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Soil solution chemistry depends largely on mineralogy and organic matter properties of soil horizons with which they interact. Differing lithologies within a given catchment area can influence variability in soil cation exchange capacities and affect solute transport. Zero-tension and tension lysimeters were used to evaluate the fast transport of solutes in the topsoil vs. slow diffusional matrix flow at the subsoil of three contrasting lithology catchments in a mid-elevation mountain forest. Our aim was to test the feasibility of lysimeters' hydrochemical data as a gauge for legacy subsoil pollution. Due to contrasting lithologies, atmospheric legacy pollution prevailing at the soil-regolith interface is differently yet consistently reflected by beryllium, lead, and chromium soil solution concentrations of the three catchments. Geochemical (dis)equilibrium between the soil and soil matrix water governed the hydrochemistry of the soil solutions at the time of collection, potentially contributing to decreased dissolved concentrations with increased depths at sites with higher soil pH. A complementary isotopic delta O-18 runoff generation model constrained potential seasonal responses and pointed to sufficiently long water-regolith interactions as to permit important seasonal contributions of groundwater enriched in chemical species to the topsoil levels. Our study also reflects subsoil equilibration with atmospheric solutes deposited at the topsoil and thus provides guidance for evaluating legacy pollution in soil profiles derived from contrasting lithology. National Technical Library in Prague; Czech Geological Survey [310470, 310690]; Fulbright Research Grant Published version Open access publishing supported by the National Technical Library in Prague. This work was funded by The Czech Geological Survey, internal project numbers 310470 and 310690 to DAP and PK, respectively. KXPR was supported by a Fulbright Research Grant.

The riverine dissolved organic carbon (DOC) flux is of similar magnitude to the terrestrial sink for atmospheric CO2, but the factors controlling it remain poorly determined and are largely absent from Earth system models (ESMs). Here, we show, for a range of European headwater catchments, that electrolyte solubility theory explains how declining precipitation ionic strength (IS) has increased the dissolution of thermally moderated pools of soluble soil organic matter (OM), while hydrological conditions govern the proportion of this OM entering the aquatic system. Solubility will continue to rise exponentially with declining IS until pollutant ion deposition fully flattens out under clean air policies. Future DOC export will increasingly depend on rates of warming and any directional changes to the intensity and seasonality of precipitation and marine ion deposition. Our findings provide a firm foundation for incorporating the processes dominating change in this component of the global carbon cycle in ESMs. More dilute rainwater, due to less polluted air, dissolves more soil organic matter, resulting in the browning of rivers.

Soil solution chemistry depends largely on mineralogy and organic matter properties of soil horizons with which they interact. Differing lithologies within a given catchment area can influence variability in soil cation exchange capacities and affect solute transport. Zero-tension and tension lysimeters were used to evaluate fast transport of solutes in the topsoil vs. slow diffusional matrix flow at the subsoil of three contrasting lithology catchments in a mid-elevation mountain forest. Our aim was to test the feasibility of lysimeters hydrochemical data as a gauge for legacy subsoil pollution. Due to contrasting lithologies, atmospheric legacy pollution prevailing at the soil-regolith interface is differently yet consistently reflected by beryllium, lead, and chromium soil solution concentrations of the three catchments. Geochemical (dis)equilibrium between the soil and soil matrix water governed the hydrochemistry of the soil solutions at the time of collection, potentially contributing to decreased dissolved concentrations with increased depths at sites with higher soil pH. A complementary isotopic data constrained potential seasonal responses and pointed to sufficiently long water-regolith interactions as to permit important seasonal contributions of groundwater enriched in chemical species to the topsoil levels. Our study also reflects subsoil equilibration with atmospheric solutes deposited at the topsoil, and thus provides guidance for evaluating legacy pollution in soil profiles derived from contrasting lithology.

Chromium isotope and chemical compositions in runoff from two felsic rock catchments, the Lysina (LYS; Czech Republic) and the Neglinka (NEG; northwest Russia), were studied. Three types of water w...

We collected soil solutions by suction lysimeters in a central European temperate forest with a history of acidification-related spruce die-back in order to interpret spatial patterns of soil nutrient partitioning, compare them with stream water chemistry and evaluate these parameters relative to concurrent loads of anions and cations in precipitation. Five lysimeter nests were installed in the 33 ha U dvou loucek (UDL) mountain catchment at different topographic positions (hilltops, slopes and valley). Following equilibration, monthly soil solution samples were interrogated over a 2-year period with regard to their SO42-, NO3-, NH4+, Na+, K+, Ca2+, Mg2+ and total dissolved Al concentrations, organic carbon (DOC) and pH. Soil pits were excavated in the vicinity of each lysimeter nest to also constrain soil chemistry. For an estimation of phosphorus (P) availability, ammonium oxalate extraction of soil samples was performed. Cation exchange capacity (CEC ≤58 meq kg−1) and base saturation (BS ≤13 %) were found to be significantly lower at UDL than in other monitored central European small catchments areas. Spatial trends and seasonality in soil solution chemistry support belowground inputs from mineral-stabilized legacy pollutants. Overall, the soil solution data suggest that the ecosystem was still chemically out of balance relative to the concurrent loads of anions and cations in precipitation, documenting incomplete recovery from acidification. Nearly 30 years after peak acidification, UDL exhibited similar soil solution concentrations of SO42, Ca2+ and Mg2+ as median values at the Pan-European International Co-operative Program (ICP) Forest sites with similar bedrock lithology and vegetation cover, yet NO3- concentrations were an order of magnitude higher. When concentrations of SO42-, NO3- and base cations in runoff are compared to soil pore waters, higher concentration in runoff points to lateral surficial leaching of pollutants and nutrients in excess than from topsoil to subsoil. With P availability being below the lowest range observed in soil plots from the Czech Republic, the managed forest ecosystem in UDL probably reflects growing inputs of C from regenerating vegetation in the N-saturated soil, which leads to P depletion in the soil. In addition, the observed spatial variability provides evidence pointing to substrate variability, C and P bioavailability, and landscape as major controls over base metal leaching toward the subsoil level in N-saturated catchments.

In 1994, a network of small catchments (GEOMON) was established in the Czech Republic to determine input–output element fluxes in semi‐natural forest ecosystems recovering from anthropogenic acidification. The network consists from 16 catchments and the primary observations of elements fluxes were complemented by monitoring of biomass stock, element pools in soil and vegetation, and the main water balance components. Over last three decades, reductions of SO₂, NOₓ and NH₃ emissions were followed by sulphur (S) and nitrogen (N) deposition reductions of 75% and 30%, respectively. Steeper declines of strong acid anion concentrations compared to cations (Ca, Mg, Na, K, NH₄) in precipitation resulted in precipitation pH increase from 4.5 to 5.2 in bulk precipitation and from 4.0 to 5.1 in spruce throughfall. Stream chemistry responded to changes in deposition: S leaching declined. However at majority of catchments soils acted as a net source of S to runoff, delaying recovery. Stream pH increased at acidic streams (pH

Highlights • Novel techniques for presenting exceedances of critical loads (CL) and their temporal development were developed. • Concentrations and fluxes of N and S compounds in deposition and runoff have decreased as a response to decreasing emissions. • Most sites with higher CL exceedances showed larger decreases in both inorganic N and H+ concentrations and fluxes in runoff. • Effects of the cumulative exceedance of the eutrophication CL were evaluated. • The results provide evidence on the link between CL exceedances and empirical impacts. Anthropogenic emissions of nitrogen (N) and sulphur (S) compounds and their long-range transport have caused widespread negative impacts on different ecosystems. Critical loads (CLs) are deposition thresholds used to describe the sensitivity of ecosystems to atmospheric deposition. The CL methodology has been a key science-based tool for assessing the environmental consequences of air pollution. We computed CLs for eutrophication and acidification using a European long-term dataset of intensively studied forested ecosystem sites (n = 17) in northern and central Europe. The sites belong to the ICP IM and eLTER networks. The link between the site-specific calculations and time-series of CL exceedances and measured site data was evaluated using long-term measurements (1990–2017) for bulk deposition, throughfall and runoff water chemistry. Novel techniques for presenting exceedances of CLs and their temporal development were also developed. Concentrations and fluxes of sulphate, total inorganic nitrogen (TIN) and acidity in deposition substantially decreased at the sites. Decreases in S deposition resulted in statistically significant decreased concentrations and fluxes of sulphate in runoff and decreasing trends of TIN in runoff were more common than increasing trends. The temporal developments of the exceedance of the CLs indicated the more effective reductions of S deposition compared to N at the sites. There was a relation between calculated exceedance of the CLs and measured runoff water concentrations and fluxes, and most sites with higher CL exceedances showed larger decreases in both TIN and H+ concentrations and fluxes. Sites with higher cumulative exceedance of eutrophication CLs (averaged over 3 and 30 years) generally showed higher TIN concentrations in runoff. The results provided evidence on the link between CL exceedances and empirical impacts, increasing confidence in the methodology used for the European-scale CL calculations. The results also confirm that emission abatement actions are having their intended effects on CL exceedances and ecosystem impacts.

Headwater catchments underlain by ultramafic bedrock may release toxic amounts of hexavalent chromium [Cr(VI)] into runoff. Redox cycling of Cr during weathering, pedogenesis and runoff generation can be constrained by studying 53Cr/52Cr isotope systematics. We report a 12-month time-series of δ53Cr values of runoff from a small serpentinite-dominated catchment in Central Europe, complemented with a 5-year monitoring of Cr and DOC concentrations. δ53Cr values of bulk bedrock, rock-forming minerals, and bulk soil were also determined. Cr(VI) concentrations in runoff exceeded the 10-ppb maximum contaminant level by 70%. Concentrations of Cr(VI) in runoff were positively correlated with water discharge and DOC concentrations. Chromium export flux in winter was significantly higher than in summer. Runoff δ53Cr exhibited a temporal trend, with negative values (− 0.6‰) in winter and positive values (0.5‰) in summer. On an annual basis, the mass-weighted δ53Cr value of runoff was − 0.4‰. Dissolved Cr exported in winter was isotopically lighter than the within-site Cr sources: δ53Cr of bulk bedrock ranged from − 0.2 to 0.0‰, and δ53Cr of soil ranged from − 0.2 to 0.3‰. Chromium isotope analysis of seven rock-forming minerals separated from serpentinites, tremolite/actinolite schists and amphibolites revealed a much wider range of δ53Cr values, from − 0.4‰ (hornblende) to 1.7‰ (albite). Most of the variability in runoff δ53Cr can be explained by incongruent oxidative weathering, with a contribution of isotope-selective processes related to pedogenesis. Isotopically light Cr was preferentially mobilized from weathered bedrock and soil in cold, water-rich periods and exported via stream water. In these periods, precipitation water more rapidly penetrates into the soil than in summer months, characterized by lower rainfall and larger evapotranspiration, and more efficiently leaches the accumulated Cr(VI).

Empirical evidence based on integrated environmental monitoring including physical, chemical and biological variables is essential for evaluating the ecosystem benefits of costly emission reduction policies. The international multidisciplinary ICP IM (International Cooperative Programme on Integrated Monitoring of Air Pollution Effects on Ecosystems) programme studies the integrated effects of air pollution and climate change on ecosystems in unmanaged and calibrated forested catchments. We calculated site-specific annual input-output budgets for sulphate (SO 4 ) and total inorganic nitrogen (TIN NO 3 -N + NH 4 -N) for 17 European ICP IM sites in 1990–2012. Temporal trends for input (deposition) and output (runoff water) fluxes and the net retention/net release of SO 4 and TIN were also analysed. Large differences in the input and output fluxes of SO 4 and TIN reflect important gradients of air pollution effects in Europe, with the highest deposition and runoff water fluxes at IM sites located in southern Scandinavia and in parts of Central and Eastern Europe and the lowest fluxes at more remote sites in northern European regions. A significant decrease in the total (wet + dry) deposition of non-marine SO 4 and bulk deposition of TIN was found at 90% and 65% of the sites, respectively. Output fluxes of non-marine SO 4 in runoff decreased significantly at 65% of the sites, indicating positive effects of the international emission abatement actions in Europe during the last 20 years. Catchments retained SO 4 in the early and mid-1990s, but this shifted towards a net release in the late 1990s, which may be due to the mobilization of legacy S pools accumulated during times of high atmospheric SO 4 deposition. Despite decreased deposition, TIN output fluxes and retention rates showed a mixed response with both decreasing (9 sites) and increasing (8 sites) trend slopes, and trends were rarely significant. In general, TIN was strongly retained in the catchments not affected by natural disturbances. The long-term annual variation in net releases for SO 4 was explained by variations in runoff and SO 4 concentrations in deposition, while a variation in TIN concentrations in runoff was mostly associated with a variation of the TIN retention rate in catchments. The net release of SO 4 from forest soils may delay the recovery from acidification for surface waters and the continued enrichment of nitrogen in catchment soils poses a threat to terrestrial biodiversity and may ultimately lead to a higher TIN runoff through N-saturation. Continued monitoring and further evaluations of mass balance budgets are thus needed.

Changes in atmospheric deposition, stream water chemistry, and solute fluxes were assessed across 15 small forested catchments. Dramatic changes in atmospheric deposition have occurred over the last three decades, including a 70% reduction in sulphur (S) deposition. These changes in atmospheric inputs have been associated with expected changes in levels of acidity, sulphate and base cations in streams. Soil retention of S appeared to partially explain rates of chemical recovery. In addition to these changes in acid–base chemistry we also observed unexpected changes in nitrogen (N) biogeochemistry and nutrient stoichiometry of stream water, including decreased stream N concentrations. Among all catchments the average flux of dissolved inorganic nitrogen (DIN) was best predicted by average runoff, soil chemistry (forest floor C/N) and levels of acid deposition (both S and N). The rate of change in stream DIN flux, however, was much more closely correlated with reductions in rates of S deposition rather than those of DIN. Unlike DIN fluxes, the average concentrations as well as the rates of decline in streamwater nitrate (NO3) concentration over time were tightly linked to stream dissolved organic carbon/dissolved organic nitrogen ratios DOC/DON and DON/TP rather than catchment characteristics. Declines in phosphorus adsorption with increasing soil pH appear to contribute to the relationship between C, N, and P in our study catchments. Our observations suggest that catchment P availability and its alteration due to environmental changes (e.g. acidification) might have profound effects on N cycling and catchment N retention that have been largely unrecognized.

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.

Calcium and strontium isotope ratios were used to identify Ca sources for bulk soil, soil solutions and runoff in the stressed forest ecosystems of Central Europe. All three study sites are underlain by Ca-poor crystalline bedrock (orthogneiss, leucogranite and serpentinite, respectively), but differ in historical rates of acid deposition. UDL, the spruce die-back affected site at the Czech–Polish border underlain by orthogneiss, received six times more acidifying compounds from the atmosphere than LYS and PLB, two paired catchments near the Czech–German border. The paired catchments near the Czech–German border, whose forests were only mildly damaged by industrial pollution, differ in their acid buffering capacity (extremely low for LYS leucogranite, extremely high for PLB serpentinite). At the spruce die-back affected catchment UDL, 19 years of monthly hydrochemical monitoring revealed six times higher atmospheric deposition and runoff fluxes of Ca, compared to the paired catchments LYS and PLB. Across the three sites, the mean δ44Ca values increased in the order: spruce bark (−0.84‰)

Reactivity of atmospherically deposited nitrate (NO3−) and ammonium (NH4+) was investigated in three mountain forest catchments and one ombrotrophic peat bog located in the northern Czech Republic. The study sites are characterized by moderate to high N pollution rates that are currently decreasing. Monitoring of hydrodynamic data and catchment hydrochemistry (precipitation, soil solutions and runoff) was complemented by δ15N analyses of dissolved inorganic N (NO3−, NH4+). Measured δ 15N data were used to calculate the extent of biogeochemical reactions and to construct N mass balances. Two-component models of runoff generation were developed using hydrological and δ18O–H2O data on local precipitation, runoff, and soil waters collected by lysimeters. Catchment discharge was formed by groundwater (60–80%) and storm precipitation (40–20%), with minimal time lags. Groundwater had a diluting effect on reactions proceeding in the soil zone, including nitrification and denitrification. The rates of nitrification were estimated by comparing the δ15N values of atmospheric input and soil water, while the rates of denitrification were derived from the differences in the δ15N values of soil water and stream discharge. The Ν isotope effect of mineralisation of organic N was assessed by comparing δ15N values of soil and soil extracts. Nitrogen release from the catchments was controlled by temperature-dependent seasonality of soil reactions. Atmospheric N entered the runoff directly only during a short late winter - early spring period, accounting for approximately 10% of the total N input. Important inputs of mineralised organically cycled soil N were observed at the beginning and the end of the growing season, with measurable denitrification occurring during the same time periods. The measured apparent N isotope fractionations were significantly lower than previously published values (−3 to −14‰ vs. −30‰ for nitrification, and −3 vs. −20‰ for denitrification). Lower 15N fractionations originated both from the dilution effect of groundwater on stream discharge and from the depletion of available ammonium during nitrification reactions. Denitrification proceeding during recharge of the groundwater body was estimated from the difference in the δ15N values of NO3− in precipitation and groundwater.

Central European forests suffered from severe, large-scale atmospheric depositions of sulfur and nitrogen due to coal-based energy production during the 20th century. High deposition of acid compounds distorted soil chemistry and had negative effects on forest physiology and growth. Since 1994, continuous data on atmospheric deposition and stream runoff fluxes have provided evidence of ecosystem recovery from acidification. In this study, we combined for the first time mass budget data (sulfur deposition and total dissolved inorganic nitrogen (DIN) export) from the GEOMON monitoring network of headwater catchments with annual trajectories of vegetation indices derived from Landsat remote sensing observations. Time series of selected vegetation indices was constructed from Landsat 5, 7, and 8 using Google Earth Engine. Linear regression between the field data and vegetation indices was analyzed using R software. Biogeochemical responses of the forested catchment to declining acid deposition (driven by SO2 emission reduction) were consistent across all catchments covering various forest stands from different regions of the Czech Republic. Significant correlations were found with total sulfur depositions, suggesting that the forests are continuously and consistently prospering from reductions in acid deposition. Disturbance index (DI) was the only vegetation index that was well-related to changes in forest cover associated with salvage loggings (due to the forest decline) during the 1980s and 1990s. A significant relationship (R2 = 0.82) was found between the change in DI and DIN export in stream water. Regrowth of young forests in these highly affected areas tracks the most pronounced changes in total DIN export, suggesting a prominent role of vegetation in nitrogen retention. With the Landsat-derived DI, we could map decennial changes in forest disturbances beyond the small scale of the catchments to the regional level (demonstrated here for two protected landscape areas). This analysis showed the peak in forest disturbances to have occurred around the mid-1990s, followed by forest recovery and regrowth. Despite the improvement in forest ecosystem functioning over the past three decades in mountainous areas, emerging threats connected to changing climate will shape forest development in the near future.

Bedrock chemistry from three drill cores and fluxes of precipitation, throughfall and runoff from the 2015 water year were examined in three forested catchments in the western Czech Republic. The coefficient of alkalinity of rocks at the granitic (felsic) LYS catchment fall in the low chemical reactivity category. Rocks from the amphibolitic (mafic) NAZ catchment have high reactivity and rocks from the serpentinitic (mostly ultramafic) PLB catchment have high or even very high reactivity. Streamwater fluxes reflected the composition of the underlying bedrock lithologies, especially for magnesium, nickel and chromium at PLB, and for calcium, arsenic and sulfur at NAZ. Streamwater at LYS reflected incomplete neutralization of acidic deposition in the catchment and had mostly negative alkalinity and correspondingly very high fluxes of potentially toxic inorganic monomeric aluminum. Internal cycling of magnesium and calcium in spruce canopy throughfall was influenced by substrate chemistry at PLB and NAZ. About half of streamwater nitrogen left the catchments in the organic form.

Evapotranspiration (ET) continues to be a difficult process to estimate in seasonal and long-term water balances in catchment models. Approaches to estimate ET typically use vegetation parameters (e.g., leaf area index LAI, interception capacity) obtained from field observation, remote sensing data, national or global land cover products, and/or simulated by ecosystem models. In this study we attempt to quantify the uncertainty that spatial evapotranspiration estimation introduces into hydrological simulations when the age of the forest is not precisely known. The Penn State Integrated Hydrologic Model (PIHM) was implemented for the Lysina headwater catchment, located 50?03'N, 12?40'E in the western part of the Czech Republic. The spatial forest patterns were digitized from forest age maps made available by the Czech Forest Administration. Two ET methods were implemented in the catchment model: the Biome-BGC forest growth sub-model (1-way coupled to PIHM) and with the fixed-seasonal LAI method. From these two approaches simulation scenarios were developed. We combined the estimated spatial forest age maps and two ET estimation methods to drive PIHM. A set of spatial hydrologic regime and streamflow regime indices were calculated from the modeling results for each method. Intercomparison of the hydrological responses to the spatial vegetation patterns suggested considerable variation in soil moisture and recharge and a small uncertainty in the groundwater table elevation and streamflow. The hydrologic modeling with ET estimated by Biome-BGC generated less uncertainty due to the plant physiology-based method. The implication of this research is that overall hydrologic variability induced by uncertain management practices was reduced by implementing vegetation models in the catchment models. We quantify the uncertainty of hydrological modeling due to spatial ET estimation.We present a series of forest management probabilities from historic forest age maps.The plant physiology-based ET estimation reduced hydrologic uncertainty.Reduced uncertainty suggests the importance of forest growth in water use studies.

Lithogenic and biologically-fractionated magnesium (Mg) and calcium (Ca) are viewed as alternative controls of the δ26Mg and δ44Ca isotope signatures of streams and rivers. Understanding of Mg–Ca isotope systematics and of runoff generation in headwater catchments is crucial for upscaling riverine variability in δ26Mg and δ44Ca values to Mg–Ca isotope inputs into the oceans, and for global climate change considerations. Here we report Mg–Ca–Sr isotope systematics in a small, spruce-forested, high-elevation catchment in western Czech Republic, which has received high Mg and Ca inputs from dissolution of base-rich bedrock amphibolite and from industrial emissions. Our study site NAZ (Slavkov Forest) experienced a relatively long period of acid rain (ca. 1950–1995), accompanied by deposition of partly soluble dust from coal-burning power plants. Bedrock contained as much as 11 and 10 wt% of MgO and CaO, respectively. Input–output monitoring revealed a large net export of Mg, Ca, but also S, from the catchment via surface runoff. The δ26Mg values increased in the order: open-area precipitation (−1.44‰)

Three small forested catchments in the Czech Republic, each underlain by chemically contrasting silicate rocks, were investigated with focus on long-term atmospheric deposition of S, and pools and fluxes of Ca and Mg. Pools of Ca and Mg reflected geological substrate (granite: Ca, Mg poor, amphibolite: Ca, Mg rich, serpentinite: Ca poor, Mg rich). Long-term fluxes of S, Ca and Mg were tightly connected.

Granitic weathering profiles display highly diverse morphologies, reflecting the complex relationships between climate and weathering rates. Some profiles exhibit abrupt transitions from fresh bedrock to highly weathered material over short (30 m granitic weathering profile from the cool, temperate, Lysina catchment in the NW Czech Republic, from which we calculated mass transfer, weathering indices, and mineral specific weathering rates. The Lysina profile exhibits limited weathering extending >30 m into fractured bedrock, dominated by albite weathering at a rate of 9.3 × 10− 17 mol m2 s− 1. To identify environmental and geological controls on weathering front morphology and chemical weathering rates, Lysina was compared to previously published granitic weathering profiles from around the world. Weathering front morphology and weathering rates were calculated for the additional sites from published data and were correlated to mean annual precipitation (MAP), mean annual temperature (MAT), and erosion rates, with MAP having the strongest relationship. Higher MAP likely promotes lower saturation indices in pore waters, allowing weathering reactions to occur further from equilibrium. Comparison of erosion rates amongst the granitic catchments revealed an inconsistent effect on chemical weathering rates, but high erosion rates may promote weathering by reducing the thickness of the regolith and exposing the bedrock to reactive fluids. Mean annual temperatures appear to only have significant impacts on weathering fronts in environments with high precipitation and high erosion rates. Fractured bedrock profiles (Lysina and Río Icacos) have higher weathering intensities, than the other sites studied here. High connected porosity in fractured rocks enhances water movement allowing more efficient removal of weathering products, thus reducing thermodynamic saturation, increasing weathering rates, and producing sharper weathering gradients. These findings indicate that CO2 drawdown on geological timescales is also likely to be governed by precipitation rates, as well as temperature, and that much of the climate-significant weathering may occur within very narrow zones of the Earth's surface.

The Czech Republic was heavily industrialized in the second half of the 20th century but the associated emissions of Hg and S from coal burning were significantly reduced since the 1990s. We studied dissolved (filtered) stream water mercury (Hg) and dissolved organic carbon (DOC) concentrations at five catchments with contrasting Hg and S deposition histories in the Bohemian part of the Czech Republic. The median filtered Hg concentrations of stream water samples collected in hydrological years 2012 and 2013 from the five sites varied by an order of magnitude from 1.3 to 18.0 ng L − 1 . The Hg concentrations at individual catchments were strongly correlated with DOC concentrations r from 0.64 to 0.93 and with discharge r from 0.48 to 0.75. Annual export fluxes of filtered Hg from individual catchments ranged from 0.11 to 13.3 μg m − 2 yr − 1 and were highest at sites with the highest DOC export fluxes. However, the amount of Hg exported per unit DOC varied widely; the mean Hg/DOC ratio in stream water at the individual sites ranged from 0.28 to 0.90 ng mg − 1 . The highest stream Hg/DOC ratios occurred at sites Pluhův Bor and Jezeři which both are in the heavily polluted Black Triangle area. Stream Hg/DOC was inversely related to mineral and total soil pool Hg/C across the five sites. We explain this pattern by greater soil Hg retention due to inhibition of soil organic matter decomposition at the sites with low stream Hg/DOC and/or by precipitation of a metacinnabar (HgS) phase. Thus mobilization of Hg into streams from forest soils likely depends on combined effects of organic matter decomposition dynamics and HgS-like phase precipitation, which were both affected by Hg and S deposition histories.

The international Long-Term Ecological Research Network (ILTER) encompasses hundreds of long-term research/monitoring sites located in a wide array of ecosystems that can help us understand environmental change across the globe. We evaluated long-term trends (1990–2015) for bulk deposition, throughfall and runoff water chemistry and fluxes, and climatic variables in 25 forested catchments in Europe belonging to the UNECE International Cooperative Programme on Integrated Monitoring of Air Pollution Effects on Ecosystems (ICP IM). Many of the IM sites form part of the monitoring infrastructures of this larger ILTER network. Trends were evaluated for monthly concentrations of non-marine (anthropogenic fraction, denoted as x) sulphate (xSO4) and base cations x(Ca + Mg), hydrogen ion (H+), inorganic N (NO3 and NH4) and ANC (Acid Neutralising Capacity) and their respective fluxes into and out of the catchments and for monthly precipitation, runoff and air temperature. A significant decrease of xSO4 deposition resulted in decreases in concentrations and fluxes of xSO4 in runoff, being significant at 90% and 60% of the sites, respectively. Bulk deposition of NO3 and NH4 decreased significantly at 60–80% (concentrations) and 40–60% (fluxes) of the sites. Concentrations and fluxes of NO3 in runoff decreased at 73% and 63% of the sites, respectively, and NO3 concentrations decreased significantly at 50% of the sites. Thus, the LTER/ICP IM network confirms the positive effects of the emission reductions in Europe. Air temperature increased significantly at 61% of the sites, while trends for precipitation and runoff were rarely significant. The site-specific variation of xSO4 concentrations in runoff was most strongly explained by deposition. Climatic variables and deposition explained the variation of inorganic N concentrations in runoff at single sites poorly, and as yet there are no clear signs of a consistent deposition-driven or climate-driven increase in inorganic N exports in the catchments. Long-term changes (1990–2015) in the atmospheric deposition and runoff water chemistry of sulphate, inorganic nitrogen and acidity for forested catchments in Europe in relation to changes in emissions and hydrometeorological conditions

Quantifying rates of weathering and erosion of mafic rocks is essential for estimating changes to the oceans alkalinity budget that plays a significant role in regulating atmospheric CO2 levels. In this study, we present catchment-wide rates of weathering, erosion, and denudation measured with cosmogenic nuclides in mafic and ultramafic rock. We use the ratio of the meteoric cosmogenic nuclide 10Be, deposited from the atmosphere onto the weathering zone, to stable 9Be, a trace metal released by silicate weathering. We tested this approach in stream sediment and water from three upland forested catchments in the north-west Czech Republic. The catchments are underlain by felsic (granite), mafic (amphibolite) and ultramafic (serpentinite) lithologies. Due to acid rain deposition in the 20th century, the waters in the granite catchment exhibit acidic pH, whereas waters in the mafic catchments exhibit neutral to alkaline pH values due to their acid buffering capability. The atmospheric depositional 10Be flux is estimated to be balanced with the streams’ dissolved and particulate meteoric 10Be export flux to within a factor of two. We suggest a correlation method to derive bedrock Be concentrations, required as an input parameter, which are highly heterogeneous in these small catchments. Derived Earth surface metrics comprise (1) Denudation rates calculated from the 10Be/9Be ratio of the “reactive” Be (meaning sorbed to mineral surfaces) range between 110 and 185 t km−2 y−1 (40 and 70 mm ky−1). These rates are similar to denudation rates we obtained from in situ-cosmogenic 10Be in quartz minerals present in the bedrock or in quartz veins in the felsic and the mafic catchment. (2) The degree of weathering, calculated from the fraction of 9Be released from primary minerals as a new proxy, is about 40–50% in the mafic catchments, and 10% in the granitic catchment. Lastly, (3) erosion rates were calculated from 10Be concentrations in river sediment and corrected for sorting and dissolved loss. These amount to 50% of denudation rates from 10Be/9Be in the mafic and ultramafic catchments, the remainder being mass loss in the dissolved form by weathering. In contrast, erosion comprises most of the mass loss in the granitic catchment. These first results are encouraging, given that we find overall good agreement between in situ and meteoric cosmogenic methods, that our denudation rates are in the range of those published for middle European river catchments, and that degrees of weathering are as expected for these diverse lithologies. This method allows quantifying rates of erosion and weathering in mafic rock over the time scale of weathering that are, unlike in situ cosmogenic 10Be, independent from the presence of quartz. 10Be/9Be therefore offers to quantify Earth surface processes in a wide range of landscapes underlain by mafic rock – rates that are of high importance for exploring climate-weathering feedbacks but that have been inaccessible to date.

Current climate warming is expected to continue in coming decades, whereas high N deposition may stabilize, in contrast to the clear decrease in S deposition. These pressures have distinctive regional patterns and their resulting impact on soil conditions is modified by local site characteristics. We have applied the VSD+ soil dynamic model to study impacts of deposition and climate change on soil properties, using MetHyd and GrowUp as pre-processors to provide input to VSD+. The single-layer soil model VSD+ accounts for processes of organic C and N turnover, as well as charge and mass balances of elements, cation exchange and base cation weathering. We calibrated VSD+ at 26 ecosystem study sites throughout Europe using observed conditions, and simulated key soil properties: soil solution pH (pH), soil base saturation (BS) and soil organic carbon and nitrogen ratio (C:N) under projected deposition of N and S, and climate warming until 2100. The sites are forested, located in the Mediterranean, forested alpine, Atlantic, continental and boreal regions. They represent the long-term ecological research (LTER) Europe network, including sites of the ICP Forests and ICP Integrated Monitoring (IM) programmes under the UNECE Convention on Long-range Transboundary Air Pollution (LRTAP), providing high quality long-term data on ecosystem response. Simulated future soil conditions improved under projected decrease in deposition and current climate conditions: higher pH, BS and C:N at 21, 16 and 12 of the sites, respectively. When climate change was included in the scenario analysis, the variability of the results increased. Climate warming resulted in higher simulated pH in most cases, and higher BS and C:N in roughly half of the cases. Especially the increase in C:N was more marked with climate warming. The study illustrates the value of LTER sites for applying models to predict soil responses to multiple environmental changes.

Acidification has adversely affected freshwater ecosystems in many areas, and recovery from acidification is often interrupted by acidic events. We lack detailed information about how benthic algae react to short-term acidic events and long-term recovery from acidification. We sampled 15 stream sites in the Czech Republic to study the effects of (a) water pH, aluminium and lead concentrations, (b) short-term acidic events, (c) 20 years of recovery from acidification and (d) high phosphorus concentrations combined with low pH on soft-bodied benthic algae. Water pH and aluminium concentrations affected benthic algal assemblages, but the acidification index periphyton (AIP) mainly reflected pH. Benthic algal assemblages reflected recent acidic events more closely than maximum or average pH. Our results indicate that the reaction of benthic algae to pH results from a fast effect of pH minima that cause sensitive species to disappear within a few months, and a slower process of dispersal and competition for resources during periods of higher pH. After an acidic event, recolonization of stream sites by sensitive species had started within 2 years, and was largely completed after 9 years. Our data indicate that acidification may mask the effect of enhanced phosphorus concentrations on benthic algal eutrophication indices.

Two small forested catchments, each underlain by geochemically contrasting silicate rock types, were studied in the western Czech Republic. The felsic (granitic) Lysina catchment exhibited low resilience to anthropogenic acidic deposition and therefore low pH, Mg and high concentration of toxic species of Al in drainage water. Pluhův Bor, underlain by ultramafic rocks (especially serpentinite), exhibited very high resilience to acidic deposition and also peculiar drainage water chemistry due to the lithology (high pH, Mg, Ni and Cr). A significant depletion trend in Mg was observed from the unweathered to weathered rocks and to the topsoils at both sites. Enrichment profiles of K and Ca within the topsoil at Pluhův Bor indicated biocycling of these limiting nutrients.

Draft abstract: Global soils provide a variety of ecosystem services. However, currently, global soils are under various threats and in specific cases catastrophic decline in these services is observed across the continents. In this context, , the European Commission published the Thematic Strategy for Soil Protection identifies a specific policy need to address the threats to soil and ecosystem services that it provides. SoilTrEC which stands for Soil Transformations in European Catchments aims to research on soil processes and functions in a CZ context and, to provide recommendations to the stakeholders to develop appropriate policies on soil protection and ecosystem services. This paper presents an overview of the SoilTrEC project, its organizational structure, the methodology and the expected outcomes., JRC.H.8-Sustainability Assessment

A synoptic study of acidified mountain streams covering six Czech sites was performed. The aim was to provide biological data from small mountain streams in catchments with historically high acid atmospheric deposition, which have so far been subject of intensive long-term monitoring of hydrology and hydrochemistry only, in order to follow the development of the structure of benthic macroinvertebrates in the course of recovery from acidification. We focused on small headwater streams with minimum human influence in the catchment and relatively low concentrations of dissolved organic matter. The sites were classified according to their water pH status: three of them were strongly acidified (pH 4.07–4.57, concentration of reactive aluminium R-Al 448–1913 μg L−1), two were moderately acidified (pH 5.08–6.38, R-Al 52–261 μg L−1) and one non-acidified (pH 7.63–7.89, R-Al 12–59 μg L−1). The largest biotic difference detected by PCA was in the presence of the caddisflies Drusus, Rhyacophila, and Chaetopteryx villosa and stoneflies Leuctra pseudocingulata and Diura bicaudata. The results indicate that at the most acidified sites (the Lysina and the right branch of the Litavka), the process of biological recovery has not started yet due to an insufficient increase in stream pH. Indeed, MAGIC modelling published earlier shows that significant increases cannot be expected in the following decades. An average pH of at least 4.5 is needed for return of less acid-tolerant taxa such as Diura bicaudata, Leuctra major, L. pseudocingulata, L. pseudosignifera, Drusus or Rhyacophila. However, at the Sklařský potok — Jizerka site,^both the clear-cut of mature spruce plantations in 1984–1990 and the regional drop in SO2 emissions in the 1990s resulted in a decline of acid deposition and rising streamwater pH. Mean annual pH at the Sklařský potok — Jizerka outlet increased from 4.0 (1982–1985) to 5.3 (1990–1994), but episodic acidification has still resulted in a delay in recovery of the biota, particularly acid-sensitive species, which may be expected within a couple decades.

This chapter summarizes the methods, results, and conclusions of a 5-year research project (SoilTrEC: Soil Transformations in European Catchments) on experimentation, process modeling, and computational simulation of soil functions and soil threats across a network of European, Chinese, and United States Critical Zone Observatories (CZOs). The study focused on the soil functions of biomass production, carbon storage, water storage and transmission, water filtration, transformation of nutrients, and maintaining habitat and genetic diversity.The principal results demonstrate that soil functions can be quantified as biophysical flows and transformations of material and energy. The functions can be simulated with mathematical models of soil processes within the soil profile and at the critical zone interfaces with vegetation and atmosphere, surface waters and the below-ground vadose zone and groundwater. A new dynamic model for soil structure development, together with data sets from the CZOs, demonstrate both seasonal fluctuations in soil structure dynamics related to vegetation dynamics and soil carbon inputs, and long-term trends (decadal) in soil carbon storage and soil structure development.Cross-site comparison for 20 soil profiles at seven field sites with variation in soil type, lithology, land cover, land use, and climate demonstrate that sites can be classified, using model parameter values for soil aggregation processes together with climatic conditions and soil physical properties, along a trajectory of soil structure development from incipient soil formation through productive land use to overly intensive land use with soil degradation.A new modeling code, the Integrated Critical Zone model, was applied with parameter sets developed from the CZO site data to simulate the biophysical flows and transformations that quantify multiple soil functions. Process simulations coupled the new model for soil structure dynamics with existing modeling approaches for soil carbon dynamics, nutrient transformations, vegetation dynamics, hydrological flow and transport, and geochemical equilibria and mineral weathering reactions. Successful calibration, testing, and application of the model with data sets from horticulture plot manipulation experiments demonstrate the potential to apply modeling and simulation to the scoping and design of new practices and policy options to enhance soil functions and reduce soil threats worldwide.

Summarization: Soil organic carbon (SOC) is a strong determinant of soil fertility through its positive effects on soil structure and soil chemical and biological properties which in turn stimulate primary production. The objective of this work was to simulate field sites that represent different land uses and management practices in three continents, in order to identify the most important factors controlling soil structure dynamics and C sequestration across different climatic and lithological conditions as well as to quantify the rates of the aforementioned processes. The carbon, aggregation, and structure turnover (CAST) model was used to simulate SOC sequestration, aggregate formation, and structure dynamics in three field sites including nontilled soils of natural ecosystems and tilled soils of agricultural fields in Europe (Critical Zone Observatories (CZO) of the SoilTrEC network) and one site in North America. Derived data from the simulations’ results of SOC stocks and water-stable aggregate (WSA) particle size distribution, together with the respective results of three additional sites (Damma Glacier CZO, Milia (Greece), and Heilongjiang Mollisols (China)), were statistically analyzed in order to determine the factors affecting SOC sequestration and soil structure development. The natural ecosystems include nontilled soils covered with natural local vegetation, while the agricultural sites include cultivated and tilled soils covered with crops. The natural ecosystems were represented by Damma Glacier CZO (Switzerland), Heilongjiang Mollisols (China), Koiliaris CZO (Greece), Clear Creek (United States), and the Slavkov Forrest CZO (Czech Republic), whereas the agricultural field sites were located at Heilongjiang Mollisols (China), Koiliaris CZO (Greece), Clear Creek (United States), Marchfeld CZO (Austria), and Milia (Greece). Principal component analysis (PCA) identified clay content, bulk density, climatic conditions (precipitation and evapotranspiration), organic matter (OM), and its decomposition rates as the most important factors that controlled soil structure development. The relative importance of each of these factors differs under differing climatic and lithological conditions and differing stages of soil development. Overall, the modeling results for both natural ecosystems and agricultural fields were consistent with the field data. The model reliably simulated C and soil structure dynamics in various land uses, climatic conditions, and soil properties providing support for the underlying conceptual and mathematical modeling and evidence that the CAST model is a reliable tool to interpret soil structure formation processes and to aid the design of sustainable soil management practices. Appearing in: Quantifying and Managing Soil Functions in Earth's Critical Zone Combining Experimentation and Mathematical Modelling

Most of soil functions depend directly or indirectly on soil water retention and transmission, which explains their importance for many environmental processes within Earth's Critical Zones. Soil hydraulic properties are essential in irrigation and drainage studies for closing water balance equation, for predicting leaching of nutrients, for water supply to plants, and for other agronomical and environmental applications. Soil hydraulic properties reflect the structure of the soil porous system comprising pores of different geometry and sizes. This investigation comprises a detailed analytical study of soil hydraulic properties and climate conditions at 18 methodologically selected sites in Damma Glacier, Slavkov Forest, Marchfeld, and Koiliaris Critical Zone Observatories of SoilTrEC project. The local moisture regimes were assessed on a long-term basis by the Newhall model. The experimental data for soil water content at different potentials were used for assessing water storage capacity, pore size distribution, parameters of fitted retention curve equation, curve slope at the inflection point, and water permeability characteristics of each soil horizon. The differences of soil water retention and transmission characteristics—as fundamental properties describing soil structure—were explained by the different stages of soil profile development, parent materials, organic matter content, and land use histories.

Critical loads for acidification and eutrophication and their exceedances were determined for a selection of ecosystem effects monitoring sites in the Integrated Monitoring programme (UNECE ICP IM). The level of protection of these sites with respect to acidifying and eutrophying deposition was estimated for 2000 and 2020. In 2020 more sites were protected from acidification (67%) than in 2000 (61%). However, due to the sensitivity of the sites, even the maximum technically feasible emission reductions scenario would not protect all sites from acidification. In 2000, around 20% of the IM sites were protected from eutrophication. In 2020, under reductions in accordance with current legislation, about one third of the sites would be protected, and at best, with the maximum technically feasible reductions, half of the sites would be protected from eutrophication. Data from intensively monitored sites, such as those in ICP IM, provide a connection between modelled critical thresholds and empirical observations, and thus an indication of the applicability of critical load estimates for natural ecosystems. Across the sites, there was good correlation between the exceedance of critical loads for acidification and key acidification parameters in runoff water, both with annual mean fluxes and concentrations. There was also evidence of a link between exceedances of critical loads of nutrient nitrogen and nitrogen leaching. The collected empirical data of the ICP IM thus allow testing and validation of key concepts used in the critical load calculations. This increases confidence in the European-scale critical loads mapping used in integrated assessment modelling to support emission reduction agreements.

Data from 32 long-term (1994–2012) monitoring sites were used to assess temporal development and spatial variability of sulphur (S) and inorganic nitrogen (N) concentrations in bulk precipitation, and S in throughfall, for the Czech Republic. Despite large variance in absolute S and N concentration/deposition among sites, temporal coherence using standardised data (Z score) was demonstrated. Overall significant declines of SO4 concentration in bulk and throughfall precipitation, as well as NO3 and NH4 concentration in bulk precipitation, were observed. Median Z score values of bulk SO4, NO3 and NH4 and throughfall SO4 derived from observations and the respective emission rates of SO2, NOx and NH3 in the Czech Republic and Slovakia showed highly significant (p < 0.001) relationships. Using linear regression models, Z score values were calculated for the whole period 1900–2012 and then back-transformed to give estimates of concentration for the individual sites. Uncertainty associated with the concentration calculations was estimated as 20% for SO4 bulk precipitation, 22% for throughfall SO4, 18% for bulk NO3 and 28% for bulk NH4. The application of the method suggested that it is effective in the long-term reconstruction and prediction of S and N deposition at a variety of sites. Multiple regression modelling was used to extrapolate site characteristics (mean precipitation chemistry and its standard deviation) from monitored to unmonitored sites. Spatially distributed temporal development of S and N depositions were calculated since 1900. The method allows spatio-temporal estimation of the acid deposition in regions with extensive monitoring of precipitation chemistry.

Growth in human population and demand for wealth creates ever-increasing pressure on global soils, leading to soil losses and degradation worldwide. Critical Zone science studies the impact linkages between these pressures, the resulting environmental state of soils, and potential interventions to protect soil and reverse degradation. New research on soil processes is being driven by the scientific hypothesis that soil processes can be described along a life cycle of soil development. This begins with formation of new soil from parent material, development of the soil profile, and potential loss of the developed soil functions and the soil itself under overly intensive anthropogenic land use, thus closing the cycle. Four Critical Zone Observatories in Europe have been selected focusing research at sites that represent key stages along the hypothetical soil life cycle; incipient soil formation, productive use of soil for farming and forestry, and decline of soil due to longstanding intensive agriculture. Initial results from the research show that soil develops important biogeochemical properties on the time scale of decades and that soil carbon and the development of favourable soil structure takes place over similar time scales. A new mathematical model of soil aggregate formation and degradation predicts that set-aside land at the most degraded site studied can develop substantially improved soil structure with the accumulation of soil carbon over a period of several years. Further results demonstrate the rapid dynamics of soil carbon; how quickly it can be lost, and also demonstrate how data from the CZOs can be used to determine parameter values for models at catchment scale. A structure for a new integrated Critical Zone model is proposed that combines process descriptions of carbon and nutrient flows, a simplified description of the soil food web, and reactive transport; all coupled with a dynamic model for soil structure and soil aggregation. This approach is proposed as a methodology to analyse data along the soil life cycle and test how soil processes and rates vary within, and between, the CZOs representing different life cycle stages. In addition, frameworks are discussed that will help to communicate the results of this science into a more policy relevant format using ecosystem service approaches.

Hydrochemical patterns resulting from differing bedrock geochemistry were ascertained by concurrent streamwater sampling in three small catchments, each underlain by geochemically contrasting silicate rock types in the western Czech Republic, Central Europe in 2001–2010. The catchments are situated 5–7 km apart in the Slavkov Forest and are occupied by Norway spruce ( Picea abies ) plantations. They have similar altitude, area, topography, mean annual air temperature, and atmospheric deposition fluxes. The amount of base cations oxides (Ca + Mg + Na + K) is markedly different among the three studied rocks (leucogranite 8%, amphibolite 22%, serpentinite 36%). The leucogranite contains a very small amount of MgO, while the serpentinite contains extremely large amounts of MgO. The amphibolite contains an intermediate amount of MgO and elevated CaO. The Lysina, on leucogranite, exhibited very small concentrations of Mg (median 0.4 mg L −1 ) in streamwater; Pluhův Bor, on serpentinite, contained extremely high concentrations of streamwater Mg (18 mg L −1 ). Streamwater in the Na Zelenem catchment, on amphibolite, contained an intermediate amount of Mg and an elevated Ca. Very low pH (4.2), negative alkalinity (−60 μeq L −1 ) and high inorganic monomeric Al concentrations (0.3 mg L −1 ) were found in the stream draining leucogranite. Serpentinite streamwater exhibited the highest pH (7.6), alkalinity (+940 μeq L −1 ) and Ni concentrations (100 μg L −1 ). Aquatic chemistry reflected the composition of the underlying rocks within the studied catchments. Contrasting streamwater compositions of the studied catchments were generated according to the MAGIC model simulations mainly by differences in chemical weathering rates of base cations (65 meq m −2 a −1 at Lysina, 198 meq m −2 a −1 at Na Zelenem, and 241 meq m −2 a −1 at Pluhův Bor).

European Union policy on soil threats and soil protection has prioritized new research to address global soil threats. This research draws on the methodology of Critical Zone Observatories (CZOs) to focus a critical mass of international, multidisciplinary expertise at specific field sites. These CZOs were selected as part of an experimental design to study soil processes and ecosystem function along a hypothesized soil life cycle—from incipient soil formation where new parent material is being deposited, to highly degraded soils that have experienced millennia of intensive land use. Further CZOs have been selected to broaden the range of soil environments and data sets to test soil process models that represent the stages of the soil life cycle. The scientific methodology for this research focuses on the central role of soil structure and soil aggregate formation and stability in soil processes. Research methods include detailed analysis and mathematical modeling of soil properties related to aggregate formation and their relation to key processes of reactive transport, nutrient transformation, and C and food web dynamics in soil ecosystems. Within this program of research, quantification of soil processes across an international network of CZOs is focused on understanding soil ecosystem services including their quantitative monetary valuation within the soil life cycle. Further experimental design at the global scale is enabled by this type of international CZO network. One example is a proposed experiment to study soil ecosystem services along planetary-scale environmental gradients. This would allow scientists to gain insight into the responses of soil processes to increasing human pressures on Earth's critical zone that arise through rapidly changing land use and climate.

Aluminum (Al) chemistry was studied in soils and waters of two catchments covered by spruce (Picea abies) monocultures in the Czech Republic that represent geochemical end-members of terrestrial and aquatic sensitivity to acidic deposition. The acid-sensitive Lysina catchment, underlain by granite, was compared to the acid-resistant Pluhův Bor catchment on serpentine. Organically-bound Al was the largest pool of reactive soil Al at both sites. Very high median total Al (Alt) concentrations (40 micromol L(-1)) and inorganic monomeric Al (Ali) concentrations (27 micromol L(-1)) were observed in acidic (pH 4.0) stream water at Lysina in the 1990s and these concentrations decreased to 32 micromol L(-1) (Alt) and 13 micromol L(-1) (Ali) in the 2000s. The potentially toxic Ali fraction decreased in response to long-term decreases in acidic deposition, but Ali remained the largest fraction. However, the organic monomeric (Alo) and particulate (Alp) fractions increased in the 2000s at Lysina. In contrast to Lysina, marked increases of Alt concentrations in circum-neutral waters at Pluhův Bor were observed in the 2000s in comparison with the 1990s. These increases were entirely due to the Alp fraction, which increased more than 3-fold in stream water and up to 8-fold in soil water in the A horizon. Increase of Alp coincided with dissolved organic carbon (DOC) increases. Acidification recovery may have increased the content of colloidal Al though the coagulation of monomeric Al.

The geoecology of a serpentinite-dominated site in the Czech Republic was investigated by rock, soil, water, and plant analyses. The 22-ha Pluhův Bor watershed is almost entirely forested by a nearly 110-year old plantation of Picea abies (Norway Spruce) mixed with native Pinus sylvestris (Scots Pine) in the highest elevations. It is mainly underlain by serpentinite, with occassional tremolite and actinolite schists and amphibolite outcrops. Tremolite schists and especially serpentinites are characterized by extremely high concentrations of Mg, Ni, and Cr and by negligible concentrations of K, creating an unusual environment for plants. The spruce growth rate is very slow, apparently as a result of K deficiency, Mg oversupply, and Ni toxicity. Foliar Ca is in the upper part of the optimum range because schists and amphibolites are important sources of Ca to the soil exchangeable pool and vegetation. Mineral weathering and atmospheric deposition generate near-neutral magnesium-bicarbonate-sulfate ...

Temporal trends in DOC concentration and flux were investigated at two geochemically distinct forested catchments in western Czech Republic. Mean discharge-weighted DOC concentrations averaged 18.8 mg L(-1) at the acidic Lysina catchment, and 20.2 mg L(-1) at base-rich and well-buffered Pluhuv Bor. Between 1993 and 2007 DOC in streamwater increased significantly in both catchments: the mean annual increase was 0.42 mg L(-1) yr(-1) (p < 0.001) at Lysina and 0.43 mg L(-1) yr(-1) (p < 0.001) at Pluhuv Bor, resulting in cumulative increases of 64 and 65%, respectively. These long-term increases in streamwater DOC were correlated with only modest increases in stream pH in both catchments, but large declines in ionic strength (IS), that resulted from declining atmospheric deposition. Neither catchment has undergone changes in soil-water pH, yet DOC concentrations tripled in the soil-water of both catchments. We conclude that changes in ionic strength of soil-water and streamwater, rather than acidity, are the primary drivers of changes in streamwater DOC in this region. Temperature, precipitation and discharge show no statistically significant trends during the study period, suggesting that climate change has played no role in the changes in DOC that we have observed.