Spatial and temporal trends in δ66Zn and 206Pb/207Pb isotope ratios along a rural transect downwind from the Upper Silesian industrial area: Role of legacy vs. present-day pollution.

Transect sampling is an under-exploited tool in isotope studies of atmospheric pollution. Few studies have combined Zn and Pb isotope ratios to investigate whether atmospheric pollution at a receptor site is dominated by a different anthropogenic source of each of these toxic elements. It has been also unclear whether pollution abatement strategies in Central Europe have already resulted in regionally well-mixed background isotope signature of atmospheric Zn and Pb. Zinc and lead isotope ratios were determined in snow collected along a rural transect downwind from the Upper Silesian industrial area (southern Poland). Spatial and temporal gradients in δ66Zn and 206Pb/207Pb ratios at four sites were compared with those of ore and coal collected in eight Czech and Polish mining districts situated at distances of up to 500 km. Snow pollution was extremely high 8 km from Olkusz in 2011 (1670 µg Zn L-1; 240 µg Pb L-1), sharply decreased between 2011 and 2018, and remained low in 2019-2021. Snow pollution was lower at sites situated 28-68 km from Olkusz. Across study sites, mean δ66Zn and 206Pb/207Pb ratios of snow were -0.13‰ and 1.155, respectively. With an increasing distance from Olkusz, the δ66Zn values first increased and then decreased, while the 206Pb/207Pb ratios first decreased and then increased. The δ66Zn values in snow plotted closer to those of Upper Silesian ores (-0.20‰) than to the δ66Zn values of Upper Silesian stone coal (0.52‰), showing predominance of smelter-derived over power-plant derived Zn pollution. The 206Pb/207Pb ratios of Upper Silesian coal (1.171) and Upper Silesian ores (1.180) were higher compared to those of snow. A206Pb/207Pb vs.208Pb/207Pb plot identified legacy pollution from leaded gasoline as the low-radiogenic mixing end-member. Across the transect sites, only the last sampling campaign exhibited a high degree of isotope homogenization for both Zn and Pb.

Cadmium contents of vertically and horizontally deposited winter precipitation in Central Europe: Spatial distribution and long-term trends.

Cadmium (Cd) and its forms has recently been a focus of attention due to its toxic effects on human health and the environment. We evaluated the atmospheric deposition of Cd during three consecutive winter seasons (2009-2011) at 10 mountain-top locations in the Czech Republic along the borders with Poland, Germany, Austria and Slovakia. Cadmium concentrations of soluble and insoluble forms in both horizontal (rime) and vertical (snow) deposition were determined using sector-field ICP-MS. Across the sites, 94% of the total winter Cd deposition occurred in the soluble (environmentally available) Cd form. Mean concentrations of soluble Cd in rime were six times higher than in snow (398 vs. 66 ng L-1). Vertical deposition contributed as much as 41% to the total winter Cd input. Between-site variability in Cd deposition was large, ranging between 13 and 108 µg m-2 winter-1. Overall, Cd concentrations in winter deposition did not reach the drinking water limits and did not pose a direct threat for human health. Long-term trends (1996-2017) in winter Cd deposition were evaluated at six GEOMON sites (a monitoring network of small forested catchments). Since 1996, Cd input in winter atmospheric deposition decreased by 73-93%. Simultaneously, we found declines in between-site variability in winter Cd inputs. The highest recent winter Cd inputs were found at sites located in the northeast of the country. A north-south pollution gradient, which has frequently been mentioned in the literature, was not observed, with both northwestern sites and southern sites being among those with the lowest Cd pollution. Backward trajectories of the HYSPLIT model for fresh snow samples identified Poland and Germany as major transboundary Cd pollution sources for the Czech Republic.

Atmospheric metal pollution records in the Kovárská Bog (Czech Republic) as an indicator of anthropogenic activities over the last three millennia.

Three peat cores were extracted from the Kovárská Bog in the central Ore Mountains to study anthropogenic pollution generated by mining and metallurgy. The core profiles were 14C dated, and concentrations of selected elements were determined by ICP MS and HG-AAS. Principal component analysis indicated that Pb, Cu, As and Ag may be useful elements for the reconstruction of historical atmospheric pollution. Total and anthropogenic accumulation rates (ARs) of Pb, Cu and As estimated for the last ca. 3500years showed similar chronologies, and revealed twelve periods of elevated ARs of Pb, As and Cu related to possible mining and metallurgic activities. In total, four periods of elevated ARs of Pb, Cu and As were detected during the Middle and Late Bronze Ages, including a distinct Late Bronze Age pollution event between 1030BCE and 910BCE. The Iron Age included three episodes of increased ARs of Pb and As; the first and the most distinctive episode, recorded between 730 and 440BCE, was simultaneous with the Bylany culture during the Hallstatt Period. The Roman Age was characterized by one pollution event, two events were detected in the Middle Ages, and the last two during the modern period. Enhanced element ARs in the late 12th and 15th centuries clearly documented the onset of two periods of intense mining in the Ore Mountains. Metal ARs culminated in ca. 1600CE, and subsequently decreased after the beginning of the Thirty Years' War. The last boom of mining between 1700CE and 1830CE represented the last period of important metallurgical operations. Late Medieval and modern period metal ARs are in good agreement with written documents. Earlier pollution peaks suggest that local metal production could have a much longer tradition than commonly believed; however, archaeological or written evidence is scarce or lacking.

Bagged neural network model for prediction of the mean indoor radon concentration in the municipalities in Czech Republic.

The purpose of the study is to determine radon-prone areas in the Czech Republic based on the measurements of indoor radon concentration and independent predictors (rock type and permeability of the bedrock, gamma dose rate, GPS coordinates and the average age of family houses). The relationship between the mean observed indoor radon concentrations in monitored areas (∼22% municipalities) and the independent predictors was modelled using a bagged neural network. Levels of mean indoor radon concentration in the unmonitored areas were predicted using the bagged neural network model fitted for the monitored areas. The propensity to increased indoor radon was determined by estimated probability of exceeding the action level of 300Bq/m3.

Using S and Pb isotope ratios to trace leaching of toxic substances from an acid-impacted industrial-waste landfill (Pozdatky, Czech Republic).

Slightly elevated concentrations of toxic species in waters sampled in the surroundings of a leaky landfill may be both a sign of an approaching contaminant plume, or a result of water-rock interaction. Isotopes can be instrumental in distinguishing between anthropogenic and geogenic species in groundwater. We studied sulfur and lead isotope ratios at an abandoned industrial-waste landfill, located in a densely populated part of Central Europe. Stable isotope variability in space and time was used to follow the movement of a groundwater plume, contaminated with toxic metals (Cd, Cr, Be), in fractured granitoids. Toxic metals had been mobilized from industrial waste by a strong pulse of sulfuric acid, also deposited in the landfill. Both tracers exhibited a wide range of values (δ(34)S between +2.6 and +18.9‰; (206)Pb/(207)Pb between 1.16 and 1.39), which facilitated identification of mixing end-members, and made it possible to assess the sources of the studied species. In situ fractionations did not hinder source apportionment. Influx of contaminated groundwater was observed neither in irrigation wells in a nearby village, nor at distances greater than 300 m from the landfill. Combination of stable isotope tracers can be used as part of an early-warning system in landscapes affected by landfills.

Experimental evidence for mobility/immobility of metals in peat.

The biogeochemical cycles of most toxic metals have been significantly altered by anthropogenic activities. Anaerobic, rain-fed organic soils are believed to record historical changes in atmospheric pollution. Suspected postdepositional mobility of trace elements, however, hinders the usefulness of peat bogs as pollution archives. To lower this uncertainty, we quantified the mobility of six trace metals in peat during an 18-month field manipulation. A replicated, reciprocal peat transplant experiment was conducted between a heavily polluted and a relatively unpolluted peatland, located 200 km apart in the Czech Republic (Central Europe). Both peatlands were Sphagnum-derived, lawn-dominated, and had water table close to the surface. A strikingly different behavior was observed for two groups of elements. Elements of group I, Fe and Mn, adjusted their abundances and vertical patterns to the host site, showing an extremely high degree of mobility. In contrast, elements of group II, Pb, Cu, Zn, and Ti, preserved their original vertical patterns at the host site, showing a high degree of immobility. Our experimental results suggest that not just lead, but also copper and zinc concentration profiles in peat are a reliable archive of temporal pollution changes within a wide pH range (2.5-5.8).

Cross-border radon index map 1:100 000 Lausitz - Jizera - Karkonosze - Region (northern part of the Bohemian Massif).

The first cross-border map describing the radon (Rn) risk from bedrock was assembled in the northern part of the Bohemian Massif at a scale 1:100 000. The map covers the area of Lausitz (Germany), Karkonosze (Czech Republic and Poland) and Jizera (Czech Republic). The map is based on 818 measurements of soil gas Rn in rock types of Precambrian to Mesozoic age with variable geology. Geographic information system (GIS) processing enabled a good coincidence of soil gas Rn concentrations between data from all three countries in lithologically adjacent rock types as well as the direct correlation to georeferenced indoor Rn values, which was tested using the Czech indoor Rn data. The method of data processing can contribute to assembling the European Geogenic Radon Map.

Mobility of trace metals in pore waters of two Central European peat bogs.

Vertical peat profiles can only be used as archives of past changes in pollution levels if atmogenic elements are immobile after their burial. For mobile elements, similar pore-water concentrations can be expected at different peat depths. Concentrations of Pb, Cu, Zn, Cr, Mn, Fe, Co and Cd were determined in surface bog water and bog pore water 40 cm below surface in two Sphagnum-dominated peat bogs in the Czech Republic. Velke jerabi jezero (VJJ) is an upland bog located in an industrial area, Cervene blato (CB) is a lowland bog located in a rural area. Metal concentrations were monitored seasonally over 3 years (2002--2005) at both sites. Higher concentrations of Pb, Cu, Zn, Cr and Cd and lower concentrations of Mn, Fe and Co were found at the less polluted CB compared to VJJ. No clear-cut seasonality was observed in metal concentrations in bog waters, despite seasonal differences in industrial emission rates of pollutants (more coal burning in winter than in summer). This contrasts with an earlier observation of distinct seasonality in sulfate concentration and isotope composition in these stagnating bog waters. Peat substrate 40 cm below current bog surface represented pre-industrial low-pollution environment, yet pore waters at such depths contained the same metal concentrations as surface waters. The only exception was Pb, whose concentration in water solutes increased with increasing depth. Lack of vertical stratification in pore-water contents of Cu, Zn, Cr, Mn, Fe and Co indicated vertical mobility of these metals.