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ABSTRACT. Time series of 6140, 613C, and concentration of atmospheric CO2 covering the last 12 years are available at the Krakow sampling site (southern Poland) representing an urban area exposed to anthropogenic pollution of both local and regional origin. The samples represent continuous monitoring in biweekly intervals. Observations covering the time period 1983-1994 show a linear decrease of the 13(/12( ratio (613C = -9.6%o in Jan. 1983) with a slope of -0.02% a'1. The decreasing tendency in the case of 14C (614C = 227% in January 1983) is weaker with a broad minimum in 1991(614C =124%o) and subsequent gradual increase by ca. 10%o, coinciding with a substantial reduction of coal consumption in Poland (26% reduction in 1991-1994 for heat and electricity production), partly compensated in agglomerations by increased gas consumption. The 12-year record of the CO2 concentration in Krakow points to a constant value fluctuating at a high level (average: 373 ppmv) reaching a maximum yearly average of 376 ppmv. These carbon isotope signatures were used for the separation of fossils from biogenic and "background" components, reflecting the strength of relevant sources. The monthly mean of the fossil component varies from ca. 10 ppmv in June to 27.5 ppmv in March while the yearly mean decreased ca. 16 ppmv since 1991.

Abstract:A comprehensive study of a sandy aquifer of deltaic origin in southern Poland included water chemistry, isotopes, dissolved trace gases and transport modelling. Tritium, sulphur hexafluoride (SF 6 ) and freons (F-11, F-12 and F-113) showed the presence of modern waters in the recharge areas and shallow confined parts of the aquifer. The presence of older Holocene waters farther from the recharge areas was indicated by lack of 3 H, SF 6 contents Ä0Ð02 fmol l 1 and relatively low 14 C values. The discharge from the system is by upward seepage in the valley of a major river. Pre-Holocene waters of a cooler climate, identified on the basis of υ 18 O, υ 2 H, 14 C, Ne and Ar data, were found in some distant wells. Concentrations of N 2 , Ne and Ar determined by gas chromatography were used for calculating the noble gas temperatures, air excess needed for correction of SF 6 , and nitrogen content released by denitrification process. The time series of 3 H content available for some wells supplied quantitative information on age distributions and the total mean ages of flow through the unsaturated and saturated zones. The derived 3 H age distributions turned out to be very wide, with mean values in the range of about 30 to 160 years. For each well with determined 3 H age, the SF 6 data showed either a lower age range or the possibility of a lower age as expected due to shorter travel times of SF 6 through the unsaturated zone, which most probably also resulted in different types of age distributions of these tracers. Freons appeared to be of little use for individual age determinations. A quantitative estimation of two-component mixing from SF 6 -3 H relations is not possible unless the travel time of 3 H through the unsaturated zone is comparable to that of SF 6 . The ratio of integrals of the response function over the age range with tracer and the whole response function yields the ratio of water with tracer to total flow of water. That ratio is a tracer-dependent function of time. Transport modelling of SF 6 tracer done with MT3D code yielded initially large discrepancies between calculated and measured tracer concentrations. Some discrepancies remained even after calibration of the transport model with SF 6 . Simulation of tritium contents with a calibrated transport model yielded reasonable agreement with measured contents in some wells and indicated a need for further investigations, particularly in the eastern part of the aquifer. The existence of distinct hydrochemical zones is consistent with the tracer data; young waters with measurable 3 H and SF 6 contents are aerobic and of HCO 3 -Ca or HCO 3 -SO 4 -Ca types. Slightly elevated Na and Cl contents, as well as the highest concentrations of SO 4 and NO 3 within this zone are due to anthropogenic influences. Anaerobic conditions prevail in the far field, under the confining cover, where pre-bomb era Holocene waters dominate. In that zone, dissolved oxygen, NO 3 and U contents are reduced, and Fe, Mn and NH 4 contents increase. In the third zone, earl...

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Time series are presented of radiocarbon and 13C contents in atmospheric carbon dioxide over eastern Europe (southern Poland), covering the periods 1983–1994 and 2000–2004. The carbon isotope composition was measured in biweekly composite samples of atmospheric CO2, collected about 20 m above the local ground level. The data for 2 observational sites are presented: i) city of Kraków (50°04′N, 19°55′E; 220 m asl; for 1983–1994 and 2000–2004); and ii) Kasprowy Wierch, Tatra Mountains (49°14′N, 19°56′E; 1989 m asl; for 2000–2004). The latter site is considered a regional reference station, relatively free of anthropogenic influences. During the period 1983–1994, observations in the Kraków area revealed a gradual decrease of 14C content with a broad minimum around 1991 and a small increase by about 10% in the subsequent years. δ13C also changes with time, showing a decreasing trend from approximately −9.6% in 1983, with a slope of −0.02%/yr. The observed trends for both isotopes coincide well with a substantial reduction of coal consumption in Poland and partial replacement of coal by natural gas, especially in urban regions. After 2000, the δ13C slightly increases, reaching a mean value of −10% in 2004, while Δ14C is below the reference level by ∼3.5%. Observations at Kasprowy Wierch (regional reference station) also reflect a diminishing input of fossil carbon into the regional atmosphere. The fossil component in atmospheric CO2, calculated with the aid of 14C data available for the 2 study periods, shows a reduction of anthropogenic input by a factor of 2, which is confirmed by annual statistics of coal consumption.

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.

Southern Poland is home to numerous large mining and energy industry facilities, which consume relatively great amounts of fossil fuels. Temporal and spatial distribution of CO2 emissions to the atmosphere were estimated on the basis of 13C and 14C isotope measurements in atmospheric CO2 and in α-cellulose from pine tree rings. The Suess effect was evaluated in the atmospheric CO2 from the High Tatra Mountains (Kasprowy Wierch) and the urban area (Kraków), as well as in tree rings from Niepołomice Forest near Kraków. Two different models were used to estimate the emission component recorded in tree ring δ13C on the background of climatic changes.