due to the resolution of absorbed particles, but is still helpful for distinguishing C(3)/C(4) plants that indicate long-distance transport of pollutants. The δ(13)C(PM10) values varied seasonally from-26.9 to-25.1‰. The δ(15)N(PM10) values showed chaotic fluctuations and varied from 5.0 to 13.7‰. Our results indicated that during the heating period, the PM10 particles in Wroclaw are derived mainly from local home heaters, whereas in the growing period, PM10 particles are derived from local transport and are partially generated by the industrial application of coal combustion outside the city of Wroclaw.

Carbon isotope signature of dissolved inorganic carbon (DIC) in precipitation and atmospheric CO2.

This paper describes results of chemical and isotopic analysis of inorganic carbon species in the atmosphere and precipitation for the calendar year 2008 in Wroclaw (SW Poland). Atmospheric air samples (collected weekly) and rainwater samples (collected after rain episodes) were analysed for CO2 and dissolved inorganic carbon (DIC) concentrations and for δ13C composition. The values obtained varied in the ranges: atmospheric CO2: 337-448 ppm; δ13CCO2 from -14.4 to -8.4‰; DIC in precipitation: 0.6-5.5 mg dm(-3); δ13CDIC from -22.2 to +0.2‰. No statistical correlation was observed between the concentration and δ13C value of atmospheric CO2 and DIC in precipitation. These observations contradict the commonly held assumption that atmospheric CO2 controls the DIC in precipitation. We infer that DIC is generated in ambient air temperatures, but from other sources than the measured atmospheric CO2. The calculated isotopic composition of a hypothetical CO2 source for DIC forming ranges from -31.4 to -11.0‰, showing significant seasonal variations accordingly to changing anthropogenic impact and atmospheric mixing processes.