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

SO(2), NO(x), 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 Świętokrzyski 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 (NO(2)) and at the highest elevation (SO(2)). The semiquinone/phenoxyl radical concentrations correlated during the heating season with the atmospheric SO(2): ln (free radicals concentrations) = 0.025 SO(2atmosphere) + 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.