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Thermodynamic modeling of the Cu-Fe-S liquid solution is carried in the framework of the modified quasichemical model. The manifold nature of Cu-Fe-S liquid solutions from highly metallic via sulfur-rich to pure liquid sulfur is described by one single Gibbs energy expression at 1 bar total pressure. The model predictive ability of an asymmetric versus symmetric approach is thermodynamically analyzed with respect to the extrapolation scheme from the binary subsystems into the ternary system. Without the need of adjustable ternary parameters predictions of sulfur potentials for the liquid phase are in line with experimental data available in the literature. High-temperature pyrrhotite optimized via the compound energy formalism and Cu-Fe-S alloy phases are taken into consideration to predict phase equilibria with the liquid solution. Four isothermal and four isoplethal sections demonstrate promising agreement between a large stock of experimental data and prediction.

Within the formalism of the one-sublattice modified quasichemical model an equation for the computation of pair fraction distributions is derived considering distinct model modifications reported in the literature. For generalization an equation system is presented to determine pair fraction distributions of multicomponent solutions. Consistency of the derived equation with the analogous relationship of former versions of the modified quasichemical model is demonstrated. The derived equation is applied to the Cu-Fe-S liquid solution and its binary subsystems. Pair fraction distributions calculated exemplarily at 1200 °C (1473 K) are used to interpret recently reported predictions of the high-temperature Cu-Fe-S system.

Die atmosphärische Stickstoff-Deposition hat bis Mitte der 1990er-Jahre zugenommen und ist seither rückläufig. Eine genauere Betrachtung zeigt, dass der Verlauf regional unterschiedlich ist je nach orografischer Lage und Nähe zu Ammoniak-Quellen. Die Nitratauswaschung aus den Waldböden ist ein Indikator für die Sättigung des Waldbodens mit Stickstoff und zeigt das Risiko einer Versauerung des Waldbodens an. Dazu kommt, dass zu viel Nitrat im Grund- und Trinkwasser für Mensch und Tier eine gesundheitliche Bedrohung darstellt.

Verfrühter Fruchtabwurf in Schweizer Buchenbeständen im Hitze- und Trockensommer 2018 Die Rotbuche (Fagus sylvatica) zeigt mit ihrer Fortpflanzungsstrategie ein klares Mastverhalten, das heisst, sie produziert nur in einzelnen Jahren sehr grosse Mengen an Blüten und Früchten (Bucheckern). Bisher wurde angenommen, dass die Buche zu den Baumarten gehört, die bei erfolgter Bestäubung in aller Regel auch Früchte produziert. Im Schweizer Hitze- und Trockensommer 2018 reagierte die Buchen an einigen Standorten aber anders: Nach einer sehr starken Blüte entwickelten sie nur wenige Früchte, oder sie warfen die unvollständig entwickelten Früchte bereits Mitte des Sommers ab. Die Analyse von Messdaten der letzten 15 bis 19 Jahre von drei Buchenuntersuchungsflächen der Langfristigen Waldökosystem-Forschung (LWF) zeigt, dass starke Hitzewellen und langanhaltende Trockenheit während der Fruchtentwicklung zu einem Abbruch der Fruchtproduktion führen können. Diese extremen Wetterverhältnisse funktionieren somit als «Umweltveto». In Jahren mit vergleichbaren Bedingungen während der Fruchtentwicklung waren die Durchschnittstemperaturen im Sommer um 1.5 °C höher, und der Niederschlag war um 45% niedriger als im langjährigen Mittel. Der angenommene Zweijahreszyklus der Buchenblüte kann somit nicht nur durch ungünstige Wetterbedingungen während der Bestäubung, sondern auch während der Fruchtentwicklung unterbrochen werden.

Central Europe has been experiencing unprecedented droughts during the last decades, stressing the decrease in tree water availability. However, the assessment of physiological drought stress is challenging, and feedback between soil and vegetation is often omitted because of scarce belowground data. Here we aimed to model Swiss forests' water availability during the 2015 and 2018 droughts by implementing the mechanistic soil-vegetation-atmosphere-transport (SVAT) model LWF-Brook90 taking advantage of regionalized depth-resolved soil information. We calibrated the model against soil matric potential data measured from 2014 to 2018 at 44 sites along a Swiss climatic and edaphic drought gradient. Swiss forest soils' storage capacity of plant-available water ranged from 53 mm to 341 mm, with a median of 137 ± 42 mm down to the mean potential rooting depth of 1.2 m. Topsoil was the primary water source. However, trees switched to deeper soil water sources during drought. This effect was less pronounced for coniferous trees with a shallower rooting system than for deciduous trees, which resulted in a higher reduction of actual transpiration (transpiration deficit) in coniferous trees. Across Switzerland, forest trees reduced the transpiration by 23% (compared to potential transpiration) in 2015 and 2018, maintaining annual actual transpiration comparable to other years. Together with lower evaporative fluxes, the Swiss forests did not amplify the blue water deficit. The 2018 drought, characterized by a higher and more persistent transpiration deficit than in 2015, triggered widespread early wilting across Swiss forests that was better predicted by the SVAT-derived mean soil matric potential in the rooting zone than by climatic predictors. Such feedback-driven quantification of ecosystem water fluxes in the soil–plant-atmosphere continuum will be crucial to predicting physiological drought stress under future climate extremes., Global Change Biology, 28 (20), ISSN:1354-1013, ISSN:1365-2486

Despite the importance of vegetation uptake of atmospheric gaseous elemental mercury (Hg(0)) within the global Hg cycle, little knowledge exists on the physiological, climatic and geographic factors controlling stomatal uptake of atmospheric Hg(0) by tree foliage. We investigate controls on foliar stomatal Hg(0) uptake by combining Hg measurements of 3,569 foliage samples across Europe with data on tree species traits and environmental conditions. To account for foliar Hg accumulation over time, we normalized foliar Hg concentration over the foliar life period from the simulated start of the growing season to sample harvest. The most relevant parameter impacting daily foliar stomatal Hg uptake was tree functional group (deciduous versus coniferous trees). On average, we measured 3.2 times higher daily foliar stomatal Hg uptake rates in deciduous leaves than in coniferous needles of the same age. Across tree species, for foliage of beech and fir, and at two out of three forest plots with more than 20 samples, we found a significant (p

A thorough review and critical evaluation of all experimental sulfur potential and phase diagram data available from the literature has been made for optimizing the Gibbs energy of the copper-sulfur liquid phase at 1 bar total pressure. The extended modified quasichemical model serves as a basis for the mathematical expression of the Gibbs energy of binary Cu-S solutions over the complete composition range. A structurally versatile molten phase ranging from highly metallic via sulfur-rich to pure sulfuric is described simultaneously by a single Gibbs energy function. In combination with the recently published Gibbs energies of all Cu-S solid phases, the complete T–x phase diagram as well as for the first time the $$ {\text{log(}}p_{{{\text{S}}2}} /{\text{bar)}} - 1 /T $$ log( p S 2 / bar) - 1 / T diagram is calculated. A limited set of obtained model parameters reproduces a large body of data within experimental uncertainties.

Most trees form symbioses with ectomycorrhizal fungi (EMF) which influence access to growth-limiting soil resources. Mesocosm experiments repeatedly show that EMF species differentially affect plant development, yet whether these effects ripple up to influence the growth of entire forests remains unknown. Here we tested the effects of EMF composition and functional genes relative to variation in well-known drivers of tree growth by combining paired molecular EMF surveys with high-resolution forest inventory data across 15 European countries. We show that EMF composition was linked to a three-fold difference in tree growth rate even when controlling for the primary abiotic drivers of tree growth. Fast tree growth was associated with EMF communities harboring high inorganic but low organic nitrogen acquisition gene proportions and EMF which form contact versus medium-distance fringe exploration types. These findings suggest that EMF composition is a strong bio-indicator of underlying drivers of tree growth and/or that variation of forest EMF communities causes differences in tree growth. While it may be too early to assign causality or directionality, our study is one of the first to link fine-scale variation within a key component of the forest microbiome to ecosystem functioning at a continental scale., The ISME Journal, 16 (5), ISSN:1751-7362, ISSN:1751-7370

Atmospheric nitrogen (N) deposition in terrestrial ecosystems is difficult to quantify, especially in forests. In this study, we compared three approaches for determining the wet and dry deposition of nitrogen (total deposition) at 17 intensively monitored forest sites in Switzerland. Specifically, we considered approaches based on: 1) measurements of bulk deposition and throughfall in 2014 (throughfall method); 2) measurements of bulk deposition and measurements of air concentrations of ammonia (NH3) and nitrogen dioxide (NO2), to which deposition velocities were applied, also in 2014 (inferential method); and 3) a model developed for Switzerland at a high spatial resolution, run for the five-year period 2013–2017 (emission based model). In addition, changes over two decades were assessed using continuous measurements of throughfall and bulk deposition. Further, air concentrations of NH3 and NO2 measured in 2014 were compared with concentrations measured in 2000 at 10 of the sites. The three approaches generally yielded comparable estimates of total deposition, with some notable differences at some sites. For both the model and the inferential method, uncertainties were related to the deposition velocities that were applied to air concentrations of N compounds, especially for NH3. The throughfall method provided a minimum estimate of the total N deposition in the forest, but the fraction of the deposited N that is directly taken up by the canopy remained difficult to quantify. Nitrogen deposition has decreased since the mid-1990s at the majority of the sites. However, deposition of the reduced forms of N seems to have stagnated at the local level. Furthermore, N deposition is still too high in comparison with the range of empirical critical loads of N (CLN). The minimum deposition estimated from throughfall exceeds the lower limit of CLN at all sites except those in the Central Alps. Deposition estimated with the model and the inferential method exceeds the lower limit of CLN at all sites and even exceeds the upper limit at several locations.

Mast seeding, the synchronised occurrence of large amounts of fruits and seeds at irregular intervals, is a reproductive strategy in many wind-pollinated species. Although a series of studies have investigated mast year (MY) patterns in European forest tree species at the regional scale, there are few recent evaluations at a European scale on the impact of weather variables (weather cues) and resource dynamics on mast behaviour. Thus the main objective of this study is to investigate the impact of specific weather conditions, as environmental drivers for MYs, on resources in Fagus sylvatica L., Quercus petraea ( Matt.) Liebl. , Quercus robur L., Picea abies (L.) Karst . and Pinus sylvestris L. at a European level and to explore the robustness of the relationships in smaller regions within Europe. Data on seed production originating from the International Co-operative Programme on Assessment and Monitoring of Air Pollution Effects on Forests (ICP Forests) were analysed. Three beta regression models were applied to investigate the impact of seasonal weather variables on MY occurrence, as well as the influence of fruiting intensity levels in the years prior to MYs. Resource dynamics are analysed at three different spatial scales (continent, countries and ecoregions). At a European scale, important weather cues for beech MYs were a cold and wet summer two years before a MY, a dry and warm summer one year before a MY and a warm spring in the MY. For spruce, a cold and dry summer two years prior to a MY and a warm and dry summer in the year before the MY showed the strongest associations with the MY. For oak, high spring temperature in the MY was the most important weather cue. For beech and spruce, and to some extent also for oak species, the best fitting models at European scale were well reflected by those found at smaller scales. For pine, best fitting models were highly diverse concerning weather cues. Fruiting levels were high in all species two years before the MY and also high one year before the MY in the oak species and in pine. In beech, fruiting levels one year before the MY were not important and in spruce, they were inconsistent depending on the region. As a consequence, evidence of resource depletion could only be seen in some regions for spruce.

There is mounting evidence demonstrating that fluxes and chemical composition of precipitation is substantially changed after passing through tree canopies, particularly in the case of atmospheric nitrogen (N) compounds, with important implications on forest N cycling. However, the processes underpinning those changes – beyond the leaf retention and/or leaching of N compounds - have been less investigated. In a previous study we provided isotopic evidence that biological nitrification in tree canopies was responsible for significant changes in the amount of NO3- from rainfall to throughfall across two UK forests at high nitrogen (N) deposition. This finding strongly suggested that forest canopies are not just passive filters for precipitation water and dissolved nutrients, and that the microbial life hidden within them can be responsible for transforming atmospheric N before it reaches the soil. We extended the isotopic approach at the European scale, and combined it to next-generation sequence analyses with the aim of elucidating canopy nitrification and identify phyllosphere microbes responsible for it. Specifically, in this study we: 1) estimated the relative contribution of NO3- derived from biological canopy nitrification vs. atmospheric deposition by using δ18O and δ17O of NO3- in rainfall and throughfall water; 2) quantified the functional genes related to nitrification, and finally 3) characterized the microbial communities harboured in tree canopies (i.e., phyllosphere) and in the underlying soils for two dominant tree species in Europe (Fagus sylvatica L. and Pinus sylvestris L.) using metabarcoding techniques. We considered twelve sites included in the European ICP Forests monitoring network, chosen along climate and N deposition gradients, spanning from Fennoscandia to the Mediterranean. We will show that presence of nitrifying microbes (as assessed through qPCR) and their activity (as derived from δ18O and δ17O) were detected in the tree canopies across most of the sites, and that canopy nitrification was significantly correlated with atmospheric N deposition. Finally, we will discuss differences in microbial community structure and composition across phyllosphere (and between the two tree species considered), water and soil samples in the investigated forests. Our study demonstrates the potential of integrating stable isotopes with microbial analyses to advance our understanding on canopy-atmosphere interactions and their contribution to N cycling.

In mountainous terrain, rainfall-induced landslides pose a serious risk to people and infrastructure. Regional landslide early warning systems (LEWS) have proven to be a cost-efficient tool to inform the public about the imminent landslide danger. While most operational LEWS are based on rainfall exceedance thresholds only, recent studies have demonstrated an improvement of the forecast quality after the inclusion of soil hydrological information. In this study, the potential of in situ soil moisture measurements for regional landslide early warning is assessed. For the first time, a comprehensive soil moisture measurement database was compiled for Switzerland and compared with a national landslide database (Swiss flood and landslide damage database, WSL). The time series were homogenized and normalized to represent saturation values. From ensembles of sensors, the mean and standard deviation saturation were calculated and infiltration events were delimited, characterized, and classified as landslide-triggering or non-triggering based on the occurrence of landslides within a specified forecast distance. A logistic regression function was applied to model the landslide activity based on the infiltration event characteristics and several models were analysed and compared with receiver operating characteristics (ROC). A strong distance dependence becomes apparent showing a forecast goodness decrease with increasing distance between water content measurement site and landslide, and a better forecast goodness for long-lasting as opposed to short-duration precipitation events. While most variability can be explained by the two event properties antecedent saturation and change of saturation during an infiltration event, event properties that describe antecedent conditions are more important for long-lasting as opposed to short-duration precipitation events that can be better explained by properties describing event dynamics. Overall, the analysis demonstrated that in situ soil moisture data effectively contains specific information useful for landslide early warning., Landslides, 17, ISSN:1612-510X

European beech is known to be a masting species, i.e. fruit production does not occur every year. It is thought to be a species which is flowering controlled, i.e. that after successful pollination, fruits and seeds would be produced. In the last two decades, years with high fruit production occurred every two to three years in Middle Europe, which may be indication for an inherent biennial cycle. However, successful fruit production can be hampered by disadvantageous weather conditions, such as frost events, during the pollination season.In Switzerland, after high beech pollen concentration was measured in spring of 2018, high fruit production was expected. However, during the extremely hot and dry European summer of 2018, beech produced no, or only small amounts of beechnuts in two of three long-term monitoring beech stands in Switzerland, which are part of the Swiss Long-Term Forest Ecosystem Research Programme. We observed that beechnuts were aborted in early summer already. Over the last decades, we found similar examples of mast failure and fruit abortion in years with hot and dry summer conditions. These extreme conditions can thus act as an “environmental veto”, similar to frost events during flowering. In years with fruit abortion, summer mean temperatures were 1.2°C higher, and precipitation sums were 45% lower than the long-term average. Our findings are evidence for a biennial masting cycle in European beech, which can be interrupted by extreme weather conditions such as extreme summer heat and drought or frost during flowering.

Pollen is known to affect forest throughfall biochemistry, but underlying mechanisms are not fully understood. We used generalized additive mixed modelling to study the relationship between long-term series of measured throughfall fluxes in spring (April–June) at forest plots and corresponding airborne pollen concentrations (Seasonal Pollen Integral, SPIn) from nearby aerobiological monitoring stations. The forest plots were part of the intensive long term monitoring (Level II) network of the UNECE International Co-operative Programme on Assessment and Monitoring of Air Pollution Effects on Forests (ICP Forests) with dominant tree genera Fagus, Quercus, Pinus and Picea, and were distributed all across Europe. We also conducted a 7-day laboratory dissolution experiment with bud scales and flower stalks of European beech (Fagus sylvatica L.), pollen of beech, common oak (Quercus robur L.), silver birch (Betula pendula L.), Scots pine (Pinus sylvestris L.), Corsican pine (Pinus nigra Arnold ssp. laricio (Poiret) Maire), Norway spruce (Picea abies (L.) Karst.) and sterilized pollen of silver birch in a nitrate (NO3--N) solution (11.3 mg N L-1). Throughfall fluxes of potassium (K+), ammonium (NH4+-N), dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) showed a positive relationship with SPIn whereas NO3--N fluxes showed a negative relationship with SPIn. In years with massive seed production of beech and oak SPIn and throughfall fluxes of K+ and DOC were higher, but fluxes of NO3--N were lower. The experiment broadly confirmed the findings based on field data. Within two hours, pollen released large quantities of K+, phosphate, DOC and DON, and lesser amounts of sulphate, sodium and calcium. After 24-48 hours, NO3--N started to disappear, predominantly in the treatments with broadleaved pollen, while concentrations of nitrite and NH4+-N increased. At the end of the experiment, the inorganic nitrogen (DIN) was reduced, presumably because it was lost as gaseous nitric oxide (NO). There was no difference for sterilized pollen, indicating that the involvement of microbial activity was limited in above N transformations. Our results show that pollen dispersal might be an overlooked factor in forest nutrient cycling and might induce complex canopy N transformations, although the net-impact on N throughfall fluxes is rather low.

Climate change and the expected increase in frequency of dry summers are likely to affect the growth of important tree species. We investigated relationships between morphological and chemical leaf traits of European beech (Fagus sylvatica L.) and environmental factors along a water availability gradient consisting of 12 sites located throughout Switzerland. We found that leaf dry mass and leaf area tended to decrease with increasing long-term mean annual precipitation (MAP) and actual to potential transpiration (AT/PT), two correlated variables that form the water availability gradient. These results contrast with those of several other studies, and might be explained by favourable temperature and humidity conditions during leaf formation in spring at the dry sites. Although the relationship was not linear over the whole gradient, the drier sites were characterized by beech with a lower specific leaf area, along with higher foliar potassium (K) and lower foliar nitrogen (N) concentrations. These patterns likely reflect strategies developed as an adaptation to reduced water availability, but they also result from variation in the availability of nutrients in soil across our sites. In the case of N, there are indications that atmospheric deposition plays a role in foliar concentrations.

The response of forest productivity to climate extremes strongly depends on ambient environmental and site conditions. To better understand these relationships at a regional scale, we used nearly 800 observation years from 271 permanent long‐term forest monitoring plots across Switzerland, obtained between 1980 and 2017. We assimilated these data into the 3‐PG forest ecosystem model using Bayesian inference, reducing the bias of model predictions from 14% to 5% for forest stem carbon stocks and from 45% to 9% for stem carbon stock changes. We then estimated the productivity of forests dominated by Picea abies and Fagus sylvatica for the period of 1960–2018, and tested for productivity shifts in response to climate along elevational gradient and in extreme years. Simulated net primary productivity (NPP) decreased with elevation (2.86 ± 0.006 Mg C ha−1 year−1 km−1 for P. abies and 0.93 ± 0.010 Mg C ha−1 year−1 km−1 for F. sylvatica). During warm–dry extremes, simulated NPP for both species increased at higher and decreased at lower elevations, with reductions in NPP of more than 25% for up to 21% of the potential species distribution range in Switzerland. Reduced plant water availability had a stronger effect on NPP than temperature during warm‐dry extremes. Importantly, cold–dry extremes had negative impacts on regional forest NPP comparable to warm–dry extremes. Overall, our calibrated model suggests that the response of forest productivity to climate extremes is more complex than simple shift toward higher elevation. Such robust estimates of NPP are key for increasing our understanding of forests ecosystems carbon dynamics under climate extremes., We assimilated extensive and long‐term monitoring data into the 3‐PG forest ecosystem model to assess how forest productivity responds to climate extremes across environmental gradients in Switzerland. Data assimilation using Bayesian inference significantly improved model predictions. During warm–dry extremes, net primary productivity increased at higher and decreased at lower elevations, with reductions in NPP of more than 25% for one‐fifth of the potential species distribution range in Switzerland.

Changing environmental conditions may substantially interact with site quality and forest stand characteristics, and impact forest growth and carbon sequestration. Understanding the impact of the various drivers of forest growth is therefore critical to predict how forest ecosystems can respond to climate change. We conducted a continental-scale analysis of recent (1995–2010) forest volume increment data (ΔVol, m3 ha−1 yr−1), obtained from ca. 100,000 coniferous and broadleaved trees in 442 even-aged, single-species stands across 23 European countries. We used multivariate statistical approaches, such as mixed effects models and structural equation modelling to investigate how European forest growth respond to changes in 11 predictors, including stand characteristics, climate conditions, air and site quality, as well as their interactions. We found that, despite the large environmental gradients encompassed by the forests examined, stand density and age were key drivers of forest growth. We further detected a positive, in some cases non-linear effect of N deposition, most pronounced for beech forests, with a tipping point at ca. 30 kg N ha−1 yr−1. With the exception of a consistent temperature signal on Norway spruce, climate-related predictors and ground-level ozone showed much less generalized relationships with ΔVol. Our results show that, together with the driving forces exerted by stand density and age, N deposition is at least as important as climate to modulate forest growth at continental scale in Europe, with a potential negative effect at sites with high N deposition.

All phase equilibria and thermodynamic data available in the literature on the copper sulfides high- and low-temperature chalcocite, djurleite and anilite have been critically analyzed for optimization of the solid-state phase diagram of the Cu-S system at 1 bar total pressure. A two-sublattice approach derived from a recently developed Gibbs energy model for digenite enables the consideration of the solid solution nature of both modifications of chalcocite and for the first time of djurleite. Anilite is considered as stoichiometric compound. The sulfur solubility of metallic copper is described by a substitutional approach. The obtained Gibbs energy functions for high- and low-temperature chalcocite, djurleite, anilite and copper alloy phase allow computations and predictions of phase equilibria and thermodynamic properties in good accordance with experimental data of the Cu-S solid-state system.

We present results of two studies on the (1) potential wood load in steep headwater streams and (2) properties of large wood (LW) transported in mountain rivers during the large August 2005 flood event in Switzerland. Ten headwater reaches of 1000 m length were surveyed in different regions of Switzerland. The potential wood load was estimated for in-channel deadwood, and possible driving factors were explored. Correlations were found with dead wood volume on hillslopes and mean channel width. We established size distributions of LW pieces and identified probable recruitment processes. Four reaches were resurveyed after an exceptionally severe flood in August 2005, showing limited LW transport in channels but considerable wood input by mass wasting processes. In addition, characteristics of deposits of LW along mountain rivers affected by the 2005 flood were investigated. Diameter and length distribution of transported and deposited pieces were comparable to those of LW from steep headwater stream...

We used data from representatively sampled trees to identify key drivers of tree growth for central European tree species. Nonlinear mixed models were fitted to individual-tree basal area increments (BAI) from the Swiss national forest inventory. Data from 1983 to 2006 were used for model fitting and data from 2009 to 2013 for model evaluation. We considered 23 potential explanatory variables specifying individual-tree characteristics, site and stand conditions, management, climate, and nitrogen deposition. Model selection was processed separately for Picea abies, Abies alba, Pinus sp., Larix sp., other conifers, Fagus sylvatica, Quercus sp., Fraxinus sp./Acer sp., and other broadleaves. The selected models explained 56–70% of the BAI variance in the model fitting dataset and 21–64% in the evaluation dataset. While some variables were relevant for all species, the combination of further variables differed among the species, reflecting their physiological properties. In general, BAI was positively related to DBH and temperature and negatively related to basal area of larger trees, stand density, mean DBH of the 100 thickest trees per ha, slope, and soil pH. For most species, harvesting had a positive effect on BAI. In general, nitrogen deposition was positively related to BAI, except for spruce and fir, for which the inverse effect was found. Increasing drought reduced BAI for most species, except for pine and oak. These BAI models incorporate many influencing factors while representing large spatial extents, making them useful for both nationwide scenario analyses and deepening the understanding of the main drivers modulating tree growth throughout central Europe.

All sulfur potential and phase diagram data available in the literature for solid-state equilibria related to digenite have been assessed. Thorough thermodynamic analysis at 1 bar total pressure has been performed. A three-sublattice approach has been developed to model the Gibbs energy of digenite as a function of composition and temperature using the compound energy formalism. The Gibbs energies of the adjacent solid-state phases covelitte and high-temperature chalcocite are also modeled treating both sulfides as stoichiometric compounds. The novel model for digenite offers new interpretation of experimental data, may contribute from a thermodynamic point of view to the elucidation of the role of copper species within the crystal structure and allows extrapolation to composition regimes richer in copper than stoichiometric digenite Cu2S. Preliminary predictions into the ternary Cu-Fe-S system at 1273 K (1000 °C) using the Gibbs energy model of digenite for calculating its iron solubility are promising.

The extreme flood event that occurred in August 2005 was the most costly (documented) natural hazard event in the history of Switzerland. The flood was accompanied by the mobilization of > 69,000 m3 of large wood (LW) throughout the affected area. As recognized afterward, wood played an important role in exacerbating the damages, mainly because of log jams at bridges and weirs. The present study aimed at assessing the risk posed by wood in various catchments by investigating the amount and spatial variability of recruited and transported LW. Data regarding LW quantities were obtained by field surveys, remote sensing techniques (LiDAR), and GIS analysis and was subsequently translated into a conceptual model of wood transport mass balance. Detailed wood budgets and transport diagrams were established for four study catchments of Swiss mountain streams, showing the spatial variability of LW recruitment and deposition. Despite some uncertainties with regard to parameter assumptions, the sum of reconstructed wood input and observed deposition volumes agree reasonably well. Mass wasting such as landslides and debris flows were the dominant recruitment processes in headwater streams. In contrast, LW recruitment from lateral bank erosion became significant in the lower part of mountain streams where the catchment reached a size of about 100 km2. According to our analysis, ~ 88% of the reconstructed total wood input was fresh, i.e., coming from living trees that were recruited from adjacent areas during the event. This implies an average deadwood contribution of 12%, most of which was estimated to have been in-channel deadwood entrained during the flood event.

Years with high fruit production, known as mast years, are the usual reproduction strategy of European beech. Harsh weather conditions such as frost during flowering can lead to pollination failure in spring. It has been assumed that mast is controlled by flowering, and that after successful pollination, high amounts of fruits and seeds would be produced. However, the extremely hot and dry European summer of 2018 showed that despite successful pollination, beechnuts did not develop or were only abundant in a few forest stands. An in-depth analysis of three forest sites of European beech from the Swiss Long-Term Forest Ecosystem Research Programme over the last 15–19 years revealed for the first time that extreme summer heat and drought can act as an “environmental veto”, leading to early fruit abortion. Within the forest stands in years with fruit abortion, summer mean temperatures were 1.5 °C higher and precipitation sums were 45% lower than the long-term average. Extreme summer heat and drought, together with frost during flowering, are therefore disrupting events of the assumed biennial fruiting cycle in European beech., Scientific Reports, 10 (1), ISSN:2045-2322

Research infrastructures play a key role in launching a new generation of integrated long-term, geographically distributed observation programmes designed to monitor climate change, better understand its impacts on global ecosystems, and evaluate possible mitigation and adaptation strategies. The pan-European Integrated Carbon Observation System combines carbon and greenhouse gas (GHG; CO2, CH4, N2O, H2O) observations within the atmosphere, terrestrial ecosystems and oceans. High-precision measurements are obtained using standardised methodologies, are centrally processed and openly available in a traceable and verifiable fashion in combination with detailed metadata. The Integrated Carbon Observation System ecosystem station network aims to sample climate and land-cover variability across Europe. In addition to GHG flux measurements, a large set of complementary data (including management practices, vegetation and soil characteristics) is collected to support the interpretation, spatial upscaling and modelling of observed ecosystem carbon and GHG dynamics. The applied sampling design was developed and formulated in protocols by the scientific community, representing a trade-off between an ideal dataset and practical feasibility. The use of open-access, high-quality and multi-level data products by different user communities is crucial for the Integrated Carbon Observation System in order to achieve its scientific potential and societal value.

Drought responses of mature trees are still poorly understood making it difficult to predict species distributions under a warmer climate. Using mature European beech (Fagus sylvatica L.), a widespread and economically important tree species in Europe, we aimed at developing an empirical stress-level scheme to describe its physiological response to drought. We analysed effects of decreasing soil and leaf water potential on soil water uptake, stem radius, native embolism, early defoliation and crown dieback with comprehensive measurements from overall nine hydrologically distinct beech stands across Switzerland, including records from the exceptional 2018 drought and the 2019/2020 post-drought period. Based on the observed responses to decreasing water potential we derived the following five stress levels: I (predawn leaf water potential-0.4 MPa): no detectable hydraulic limitations; II (-0.4 to -1.3): persistent stem shrinkage begins and growth ceases; III (-1.3 to -2.1): onset of native embolism and defoliation; IV (-2.1 to -2.8): onset of crown dieback; V (-2.8): transpiration ceases and crown dieback is20%. Our scheme provides, for the first time, quantitative thresholds regarding the physiological downregulation of mature European beech trees under drought and therefore synthesises relevant and fundamental information for process-based species distribution models. Moreover, our study revealed that European beech is drought vulnerable, because it still transpires considerably at high levels of embolism and because defoliation occurs rather as a result of embolism than preventing embolism. During the 2018 drought, an exposure to the stress levels III-V of only one month was long enough to trigger substantial crown dieback in beech trees on shallow soils. On deep soils with a high water holding capacity, in contrast, water reserves in deep soil layers prevented drought stress in beech trees. This emphasises the importance to include local data on soil water availability when predicting the future distribution of European beech.

International audience; Published by Copernicus Publications on behalf of the European Geosciences Union. 5568 M. Camino-Serrano et al.: Trends in soil solution dissolved organic carbon Abstract. Dissolved organic carbon (DOC) in surface waters is connected to DOC in soil solution through hydrological pathways. Therefore, it is expected that long-term dynamics of DOC in surface waters reflect DOC trends in soil solution. However, a multitude of site studies have failed so far to establish consistent trends in soil solution DOC, whereas increasing concentrations in European surface waters over the past decades appear to be the norm, possibly as a result of recovery from acidification. The objectives of this study were therefore to understand the long-term trends of soil solution DOC from a large number of European forests (ICP Forests Level II plots) and determine their main physico-chemical and biological controls. We applied trend analysis at two levels: (1) to the entire European dataset and (2) to the individual time series and related trends with plot characteristics , i.e., soil and vegetation properties, soil solution chemistry and atmospheric deposition loads. Analyses of the entire dataset showed an overall increasing trend in DOC concentrations in the organic layers, but, at individual plots and depths, there was no clear overall trend in soil solution DOC. The rate change in soil solution DOC ranged between −16.8 and +23 % yr −1 (median = +0.4 % yr −1) across Eu-rope. The non-significant trends (40 %) outnumbered the increasing (35 %) and decreasing trends (25 %) across the 97 ICP Forests Level II sites. By means of multivariate statistics , we found increasing trends in DOC concentrations with increasing mean nitrate (NO − 3) deposition and increasing trends in DOC concentrations with decreasing mean sulfate (SO 2− 4) deposition, with the magnitude of these relationships depending on plot deposition history. While the attribution of increasing trends in DOC to the reduction of SO 2− 4 deposi-tion could be confirmed in low to medium N deposition areas, in agreement with observations in surface waters, this was not the case in high N deposition areas. In conclusion, long-term trends of soil solution DOC reflected the interactions between controls acting at local (soil and vegetation properties) and regional (atmospheric deposition of SO 2− 4 and inorganic N) scales.

Air pollution affects forest health through atmospheric deposition of acidic and nitrogen compounds and elevated levels of tropospheric ozone (O3). In 1985, a monitoring network was established across Europe and various research efforts have since been undertaken to define critical values. We measured atmospheric deposition of acidity and nitrogen as well as ambient levels of O3 on 12, 13, and 14 plots, respectively, in the framework of the Swiss Long-Term Forest Ecosystem Research (LWF) in the period from 1995 to 2002. We estimated the critical loads of acidity and of nitrogen, using the steady state mass balance approach, and calculated the critical O3 levels using the AOT40 approach. The deposition of acidity exceeded the critical loads on 2 plots and almost reached them on 4 plots. The median of the measured molar ratio of base nutrient cations to total dissolved aluminium (Bc/Al) in the soil solution was higher than the critical value of 1 for all depths, and also at the plots with an exceedance of the critical load of acidity. For nitrogen, critical loads were exceeded on 8 plots and deposition likely represents a long-term ecological risk on 3 to 10 plots. For O3, exceedance of critical levels was recorded on 12 plots, and led to the development of typical O3-induced visible injury on trees and shrubs, but not for all plots due to (1) the site specific composition of O3 sensitive and tolerant plant species, and (2) the influence of microclimatic site conditions on the stomatal behaviour, i.e., O3 uptake.

Explaining the large-scale diversity of soil organisms that drive biogeochemical processes—and their responses to environmental change—is critical. However, identifying consistent drivers of belowground diversity and abundance for some soil organisms at large spatial scales remains problematic. Here we investigate a major guild, the ectomycorrhizal fungi, across European forests at a spatial scale and resolution that is—to our knowledge—unprecedented, to explore key biotic and abiotic predictors of ectomycorrhizal diversity and to identify dominant responses and thresholds for change across complex environmental gradients. We show the effect of 38 host, environment, climate and geographical variables on ectomycorrhizal diversity, and define thresholds of community change for key variables. We quantify host specificity and reveal plasticity in functional traits involved in soil foraging across gradients. We conclude that environmental and host factors explain most of the variation in ectomycorrhizal diversity, that the environmental thresholds used as major ecosystem assessment tools need adjustment and that the importance of belowground specificity and plasticity has previously been underappreciated.

Studying the effects of atmospheric pollution to forest ecosystems requires an evaluation of air quality and of the amount of pollutants carried to the forests by atmospheric deposition. Pollutant flux towards ecosystems through deposition mainly follows two pathways: wet deposition of compounds dissolved in rain and snow and dry deposition of particulate matter through gravity or filtration, for example by forest canopy. Pollutant deposition shows a relatively high local variability, related to the distribution of pollutant sources and the local topography, and in-situ measurement is needed to obtain accurate evaluations and to validate model estimates. In 2016, the chemical composition of atmospheric deposition was measured in 276 Level II permanent plots. In this report, we focus on acidifying, buffering, and eutrophying compounds. High throughfall deposition of nitrate was mainly found in central Europe (Germany, Switzerland), Denmark, and Belgium, while for ammonium high deposition was also found in northern Italy. The area of high deposition is smaller for sulphate, including some plots in Germany and Poland. High values were also measured in Belgium, but they are partially due to deposition of marine aerosol, and they are less evident after sea-salt correction. High deposition in southern Italy may be related to local anthropogenic sources and to volcanic contribution. Calcium, potassium, and magnesium deposition can buffer the acidifying effect of atmospheric deposition. High values of calcium throughfall deposition were reported for southern Europe, where it is often related to the deposition of Saharan dust, and for Eastern Europe. The correction for the marine contribution does not affect its spatial pattern. On the contrary, for magnesium, the number of sites with the highest values is markedly reduced by the sea salt correction.

For long-term environmental investigations, tree-ring δ 15 N values are inappropriate proxies for foliar δ 15 N for both Fagus sylvatica and Picea abies under moderate N loads. Currently it is unclear whether stable nitrogen isotope signals of tree-rings are related to those in foliage, and whether they can be used to infer tree responses to environmental changes. We studied foliar and tree-ring nitrogen (δ15N) and carbon (δ13C) isotope ratios in European beech (Fagus sylvatica L.) and Norway spruce (Picea abies L.) from six long-term forest monitoring sites in Switzerland together with data on N deposition and soil N availability, as well as a drought response index over the last two decades. For both species, tree-ring δ15N and δ13C values were less negative compared to foliar δ15N and δ13C values, most likely due to recycling and reallocation of N within the tree and fractionation processes associated with the transport of sucrose and the formation of tree-rings, respectively. Temporal trends recorded in foliar δ15N were not reflected in tree-ring δ15N, with much higher variations in tree-rings compared to foliage. Soil N availability and N deposition were partially able to explain changes in foliar δ13C, while there were no significant correlations between environmental variables and either tree-ring or foliar δ15N. Our results suggest an uncoupling between the N isotopic composition of tree-rings and foliage. Consequently, tree-ring δ15N values are inappropriate proxies of foliar δ15N values under low-to-moderate N deposition loads. Furthermore, at such low levels of deposition, tree-ring δ15N values are not recommended as archives of tree responses to soil C/N or bulk N deposition.

Gibbs energy modeling for sulfur solving liquid and solid iron–chromium phases with body- and face-centered cubic structure has been carried out using a substitutional approach. Experimental data available from the literature on sulfur potentials in the temperature range 1 525 to 1 755 °C for the liquid metallic phase and 1 000 to 1 300 °C for the solid alloys have been taken into consideration. Recent thermodynamic evaluations of the Fe–S and Cr–S binary subsystems served as basis for the presented work. The obtained models allow a satisfactory reproduction of the majority of the sulfur potential data as well as the prediction of an isothermal partial section at 1 300 °C. Consistent embedding of the optimized Gibbs energies within a recent thermodynamic modeling of the complete Cr–Fe–S system is achieved.

Dead wood and stand structural parameters were sampled in eleven countries using standardized methods at about 90 intensive forest monitoring sites across large parts of Europe. Besides descriptions and correlation analyses of dead wood and stand structure parameters, a joint evaluation of both fields was performed by principal component analysis (PCA). The extracted principal components were subsequently regressed against important numerical and categorical site-related parameters like soil pH, altitude, or forest type. Dead wood volumes varied largely across plots, however, 77 percent of them had volumes below 25 cubic meter per hectare. While all fractions of dead wood - except cut stumps - reveal high intercorrelation, different aspects of stand structure varied more independently. Clark-Evans index, number of tree species and standard deviation of tree trunk diameters revealed as most self-contained. The 1st PCA axis covered 46 percent of the total variance and was mostly loaded by total dead wood volume denoting it as the feature differentiating forests most. The 2nd axis was primarily loaded by tree species diversity together with stem density and the Clark-Evans index. On the 3rd axis diameter differentiation of trees together with the volume of cut stumps prevailed, while the 4th was mainly related to the decay class of woody debris. Bivariate ex post analyses revealed country as a significant predictor of all PCA axes, underlining national forest legislations and management rules as crucial for all investigated structural features of forests. Forest type was related only to the 3rd and 2nd axis. Only the 3rd axis revealed significant relationships with some ecological site factors (age, number of tree layers, latitude, altitude). The outcome underlines the significance of nationally enacted forest legislations for both important structural and biodiversity-relevant features of forest ecosystems and encourages similar approaches with data from national forest inventories or monitoring systems.

Atmospheric deposition to forests has been monitored within the International Cooperative Programme on Assessment and Monitoring of Air Pollution Effects on Forests (ICP Forests) with sampling and analyses of bulk precipitation and throughfall at several hundred forested plots for more than 15 years. The current deposition of inorganic nitrogen (nitrate and ammonium) and sulphate is highest in central Europe as well as in some southern regions. We compared linear regression and Mann-Kendall trend analysis techniques often used to detect temporal trends in atmospheric deposition. The choice of method influenced the number of significant trends. Detection of trends was more powerful using monthly data compared to annual data. The slope of a trend needed to exceed a certain minimum in order to be detected despite the short-term variability of deposition. This variability could to a large extent be explained by meteorological processes, and the minimum slope of detectable trends was thus similar across sites and many ions. The overall decreasing trends for inorganic nitrogen and sulphate in the decade to 2010 were about 2% and 6%, respectively. Time series of about 10 and 6 years were required to detect significant trends in inorganic nitrogen and sulphate on a single plot. The strongest decreasing trends were observed in western central Europe in regions with relatively high deposition fluxes, whereas stable or slightly increasing deposition during the last 5 years was found east of the Alpine region as well as in northern Europe. Past reductions in anthropogenic emissions of both acidifying and eutrophying compounds can be confirmed due to the availability of long-term data series but further reductions are required to reduce deposition to European forests to levels below which significant harmful effects do not occur according to present knowledge. © 2014 The Authors.

RATIONALE The use of stable nitrogen (N) isotope ratios (δ15N values) in dendroecological studies is often preceded by an extraction procedure using organic solvents to remove mobile N compounds from tree-rings. Although these mobile N compounds may be capable of distorting potential environmental signals in the tree-ring δ15N values, recent investigations question the necessity of such an extraction. METHODS We used an on-going experiment with simulated elevated N deposition previously labelled with 15N, in conjunction with control trees, to investigate the necessity of extracting mobile N compounds (using a rapid extraction procedure) for tree-ring δ15N and δ13C studies, as well as N and C concentration analyses. In addition, we examined the magnitude of radial redistribution of N across tree-rings of Norway spruce (Picea abies). RESULTS The 15N label, applied in 1995/96, was found in tree-rings as far back as 1951, although the increased N availability did not cause any significant relative increase in tree growth. The rapid extraction procedure had no significant effect on tree-ring δ15N or δ13C values in either labelled or control trees, or on N concentration. The C concentrations, however, were significantly higher after extraction in control samples, with the opposite effect observed in labelled samples. CONCLUSIONS Our results indicate that the extraction of mobile N compounds through the rapid extraction procedure is not necessary prior to the determination of Norway spruce δ15N or δ13C values in dendrochemical studies. δ15N values, however, must be interpreted with great care, particularly when used as a proxy for the N status of trees, due to the very high mobility of N within the tree stem sapwood of Norway spruce over several decades. Copyright © 2014 John Wiley & Sons, Ltd.

Forest growth is affected by various concurrent and counteracting climate change related factors and the overall impact of environmental changes on forest growth is still uncertain. In order to evaluate the variability of tree and forest growth and the possible impact of climate change, we analysed 15 years (1995–2010) of tree growth data from 18 Level II plots in Switzerland, spanning a wide range of altitude, temperature and precipitation conditions. Stem diameter of all trees within the Level II plots was measured every 5 years. Other above- and belowground parts of the trees were modelled by allometric relationships and validated with measurements if available. We analysed individual tree growth (basal area increment, bai) and the whole forest net primary productivity (NPP), here the sum of carbon gain by tree growth within the plot during three inventory periods. Additionally, annual stem diameter increment, assessed on single trees at each plot since 2001, was used to approximate annual NPP of the forest. Temporal patterns of NPP could not easily be related to climate conditions, since forest management and disturbance events (e.g. storms, diseases) overshadowed the climate impact on NPP. However, when looking at the individual trees, a clear decrease of bai by 2–30% (mean 19.3%) was observed for most of the sites during the second inventory period (2000–2005), which could not solely be explained by increasing stand density over time. Tree growth was most likely reduced due to the dry conditions during this period that included the extreme year 2003. An increased tree growth during the third inventory period (2006–2010) at a few sites could be clearly related to growth enhancement after stand density reducing events, such as storms or thinning. Thus, understanding climate impact on forest growth requires detailed site history knowledge and available long-term data sets. The variability of mean NPP levels could be described with a function of the sites’ climate conditions and nutrient deposition (adj. r2 = 0.86), with N deposition enhancing forest productivity up to a threshold of 20–25 kg ha−1 yr−1 of N and with no further growth increase beyond that threshold.

The applicability of the dynamic soil model CHUM-AM was tested to simulate concentrations of Cd, Pb and Hg in five Swiss forest soils. Soil cores of up to 50 cm depth were sampled and separated into two defined soil layers. Soil leachates were collected below the litter by zero-tension lysimeters and at 15 and 50 cm soil depths by tension lysimeters over two years. The concentrations of Cd, Pb and Hg in the solid phase and soil solution were measured by ICP-MS (Cd, Pb) or CV-AFS (Hg). Measured metal concentrations were compared with modelled concentrations using CHUM-AM. Additionally we ran the model with three different deposition scenarios (current deposition; maximum acceptable deposition according to the Swiss ordinance on Air Pollution Control; critical loads according to CLRTAP) to predict metal concentrations in the soils for the next 1000 years. Assuming current loads concentrations of Cd and Pb showed varying trends (increasing/decreasing) between the soils. Soils rich in organic carbon or with a high pH value showed increasing trends in Cd and Pb concentrations whereas the concentrations in the other soils decreased. In contrast Hg concentrations are predicted to further increase in all soils. Critical limits for Pb and Hg will partly be exceeded by current loads or by the critical loads proposed by the CLRTAP but the critical limits for Cd will rarely be reached within the next 1000 years. In contrast, maximal acceptable deposition will partly lead to concentrations above the critical limits for Pb in soils within the next 400 years, whereas the acceptable deposition of Cd will not lead to concentrations above the proposed critical limits. In conclusion the CHUM-AM model is able to accurately simulate heavy metal (Cd, Pb and Hg) concentrations in Swiss forest soils of various soil properties.

All known phases of the chromium-iron-sulfur ternary system are taken into consideration within a thermodynamic analysis of phase equilibria and thermodynamic data at 1 bar total pressure over the entire composition range between 298.15 K (25 °C) and temperatures greater than the liquidus. The modeling is based on recent evaluations of the Fe-S and Cr-S binary subsystems. The extended modified quasi-chemical model is applied for the liquid chromium-iron-sulfur phase. The Gibbs energy of solid solution phases as high-temperature chromium-iron pyrrhotite and the thiospinel Daubreelite is described by sublattice models within the framework of the compound energy formalism. Analysis of complex phase relations is now possible on the basis of a consistent thermodynamic description of the system. The thermodynamic modeling presented can be combined with models of other metal-sulfur systems to develop a thermodynamic multicomponent/multiphase database.

Impacts of atmospheric acid deposition on soil solutions in forests After a massive input of acidifying components on the environment in the middle of the 20th century, atmospheric acid deposition has decreased as a result of sulphur emission reduction. The continuous acid input might affect the chemistry of soils and drainage waters and accelerate soil acidification. In the framework of the Swiss Long-Term Forest Ecosystem Research (LWF), we examined whether acid deposition has continued to decline in the last ten years in different forest ecosystems and how the chemistry of soil water reacted to the improvement in air quality. Acid deposition decreased significantly at only three out of the nine study sites. Sulphur deposition declined at all sites, but due to the relatively low sulphur load compared to nitrogen deposition, it did not contribute to decrease acid deposition. Chemistry of soil solution remained quite constant since the beginning of the measurements about ten years ago. We did not observe any acidification of soil solution in six out of eight sites. In contrast, changes in soil solution chemistry at two sites showed a rapid acidification. At three sites, the deeper soil layer released large amount of sulphate coupled with base cations, which likely contributed to deplete the soil in nutrients. The analysis of the base saturation in 1039 soil profiles across Switzerland shows a high risk of relatively fast acidification of soil solution in almost 20% of sites.