Response of spring yield dynamics to climate change across altitude gradient and varied hydrogeological conditions.

Springs offer insights into groundwater dynamics. Long-term monitoring of spring yields can reflect the response of groundwater storage to climate change. We analyzed the yield trends of 136 springs across 18 hydrogeological regions in Czechia from 1971 to 2020. The trend-free pre-whitening Mann-Kendall test and linear mixed-effects models were used to assess environmental impacts on spring yields. Overall, 71 % of the springs showed no long-term trends, 28 % exhibited decreasing trends, and 1.5 % showed increasing trends in annual spring yields. Altitude has been demonstrated as a contributing factor influencing spring responses to climate change. Lowland springs (<300 m a.s.l.) exhibited the highest proportion of decreasing annual trends (41 %), while uplands (300-600 m a.s.l.) and highlands (>600 m a.s.l.) showed declines in 26 % and 25 % of springs, respectively. Moreover, highlands recorded a 7 % yield increase, indicating a complex interplay between altitude and spring response to climatic factors. A strong positive correlation was found between precipitation and yields (p < 0.01), whereas temperature increases negatively affected spring yields (p < 0.01). The interaction between temperature changes and region transmissivity highlighted the vulnerability of springs in low-transmissivity regions, predominantly those in crystalline and flysch bedrock areas, to climatic shifts. Generally, these regions have lower spring yields compared to the high-transmissivity areas of the Cretaceous basins. Although these lower-yield regions are not used as a primary water source for large areas, unlike regions with high-transmissivity bedrock, they provide water resources for local supply. Analysis of annual spring maxima frequencies revealed a shift in the culmination of maxima occurrences from April to March, with a significant decrease in April (p < 0.05) and May (p < 0.1) and an increase in March (p < 0.05), suggesting a change in spring yield seasonality. The 2015-2020 drought significantly accelerated declining spring yield trends across hydrogeological regions.

Comparison of vertical and horizontal atmospheric deposition of nitrate at Central European mountain-top sites during three consecutive winters.

Nitrogen (N) deposition, a key process of atmospheric self-cleaning, represents an important pathway for nutrients and pollutants to ecosystems. Enhanced N deposition flux contributes to acidification, eutrophication and loss of biodiversity. N-NO3- concentrations in rime and snow were measured at 10 Czech plots situated in borderline mountains in 2009-2011 winters. The results were put in context with data-driven geostatistical modelling results of annual wet vertical and horizontal deposition. Our hypotheses were that: (i) rime and snow would be more polluted in the highly industrialized north than in the south, (ii) the N-NO3- concentrations would differ in the three winters studied, and (iii), that N-NO3- rime deposition is not negligible in Central European mountain ranges. Our results indicated that winter N-NO3- concentrations were significantly higher in rime than in snow and that there were much larger between-site differences in N-NO3- concentrations for rime than for snow. Relatively large differences were found between individual years. Atmospheric input of N-NO3- in winter was dominated by vertical deposition, i.e., snow. Modelled results showed that mean winter rime deposition corresponded to about 6-25 %, and mean winter snow deposition made up 25-72.5 % of mean annual N-NO3- wet-only deposition. Model N-NO3-occult deposition estimated from throughfall and total (wet and dry) deposition is highly uncertain, however: N throughfall is not a relevant proxy for estimation of realistic total N deposition due to N exchange between the tree canopy and atmosphere.

Atmospheric deposition and trajectories of antimony in Central Europe.

Antimony (Sb) concentrations were measured in wet atmospheric deposition at 10 high-elevation sites in the Czech Republic (Central Europe) during three winter seasons (2009-2011). Soluble and insoluble Sb forms were quantified in snow (vertical deposition) and rime (horizontal deposition) on mountain summits located equidistantly near the Czech borders with Austria, Germany and Poland. The highest Sb concentrations were found in the soluble form in rime (0.47 µg L-1), while the lowest Sb concentrations were those in the insoluble form in snow (0.017 µg L-1). The estimated average Sb deposition rate in Central Europe amounted to 1.3. 10-4 g m-2 yr-1. Most Sb was deposited in the soluble form in snow (7.9. 10-5 g m-2 yr-1), followed by the soluble form in rime (3.5. 10-5 g m-2 yr-1). The corresponding insoluble fraction contained less Sb, namely 1.2. 10-5 g m-2 yr-1 in snow and 2.3. 10-6 g m-2 yr-1 in rime. The average Sb deposition in Central Europe, measured at an altitude of 1000 m a.s.l., was by six orders of magnitude higher compared to Sb deposition in the Arctic (7. 10-10 g m-2 yr-1), and by four orders of magnitude lower compared to Sb deposition in a Sb-Hg mining district in China (7 g m-2 yr-1). Using the HYSPLIT model, backward trajectories of air masses indicated that the Sb sources were predominantly situated in Upper and Lower Silesia.

Winter arsenic pollution in 10 forest ecosystems in the mountainous border regions of the Czech Republic.

Arsenic (As) concentrations and deposition fluxes were measured in snow and rime at 10 mountain-top sites near the borders between the Czech Republic and Austria, Germany, Poland, and Slovakia during three consecutive winter seasons (2009-2011). Our study was performed at a time following several decades of sharply decreasing regional atmospheric pollution and following the 2006 implementation of stricter air quality standards across Europe. Our objective was to compare vertical and horizontal depositions of soluble and insoluble As forms throughout the Czech Republic and define a recent Central European As pollution gradient. Arsenic soluble in weak nitric acid contributed 83 to 85% to the total As deposition, with the remaining 17-15% bound to stable particulate forms. The highest As deposition rates were recorded in the eastern Czech Republic near the borders with Poland and Slovakia. Complementary hydrochemical monitoring in four mountain-slope catchments situated near selected main study sites revealed a further decrease in open-area As deposition by the end of 2018 in the east of the country. In contrast, spruce canopy throughfall flux did not change significantly between 2009-2011 and 2016-2018. The site-specific relative roles of coal-burning-derived and ore-smelting-derived atmospheric As are discussed.

Controls on δ26Mg variability in three Central European headwater catchments characterized by contrasting bedrock chemistry and contrasting inputs of atmospheric pollutants.

Magnesium isotope ratios (26Mg/24Mg) can provide insights into the origin of Mg pools and fluxes in catchments where Mg sources have distinct isotope compositions, and the direction and magnitude of Mg isotope fractionations are known. Variability in Mg isotope compositions was investigated in three small, spruce-forested catchments in the Czech Republic (Central Europe) situated along an industrial pollution gradient. The following combinations of catchment characteristics were selected for the study: low-Mg bedrock + low Mg deposition (site LYS, underlain by leucogranite); high-Mg bedrock + low Mg deposition (site PLB, underlain by serpentinite), and low-Mg bedrock + high Mg deposition (site UDL, underlain by orthogneiss). UDL, affected by spruce die-back due to acid rain, was the only investigated site where dolomite was applied to mitigate forest decline. The δ26Mg values of 10 catchment compartments were determined on pooled subsamples. At LYS, a wide range of δ26Mg values was observed across the compartments, from -3.38 ‰ (bedrock) to -2.88 ‰ (soil), -1.48% (open-area precipitation), -1.34 ‰ (throughfall), -1.19 ‰ (soil water), -0.99 ‰ (xylem), -0.95 ‰ (needles), -0.82 ‰ (bark), -0.76 ‰ (fine roots), and -0.76 ‰ (runoff). The δ26Mg values at UDL spanned 1.32 ‰ and were thus less variable, compared to LYS. Magnesium at PLB was isotopically relatively homogeneous. The δ26Mg systematics was consistent with geogenic control of runoff Mg at PLB. Mainly atmospheric/biological control of runoff Mg was indicated at UDL, and possibly also at LYS. Our sites did not exhibit the combination of low-δ26Mg runoff and high-δ26Mg weathering products (secondary clay minerals) reported from several previously studied sites. Six years after the end of liming at UDL, Mg derived from dolomite was isotopically undetectable in runoff.

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.

Retraction Statement: Comparison of nitrogen inputs and accumulation in 210 Pb-dated peat cores: Evidence for biological N2 -fixation in Central European peatlands despite decades of atmospheric N pollution.

"Comparison of nitrogen inputs and accumulation in 210 Pb-dated peat cores: Evidence for biological N2 -fixation in Central European peatlands despite decades of atmospheric N pollution" https://doi.org/10.1111/gcb.14505, by Martin Novak, Melanie A. Vile, Jan Curik, Bohuslava Cejkova, Jiri Barta, Marketa Stepanova, Ivana Jackova, Frantisek Buzek, Leona Bohdalkova, Eva Prechova, Frantisek Veselovsky, Marie Adamova, Ivana Valkova and Arnost Komarek. The above article, first published online in Wiley Online Library (wileyonlinelibrary.com) in Global Change Biology, has been retracted by agreement between the authors, the journal Editor-in-Chief, Stephen P. Long, and John Wiley & Sons Ltd. Since publication of the above article, it was brought to the attention of the authors that the peat accretion rates violate reasonable ranges of peatland C/N/P stoichiometry, placing the quantitative conclusions of the article in serious error. The authors apologize for any inconvenience the publication of this work may have caused our readers. REFERENCE Novak, M., Vile, M. A., Cejkova, B., Barta, J., Stepanova, M., Jackova, I., Buzek, F., Bohdalkova, L., Prechova, E., Veselovsky, F., Adamova, M., Valkova, I., & Komarek, A. (2018). Comparison of nitrogen inputs and accumulation in 210 Pb-dated peat cores: Evidence for biological N2 -fixation in Central European peatlands despite decades of atmospheric N pollution. Global Change Biology.. https://doi.org/10.1111/gcb.14505.

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.

Cu-Zn isotope constraints on the provenance of air pollution in Central Europe: Using soluble and insoluble particles in snow and rime.

Copper (Cu) and zinc (Zn) isotope ratios can be used to fingerprint sources and dispersion pathways of pollutants in the environment. Little is known, however, about the potential of δ65Cu and δ66Zn values in liquid and solid forms of atmospheric deposition to distinguish between geogenic, industrial, local and remote sources of these potentially toxic base metals. Here we present Cu-Zn deposition fluxes at 10 mountain-top sites in the Czech Republic, a region affected by extremely high industrial emission rates 25 years ago. Additionally, we monitored isotope composition of Cu and Zn in vertical and horizontal atmospheric deposition at two sites. We compared δ65Cu and δ66Zn values in snow and rime, extracted by diluted HNO3 and concentrated HF. Cu and Zn isotope signatures of industrial pollution sources were also determined. Cu and Zn deposition fluxes at all study sites were minute. The mean δ65Cu value of atmospheric deposition (-0.07‰) was higher than the mean δ65Cu value of pollution sources (-1.17‰). The variability in δ65Cu values of atmospheric deposition was lower, compared to the pollution sources. The mean δ66Zn value of atmospheric deposition (-0.09‰) was slightly higher than the mean δ66Zn value of pollution sources (-0.23‰). The variability in δ66Zn values of atmospheric deposition was indistinguishable from that of pollution sources. The largest isotope differences (0.35‰) were observed between the insoluble and soluble fractions of atmospheric deposition. These differences may result from different sources of Cu/Zn for each fraction. The difference in isotope composition of soluble and insoluble particles appears to be a promising tool for pollution provenance studies in Central Europe.

The fate of atmospherically derived Pb in Central European catchments: insights from spatial and temporal pollution gradients and Pb isotope ratios.

Soils in polluted regions are generally regarded as a delayed, long-lasting source for Pb contamination of aquatic systems. Lead deposited on topsoil is slowly transported downward with particulate and colloidal organic matter, driven by infiltrating precipitation. Then, Pb is tightly retained in mineral soil. Lead export from catchments is extremely low and decoupled from the atmospheric input. We tested this hypothesis in 11 small catchments, differing in pollution levels. Input/ouput Pb fluxes were monitored for 14-15 years in an era of decreasing industrial Pb emission rates. Between 1996/1997 and 2010, Pb deposition fluxes decreased significantly, on average by 80%. At the beginning of the monitoring, Pb export constituted 2 to 58% of Pb input. At the end of the monitoring, Pb export constituted 2 to 95% of Pb input. Highly polluted sites in the northeast exported significantly more Pb than less polluted sites further south. The (206)Pb/(207)Pb isotope ratios of runoff (1.16) were identical to those of topsoil and present-day deposition, and different from mineral soil and bedrock. Lead isotope systematics and between-site flux comparisons indicated that a portion of the incoming Pb had a relatively short residence time in the catchments, on the order of decades.

Atmospheric deposition of beryllium in Central Europe: comparison of soluble and insoluble fractions in rime and snow across a pollution gradient.

Little is known about atmospheric input of beryllium (Be) into ecosystems, despite its highly toxic behavior. For three consecutive winters (2009-2011), we measured Be concentrations in horizontal deposition (rime) and vertical deposition (snow) at 10 remote mountain-top locations in the Czech Republic, Central Europe. Beryllium was determined both in filtered waters, and in HF digests of insoluble particles. Across the sites, soluble Be concentrations in rime were 7 times higher, compared to snow (6.1 vs. 0.9ng·L(-1)). Rime scavenged the pollution-rich lower segments of clouds. The lowest Be concentrations were detected in the soluble fraction of snow. Across the sites, 34% of total Be deposition occurred in the form of soluble (bioavailable) Be, the rest were insoluble particles. Beryllium fluxes decreased in the order: vertical dry deposition insoluble>vertical dry deposition soluble>horizontal deposition soluble>vertical wet deposition insoluble>vertical wet deposition soluble>horizontal deposition insoluble. The average contributions of these Be forms to total deposition were 56, 21, 8, 7, 5 and 3%, respectively. Sites in the northeast were more Be-polluted than the rest of the country with sources of pollution in industrial Silesia.