Quantification of geogenic inputs of magnesium (Mg) and calcium (Ca) as essential nutrients, and strontium (Sr) as a Ca proxy, into biomass and catchment runoff is indispensable for studies of forest sustainability in an era of persisting acidification and climatic change. Supergene processes control the isotope composition of base cations released from bedrock into solution. Isotope signatures of dissolved Mg2+, Ca2+ and Sr2+ are complementary to the isotope composition of weathered rock because both are derived from the same parent material. We investigated shifts in S26Mg, S44Ca, and 87Sr/86Sr isotope ratios from fresh bedrock toward the weathering front in six common crystalline lithologies, including leucocratic granite, quartz diorite, melasyenite, melagranite, augen gneiss and amphibolite. About 20 cm below the deepest soil horizon, the isotopic composition of Mg, Ca and Sr in weathered rock differed significantly from that of fresh rock in nine out of 18 cases. Bulk-rock S26Mg and S44Ca values were less sensitive to partial dissolution of minerals than 87Sr/86Sr ratios. Statistically significant shifts in 87Sr/86Sr were observed in all six lithologies. Weathered rock had higher 87Sr/86Sr ratios than fresh rock in three cases, and lower 87Sr/86Sr ratios in another three cases. The site-specific 87Sr/86Sr shift was explained by contrasting weathering rates of Rb-rich and Rb-poor minerals in most rocks. Both lower S26Mg and higher S44Ca values of weathered amphibolite were likely related to isotope fractionations accompanying in-situ formation of secondary smectite. Continuing mineral dissolution in overlaying soils may cause additional Mg, Ca and Sr isotope effects.

A Central European catchment underlain by base-poor orthogneiss was studied using mass budgets and Mg–Ca–Sr isotope systematics. For 50 years, the catchment received large amounts of partly soluble dust from a nearby cluster of coal-burning power plants, while suffering from acid rain and severe spruce die-back. Our objective was to investigate to what extent anthropogenic dust contributes to Mg and Ca in runoff and to identify fractionations affecting Mg and Ca isotope composition of 13 ecosystem pools and fluxes. We hypothesized that if Mg and Ca runoff fluxes were significantly larger than their atmospheric inputs, Mg and Ca isotope ratios in runoff would converge to those of bedrock Mg and Ca. This relationship could be obscured by isotope fractionations. Strontium characterized by negligible isotope fractionations served as a Ca proxy. There was a strong positive correlation between Mg and Ca fluxes via spruce throughfall and catchment runoff. Monitoring of rainfall, canopy throughfall and runoff fluxes revealed a 20-, 15- and 15-fold excess of Mg, Ca and Sr in runoff, respectively, compared to atmospheric deposition fluxes. This sizeable excess per se would indicate predominance of geogenic base cations in runoff. The behavior of Mg and Ca isotopes was de-coupled. Petrographic study indicated that 92

Nutrient imbalances may negatively affect the health status of forests exposed to multiple stress factors, including drought and bark beetle calamities. We studied the origin of base cations in runoff from a small Carpathian catchment underlain by base-poor flysch turbidites using magnesium (Mg), calcium (Ca) and strontium (Sr) isotope composition of 10 ecosystem compartments. Our objective was to constrain conclusions drawn from long-term hydrochemical monitoring of inputs and outputs. Annual export of Mg, Ca and Sr exceeds 5-to-15 times their atmospheric input. Mass budgets per se thus indicate sizeable net leaching of Mg, Ca and Sr from bedrock sandstones and claystones. Surprisingly, δ26Mg, δ44Ca and 87Sr/86Sr isotope ratios of runoff were practically identical to those of atmospheric deposition and soil water but significantly different from bedrock isotope ratios. We did not find any carbonates in the studied area as a hypothetical, easily dissolvable source of base cations whose isotope composition might corroborate the predominance of geogenic base cations in the runoff. Marine carbonates typically have lower δ26 Mg and 87Sr/86Sr ratios, and silicate sediments often have higher δ26Mg and 87Sr/86Sr ratios than runoff at the study site. Mixing of these two sources, if confirmed, could reconcile the flux and isotope data.

Knowledge of the origin of magnesium (Mg) and calcium (Ca) in soil solutions and catchment runoff helps to predict forest ecosystems’ vulnerability to deficiencies in essential nutrients in an era of climate change, environmental pollution and bark-beetle calamities. Here we discuss isotope aspects of Mg, Ca and strontium (Sr) cycling in a spruce-forested headwater catchment in a relatively unpolluted part of Central Europe. We investigated to what extent Mg and Ca isotope signatures of runoff reflect the isotope compositions of specific Mg- and Ca-rich minerals that easily dissolve during the weathering of paragneiss, and compared the isotope variability of Mg and Ca in fresh bedrock minerals, soils and other ecosystem reservoirs. We also compared conclusions from Mg and Ca isotope systematics with inferences from catchment input–output mass budgets. Long-term input–output monitoring in the studied catchment situated near the Czech–German border (Central Europe) revealed 3.5–7 times higher outputs of Mg, Ca, and Sr via surface runoff relative to their present-day atmospheric inputs. It follows that hydrological exports of recent atmospheric Mg, Ca and Sr are minor. Release of geogenic base cations into the runoff results from the interplay between mineral abundances, concentrations of the studied elements in the minerals, and their dissolution rates. Chemical depletion fractions for the studied elements from bedrock to the soil were 50–70 %, and the losses of dominant soluble minerals in the soil were 30–80 %. Exports of residual Mg, Ca and Sr following partial incorporation of these elements into secondary phyllosilicates are probably low because newly-formed clay minerals are not abundant in the soil. Residual Ca following preferential incorporation of isotopically light Ca into growing tree biomass may contribute to the isotopically heavy runoff Ca. Isotope ratios of base cations were obtained for six minerals (plagioclase, orthoclase, biotite, muscovite, apatite, and ilmenite). Mineral fractions differ greatly in δ26Mg and δ44Ca values and 87Sr/86Sr ratios. 80–97 % of each of the three studied base cations are present in the bedrock in a single relatively easily dissolvable mineral: Mg in biotite, and Ca and Sr in plagioclase. The isotope composition of Mg in biotite was similar to the isotope composition of Mg in runoff. The isotope compositions of Ca and Sr in plagioclase were also similar to Ca and Sr isotope compositions in runoff. Thus, the dominant geogenic source of each of the studied elements (Mg, Ca and Sr) in the investigated paragneiss catchment can be represented by one relatively soluble mineral.

Magnesium, calcium and strontium isotope systematics were studied in a Central European headwater catchment underlain by granite. The Uhlirska catchment (Czech Republic) is recovering from acidification following 40 years of acid rain. A combination of isotope and non-isotope data was used to constrain the origin of base cations in runoff. Whole-rock delta 26Mg, delta 44Ca values and 87Sr/86Sr ratios were complemented by isotope analysis of apatite, biotite, plagioclase, orthoclase and titanite. Isotope composition of Mg, Ca and Sr in precipitation, throughfall and runoff was monitored for 12 months. Soil, soil solutions and Norway spruce tissues were also analyzed. Non -isotope data included a 24-year time-series of input/output Mg and Ca fluxes. Biotite was the likely main source of geogenic Mg. Apatite and plagioclase were the likely main sources of geogenic Ca, and plagioclase was the likely main source of geogenic Sr. Magnesium in biotite was isotopically too heavy to dominate runoff. Calcium in apatite and plagioclase was isotopically indistinguishable from whole-rock Ca and could play a major role in runoff generation. Plagioclase had a significantly lower 87Sr/86Sr ratio than bulk bedrock, close to the low 87Sr/86Sr ratio of runoff. Plagioclase weathering was consistent with a sizeable geogenic Sr contribution to runoff but if only bulk-rock 87Sr/86Sr was considered predominance of geogenic Sr in runoff would be unlikely. Higher Mg, Ca and Sr runoff fluxes, compared to deposition, suggested geogenic control of runoff. A decrease in runoff fluxes of Mg and Ca coincided with a decrease in deposition fluxes but there may not be a causal relationship pointing to a large atmospheric contribution of base cations to runoff. Decreasing fluxes of base cations via runoff were mostly related to decreasing sulfate export accompanying retreat of acidification. Mg/Ca/Sr isotope sys-tematics at Uhlirska are discussed in light of analogous data from four other headwater catchments.

Atmospheric deposition of antimony (Sb) varies within ten orders of magnitude globally. The lowest Sb deposition rates are found in Antarctica amounting to 7E-10 g m -2 yr -1 . In contrast, very high Sb deposition rates are reported from a Sb-Hg mining district in China extending to 7 g m -2 yr -1 . The current Sb deposition rate in Central Europe, sampled at 10 stations in mountain ranges ringing the Czech Republic, amounts to 1 E-4 g m -2 yr -1 . These sampling sites in the Czech Republic were located at elevations of about 1000 m a.s.l. Most of the Sb was deposited in soluble form in snow (7.9 E-5 g m -2 yr -1 ), followed by soluble Sb in rime (3.5 E-5 g m -2 yr -1 ). The corresponding insoluble fraction contained much less Sb, namely 1.2 E-5 g m -2 yr -1 in snow and 2.3 E-6 g m -2 yr -1 in rime. The highest Sb concentration was found in soluble form in rime (0.47 µg L -1 ), while the lowest Sb concentration was determined in insoluble form in snow (0.017 µg L -1 .). Using the HYSPLIT model, backward trajectories of air masses containing Sb were calculated suggesting Sb sources predominantly in the Pol

In the low-nutrient, redox-stratified Lake Medard (Czechia), reductive Fe(III) dissolution outpaces sulfide generation from microbial sulfate reduction (MSR) and ferruginous conditions occur without quantitative sulfate depletion. The lake currently has marked overlapping C, N, S, Mn and Fe cycles occurring in the anoxic portion of the water column. This feature is unusual in stable, natural, redox-stratified lacustrine systems where at least one of these biogeochemical cycles is functionally diminished or undergoes minimal transformations because of the dominance of another component or other components. Therefore, this post-mining lake has scientific value for (i) testing emerging hypotheses on how such interlinked biogeochemical cycles operate during transitional redox states and (ii) acquiring insight into redox proxy signals of ferruginous sediments underlying a sulfatic and ferruginous water column. An isotopically constrained estimate of the rates of sulfate reduction (SRRs) suggests that despite high genetic potential, this respiration pathway may be limited by the rather low amounts of metabolizable organic carbon. This points to substrate competition exerted by iron- and nitrogen-respiring prokaryotes. Yet, the planktonic microbial succession across the nitrogenous and ferruginous zones also indicates genetic potential for chemolithotrophic sulfur oxidation. Therefore, our SRR estimates could rather be portraying high rates of anoxic sulfide oxidation to sulfate, probably accompanied by microbially induced disproportionation of S intermediates. Near and at the anoxic sediment–water interface, vigorous sulfur cycling can be fuelled by ferric and manganic particulate matter and redeposited siderite stocks. Sulfur oxidation and disproportionation then appear to prevent substantial stabilization of iron monosulfides as pyrite but enable the interstitial precipitation of microcrystalline equant gypsum. This latter mineral isotopically recorded sulfur oxidation proceeding at near equilibrium with the ambient anoxic waters, whilst authigenic pyrite sulfur displays a 38 ‰ to 27 ‰ isotopic offset from ambient sulfate, suggestive of incomplete MSR and open sulfur cycling. Pyrite-sulfur fractionation decreases with increased reducible reactive iron in the sediment. In the absence of ferruginous coastal zones today affected by post-depositional sulfate fluxes, the current water column redox stratification in the post-mining Lake Medard is thought relevant for refining interpretations pertaining to the onset of widespread redox-stratified states across ancient nearshore depositional systems.

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.

In the aqueous oligotrophic ecosystem of a post-mining lake (Lake Medard, Czechia), reductive Fe(II) dissolution outpaces sulfide generation from microbial sulfate reduction (MSR), and ferruginous conditions occur without quantitative sulfate depletion. An isotopically constrained estimate of the rates of sulfate reduction (SRR) suggests that despite a high genetic potential, this respiration pathway is limited by the rather low amounts of metabolizable organic carbon. This points to substrate competition exerted by iron and nitrogen respiring prokaryotes. Yet, the microbial succession across the nitrogenous and ferruginous zones of the bottom water column also indicates sustained genetic potential for chemolithotrophic sulfur oxidation. Therefore, our isotopic SRR estimates could be rather portraying high rates of anoxic sulfide oxidation to sulfate, probably accompanied by microbially induced disproportionation of S intermediates. Near and at the anoxic sediment-water interface, vigorous sulfur cycling can be fuelled by ferric and manganic particulate matter and redeposited siderite stocks. Sulfur oxidation and disproportionation then appear to prevent substantial stabilization of iron monosulfides as pyrite but can enable the interstitial precipitation of small proportions of equant microcrystalline gypsum. This latter mineral isotopically fingerprints sulfur oxidation proceeding at near equilibrium with the ambient anoxic waters, whilst authigenic pyrite-sulfur displays a 38 to 27 ‰ isotopic offset from ambient sulfate, suggestive of incomplete MSR and likely reflective also of an open sulfur cycling system. Pyrite-sulfur fractionation decreases with increased reducible reactive iron in the sediment. In the absence of ferruginous coastal zones today, the current water column redox stratification in the post-mining Lake Medard has scientific value for (i) testing emerging hypotheses on how a few interlinked biogeochemical cycles operated in nearshore paleoenvironments during redox transitional states; and (ii) to acquire insight on how similar early diagenetic redox proxy signals developed in sediments affected by analogue transitional states in ancient water columns.

Field measurements of hydraulic properties of the rock matrix and in low permeability hard rocks generally require highly accurate and sensitive technical equipment and special methods of measurement. Hydraulic conductivity of intact rocks is mostly measured in the laboratory conditions; field measurements are less common. The Czech geological survey developed equipment, which allows measurements of very low consumption of water during WPT (water pressure tests). This device enables to implement the same testing methodology for all sections of the borehole and subsequently compare the obtained results from low-permeability as well as more permeable sections. Hydraulic conductivity of eight different granitoids was studied in the Bohemian Massif in the Czech Republic. Mean values of hydraulic conductivity of fractured rock are on the order of 10-8 to 10-7 m·s-1, while hydraulic conductivity of rock matrix was most frequently on the order of 10–11 to10-12 m·s-1. The difference of values measured in laboratory and field is caused by scale effect. The significance of scale effect in rock matrix is determined mainly by the connectivity of a network of microfissures. Length and aperture of microfissures govern mainly the connectivity of fissure net in rock matrix. Coarse-grained granitoids have greater length and aperture of microfissures, higher connectivity and hydraulic conductivity, and the scale effect is less significant. The fracture network appearance and hydraulic conductivity of rock matrix is similar and characteristic for different types of granitoid rocks.

Two models of reversible and irreversible water – mineral interaction are developed to simulate geochemical evolution of old groundwater in the Cenomanian and Turonian sandstone aquifers in the Bohemian Cretaceous Basin in Central Europe. The kinetic constants of dissolution and equilibrium constants of reversible reactions are results of laboratory experiments published in literature. Reactive surface areas of minerals are calculated. The model simulates the evolution of the chemical composition of groundwater whose age was derived from isotopic data. The results are compared to the chemical composition of groundwater along the trajectory of the prevailing flow. The model represents the interaction between groundwater and sandstones containing quartz, amorphous silica, a mixture of clay minerals, calcite and traces of residual feldspars. The three processes of water rock interaction are the irreversible dissolution of feldspars and carbonate, aluminium and silica equilibrium. The composition of groundwater in the Cenomanian aquifer with a confined water table is a result of geochemical evolution during the last 26,000 years, while the groundwater in the Turonian aquifer with a free water table is a mixture of old groundwater and recent water infiltrated from the surface. The proposed models are applicable to confined aquifers with residual rock matrix derived from granitic rocks decomposed by weathering without mixing of waters of different ages.

A deep geological repository of spent nuclear fuel has to be safe for at least 100 thousand years. During this time, water–rock interaction on surface as well as in the rock around the repository will progress. All exogenous processes will depend on future evolution of climate. Based on the research of Quaternary sediments, three limiting scenarios of future climate evolution are considered: Maximum cooling and drying in glacial periods; maximum warming and moistening in interglacial periods and climate evolution affected by elevated concentrations of CO2 in the atmosphere. Formation of permafrost, infiltration of melted water and oxidation will influence chemical composition of ground water. Two analogues of the changes are presented. They are ground waters in two mines in the Bohemian massive: (1) Mine “Svornost” in an abandoned historical uranium deposit Jáchymov (Joachimstahl), (2) underground research facility of “Bukov” near the uranium deposit of Rožná. Ground water was sampled from surface to a depth of 1200 m. The water–rock interaction during the infiltration and flow of ground water is the cause of the observed stratification of the chemical composition. The chemical composition of the collected samples indicate a probable future composition of ground water within the repository.

This work focuses on a model of water-rock geochemical interaction and its testing on data from hydrogeological and isotopic research of rates of percolation of ground water in Cenomanian and Turonian aquifers of the Bohemian Cretaceous Basin. A simple geochemical model of percolation in Cenomanian and Turonian aquifers is presented. Using calibration with measured data, the dissolution rates of minerals or reaction surfaces of minerals are obtained. The results are discussed.

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.

Inputs of As to a small catchment due to chemical weathering of bedrock, mechanical weathering of bedrock, and atmospheric precipitation were 71.53, 23.98 and 0.02 g ha−1 year−1, respectively. The output fluxes of As due to mechanical erosion of soil, biological uptake, stream discharge, and groundwater flow were 6.32, 4.77, 0.37 and 0.02 g ha−1 year−1, respectively. The results indicate that arsenic accumulates in soil and regolith with a very high rate. This is attributed to the selective weathering and erosion with respect to arsenic and fixation of arsenic in the secondary solids produced by weathering. The output fluxes of As in stream and groundwater in Vydrica catchment in Slovak Republic (0.39 g ha−1 year−1) based on muscovite–biotite granites and granodiorites were much lower compared to catchments in a gold district in the Czech Republic. These results may be ascribed to the low levels of arsenic pollution measured in Vydrica catchment. The arsenic fluxes were estimated by calculation of mechanical and chemical weathering rates of the bedrocks in Vydrica catchment from mass balance data on sodium and silica. The justification of the steady state of Na and Si is that neither of the elements is appreciably accumulated in plants and in exchangeable pool of ions in soil.

Arsenic in natural waters and in soils represents a serious health hazard. Natural sources of this element in soil are the subject of this communication. Weathering mass balance of As and rates of weathering in soils are evaluated from monitored inputs and outputs in two small watersheds. These watersheds are located within the Celina-Mokrsko gold district, Czech Republic. Annual chemical weathering fluxes of As are calculated from the monthly weighted means of stream water and groundwater. The fluxes are corrected for atmospheric precipitation, agrochemical inputs, and biological uptake. Mechanical and chemical weathering rates of the arsenopyrite-bearing rocks in the watersheds were estimated from mass balance data on sodium and silica. The input of As due to total weathering of bedrock was estimated to be 1369 g ha(-1)yr(-1) in the Mokrsko watershed (MW) and 81 g ha(-1)yr(-1) in the Celina watershed (CW). These results indicate that the annual weathering rate of As in the watersheds represents more than 95% of the total As input to the soil. Accumulation rate of As in the soil was estimated at 311 g ha(-1)yr(-1) in MW and 69 g ha(-1)yr(-1) in CW. The mass balance method for calculation of weathering rate of As was used, and the results suggest that weathering could be the most important process in the As biogeochemistry of the areas with elevated As content in the bedrock. Simple model of weathering and erosion can be used successfully in estimating their role in As pollution on the scale of small watershed. The method is also useful for indicating the mass balance of As in soils that is controlled by both the natural and anthropogenic inputs and outputs of As.

The concentration of the estrogens 17β-estradiol, estriol, estrone, 17α-ethinylestradiol, mestranol and norethisterone and of the anthropogenic gadolinium (Gdant) has been determined in the creeks and rivers, sewage treatment plants and water works of the city of Prague. The rapid degradation of estrogens in surface water allows the estrogen concentration gradient to be used as a very precise and sensitive guideline by which to pin-point sewage leaks into surface run-off water. The rather conservative behavior of Gdant in surface and ground water documents in the present case the presence of sewage water in the surface water cycle.