Maciej Górka

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 Wrocław (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.

Carbon and nitrogen isotope analyses coupled with palynological data of PM10 in Wrocław 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 Wrocław (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 C3/C4 plants that indicate long-distance transport of pollutants. The δ13C(PM10) values varied seasonally from−26.9 to−25.1‰. The δ15N(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 Wrocław 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 Wrocław.

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

This paper describes the results of isotopic analyses of (i) hydrogen and oxygen in water (δ D and δ18O ) and (ii) sulphur and oxygen in sulphates (δ34Ssulphate and δ18Osulphate) from atmospheric precipitation collected within a one-year period between 25 May 2004 and 25 May 2005 in Wrocław (SW Poland). The resulting equation of Local Meteoric Water Line for Wrocław is δ D=6.373×δ18O−0.047, (r 2=0.97, n=32). The δ34Ssulphate varies from 1.1 to 4.2‰ (with an average of 2.5‰), δ18Osulphate varies from 9.0 to 16.7‰ (with an average of 13.8‰) and δ18O varies from−0.8 to−16.3‰ (with an average of−8.2‰). The above results indicate two main sources of sulphates in Wrocław precipitation: (i) low-temperature secondary sulphates forming in situ in Wrocław 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 SO 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 Wrocław. †Revised version of a paper presented at the 9th. Symposium of the European Society for Isotope Research (ESIR), 23 to 28 June 2007, Cluj-Napoca, Romania.

δ34s 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.

The coupled study of metal concentrations and electron paramagnetic resonance (EPR) of lichens (Hypogymnia physodes) from the Świętokrzyski 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 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 (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, Nitrogen and Sulphur concentration and δ13C, δ15N values in Hypogymnia physodes within the montane area – preliminary data

Abstract The contribution of C, N and S, as well as the isotopic composition of C and N of atmospheric pollutants, are assumed to be reflected in the organic compounds inbuilt into the lichen thallus. The chemical and isotopic analyses were carried out on lichen Hypogymnia physodes samples gathered from Picea abies and Larix decidua, collected in 13 sampling points located in Karkonoski National Park and its closest vicinity in 2011. The results for %C, %N and %S varied from 43.44 to 46.79%, from 0.86 to 1.85% and from 0.07 to 0.27 %, respectively. The δ13C values ranged from −26.6 to −24.6‰, whereas δ15N values varied from −13.0 to −6.8‰. The ranges in isotope composition suggest different sources of C and N for Karpacz compared to the remaining sampling sites. For Karpacz, the δ13C values suggest (in case the fractionation product-substrate does not exist and Δ=0) that the dominant sources are coal combustion processes, whereas for remaining sampling points, the δ13C values are ambiguous and are masked by many mixed natural and anthropogenic processes. With the same assumption that Δ=0, the δ15N values suggest that transport is not a dominant source of nitrogen within Karpacz city. Moreover, in this study we tested the possible fractionation (Δ) for carbon and nitrogen, assuming that within the investigated area, the source of carbon is probably CO2 and/or DIC (HCO3−) dissolved in precipitation, while the source of nitrogen is NOx and/or NO3− ion. The calculated fractionation factors were: (i) for gaseous carbon compounds ΔCO2-Corg value from −13.4 to −11.4‰, whereas for the ions form ΔHCO3−-Corg value from −16.6 to −14.6‰, (ii) for nitrogen gaseous compounds ΔNOx-Norg value between apx. −17 and −5‰, whereas for the ions form ΔNO3−-Norg value between −9.9 and −3.7‰.

Preliminary results of sulphur isotope studies on sulfides from selected ore deposits and occurrences in the Karkonosze–Izera Massif (the Sudety Mts., Poland)

Abstract Preliminary sulphur isotope data are presented for selected ore deposits and occurrences in the Karkonosze-Izera Massif, namely, polymetallic mineralization sites at Budniki, Ciechanowice, Izerskie Garby and Sowia Dolina, and the pyrite deposit at Wieściszowice. The data reveal two populations of δ34S values: from 2.74 to 3.95‰ (pyrrhotites and pyrites in Sowia Dolina, and some pyrites in Wieściszowice) and from 0.79 to 1.8‰ (pyrites in Budniki, Ciechanowice and Izerskie Garby, and some pyrites from Wieściszowice). All of the data are indicative of endogenic sulphur typical of hydrothermal mineralization despite the genetic differences between the sites.