Polychlorinated biphenyls (PCB) both continue to spread into the environment and to bioaccumulate from primary urban and industrial sources as well as from secondary sources such as soils and the oceans. Fractions of congeners in PCB mixtures, i.e. PCB profiles, can be used as fingerprints to trace contamination pathways from sources to sinks because PCB mixtures fractionate during transport due to congener specific phase changes and degradation. Using a statistical analysis of a total of 8584 PCB profiles with seven congeners (CB28, CB52, CB101, CB118, CB138, CB153, CB180) for contaminated fish from two international datasets as well as a modelling of profiles, two major fractionation processes related to distinct contamination pathways were identified: (1) A relative enrichment of lighter congeners (CB28, CB52, CB101) in seawater fish due to a predominantly atmospheric transport, whereas freshwater and some coastal fish had higher fractions of heavier congeners (CB138, CB153) because those were mainly contaminated by particle -sorbed PCB from surface runoff. (2) A temperature driven fractionation tended to affect congeners with a medium molecular weight (CB118) as well as the heaviest congeners (CB180), a fractionation process which was conceptually associated with transport of PCB from secondary sources. Specifically, medium chlorinated PCB is sufficiently volatile and persistent for a preferred transport into cooler waters. In warmer climates, only the highest chlorinated congeners are persistent enough to ultimately accumulate in fish. Our analysis and modelling provide a starting point for the development of systems to trace - better than before - sources of PCB contaminations observed in fish.

Depending on the ambient pH, ionizable substances are present in varying proportions in their neutral or charged form. The extent to which these two chemical species contribute to the pH-dependant toxicity of ionizable chemicals and whether intracellular ion trapping has a decisive influence in this context is controversially discussed. Against this background, we determined the acute toxicity of 24 ionizable substances at up to 4 different pH values on the embryonic development of the zebrafish, Danio rerio, and supplemented this dataset with additional data from the literature. The LC50 for some substances (diclofenac, propranolol, fluoxetine) differed by a factor of even >103 between pH5 and pH9. To simulate the toxicity of 12 acids and 12 bases, six models to calculate a pH-dependant logD value as a proxy for the uptake of potentially toxic molecules were created based on different premises for the trans-membrane passage and toxic action of neutral and ionic species, and their abilities to explain the real LC50 data set were assessed. Using this approach, we were able to show that both neutral and charged species are almost certainly taken up into cells according to their logD-based distribution, and that both species exert toxicity. Since two of the models that assume all intracellular molecules to be neutral overestimated the real toxicity, it must be concluded, that the toxic effect of a single charged intracellularly present molecule is, on the average, lower than that of a single neutral molecule. Furthermore, it was possible to attribute differences in toxicity at different pH values for these 24 ionizable substances to the respective deltas in logD at these pH levels with high accuracy, enabling particularly a full logD-based model on the basis of logPow as a membrane passage descriptor to be used for predicting potential toxicities in worst-case scenarios from existing experimental studies, as stipulated in the process of registration of chemicals and the definition of Environmental Quality Standards (EQS).

Mercury has become a ubiquitous hazardous element even ending up in pristine areas such as the Arctic, where it biomagnifies and leaves especially top predators vulnerable to potential health effects. Here we investigate total mercury (THg) concentrations and dietary proxies for trophic position and habitat foraging (δ15N and δ13C, respectively) in fur of 30 Arctic wolves collected during 1869-1998 in the Canadian High Arctic and Greenland. Fur THg concentrations (mean ± SD) of 1.46 ± 1.39 μg g -1 dry weight are within the range of earlier reported values for other Arctic terrestrial species. Based on putative thresholds for Hg-mediated toxic health effects, the studied Arctic wolves have most likely not been at compromised health. Dietary proxies show high dietary plasticity among Arctic wolves deriving nutrition from both marine and terrestrial food sources at various trophic positions. Variability in THg concentrations seem to be related to the wolves' trophic position rather than to different carbon sources or regional differences (East Greenland, the Foxe Basin and Baffin Bay area, respectively). Although the present study remains limited due to the scarce, yet unique historic study material and small sample size, it provides novel information on temporal and spatial variation in Hg pollution of remote Arctic species.

Environmental risk assessments of organic chemicals usually do not consider pH as a key factor. Hence, most substances are tested at a single pH only, which may underestimate the toxicity of ionisable substances with a pKa in the range of 4-10. Thus, the ability to consider the pH-dependent toxicity would be crucial for a more realistic assessment. Moreover, there is a tendency in acute toxicity tests to focus on mortality only, while little attention is paid to sublethal endpoints. We used Danio rerio embryos exposed to ten ionisable substances (the acids diclofenac, ibuprofen, naproxen and triclosan and the bases citalopram, fluoxetine, metoprolol, propranolol, tramadol and tetracaine) at four external pH levels, investigating the endpoints mortality (LC50) and heart rate (EC20). Dose-response curves were fitted with an ensemble-model to determine the true uncertainty and variation around the mean endpoints. The ensemble considers eight (heart rate) or twelve (mortality) individual models for binominal and Poisson distributed data, respectively, selected based on the Akaike Information Criterion (AIC). In case of equally good models, the mean endpoint of all models in the ensemble was calculated, resulting in more robust ECx estimates with lower 'standard errors' as compared to randomly selected individual models.& nbsp;We detected a high correlation between mortality (LC50) at 96 hpf and reduced heart rate (EC20) at 48 hpf for all compounds and all external pH levels (r = 0.98). Moreover, the observed pH-dependent effects were strongly associated with log D and thus, likely driven by differences in uptake (toxicokinetic) rather than internal (toxicodynamic) processes.

Salinization is a well‐known problem in agricultural areas worldwide. In the last 20–30 yr, rising salinity in the upper, unconfined aquifer has been observed in the Freepsumer Meer, a grassland near the German North Sea coast. For investigating long‐term development of salinity and water balance during 1961–2099, the one‐dimensional Soil–Water–Atmosphere–Plant (SWAP) model was set up and calibrated for a soil column in the area. The model setup involves a deep aquifer as the source of salt through upward seepage. In the vertical salt transport equation, dispersion and advection are included. Six different regional outputs of statistical downscaling methods were used as climate scenarios. These comprise different rates of increasing surface temperature and different trends in seasonal rainfall. The simulation results exhibit opposing salinity trends for topsoil and deeper layers. Although projections of some scenarios entail decreasing salinities near the surface, most of them project a rise in subsoil salinity, with the strongest trends of up to +0.9 mg cm−3 100 yr−1 at −65 cm. The results suggest that topsoil salinity trends in the study area are affected by the magnitude of winter rainfall trends, whereas high subsoil salinities correspond to low winter rainfall and high summer temperature. How these projected trends affect the vegetation and thereby future land use will depend on the future management of groundwater levels in the area.

The minimum detectable difference (MDD) is a measure of the difference between the means of a treatment and the control that must exist to detect a statistically significant effect. It is a measure at a defined level of probability and a given variability of the data. It provides an indication for the robustness of statistically derived effect thresholds such as the lowest observed effect concentration (LOEC) and the no observed effect concentration (NOEC) when interpreting treatment-related effects on a population exposed to chemicals in semi-field studies (e.g., micro-/mesocosm studies) or field studies. MDD has been proposed in the guidance on tiered risk assessment for plant protection products in edge of field surface waters (EFSA Journal 11(7):3290, 2013 ), in order to better estimate the robustness of endpoints from such studies for taking regulatory decisions. However, the MDD calculation method as suggested in this framework does not clearly specify the power which is represented by the beta-value (i.e., the level of probability of type II error). This has implications for the interpretation of experimental results, i.e., the derivation of robust effect values and their use in risk assessment of PPPs. In this paper, different methods of MDD calculations are investigated, with an emphasis on their pre-defined levels of type II error-probability. Furthermore, a modification is suggested for an optimal use of the MDD, which ensures a high degree of certainty for decision-makers.

Soil water content and matric potential are central hydrological state variables. A large variety of automated probes and sensor systems for state monitoring exist and are frequently applied. Most applications solely rely on the calibration by the manufacturers. Until now, there has been no commonly agreed-upon calibration procedure. Moreover, several opinions about the capabilities and reliabilities of specific sensing methods or sensor systems exist and compete. A consortium of several institutions conducted a comparison study of currently available sensor systems for soil water content and matric potential under field conditions. All probes were installed at 0.2 m b.s. (metres below surface), following best-practice procedures. We present the set-up and the recorded data of 58 probes of 15 different systems measuring soil moisture and 50 further probes of 14 different systems for matric potential. We briefly discuss the limited coherence of the measurements in a cross-correlation analysis. The measuring campaign was conducted during the growing period of 2016. The monitoring data, results from pedophysical analyses of the soil and laboratory reference measurements for calibration are published in Jackisch et al. (2018, https://doi.org/10.1594/PANGAEA.892319).

Department of Geography, Philipps‐University Marburg, Marburg, Germany Department of Hydrology, German Research Centre for Geosciences Potsdam, Potsdam, Germany Department of Physical Geography, (formerly Katja Heller) University of Technology Dresden, Dresden, Germany Department of Hydrology, University of Bayreuth, Bayreuth, Germany Department of Geography – Hydrology and Climate, University of Zürich, Zurich, Switzerland German Environment Agency, Dessau‐Roßlau, Germany Department of Physical Geography, University of Trier, Trier, Germany Department of Hydrology, Albert‐Ludwigs‐University of Freiburg, Freiburg im Breisgau, Germany Department of Natural Hazards, Austrian Research Centre for Forests Innsbruck, Innsbruck, Austria 10 Institute of Environmental Physics, Ruprecht‐Karls‐University of Heidelberg, Heidelberg, Germany Department of Applied Physical Geography, Freie Universitaet Berlin, Berlin, Germany Unit for Hydraulic Engineering, University of Innsbruck, Innsbruck, Austria

Uncertainty is an inherent property of monitoring, analysis and modelling of coupled human-environmental systems. The interdisciplinary RUINS project (Risk, Uncertainty and Insurance under Climate Change. Coastal Land Management on the German North Sea.) assesses land management options in coastal areas as adaptation to changing climate under uncertainty. Especially when it comes to future predictions of ecosystem services, to convey the information within the blur of stacked and interconnected uncertainties to the decision makers becomes challenging.

Maintenance and repair of the coastal dunes of the conservation area, Hutelmoor und Heiligensee" have been ceased for renaturation purposes since the year 2000 to aid flooding of the area during high water levels of the Baltic Sea. On January 4th and 5th 2017, the Baltic Sea experienced a storm surge resulting in a water level in Warnemunde with a 10-to 20-year reoccurrence rate. Nevertheless, the event caused neither a dune failure nor a sea-sided flooding, but did result in an upstream inflow of salt and brackwater through the trench which normally drains the area into the Baltic Sea via the Warnow. Water levels and salinity concentrations rose in the south-western part of the area due to the influx via a ground sill, which normally acts as the outlet of the lowland. The effects within the lowland were less pronounced with increasing distance to the ground sill, which proved to be even more significant for the water levels than for salinities due to the retention capabilities of the area. While water levels increased extensively as a result of the flooding, the salinity front is presumed to have spread primarily along the former draining channels. This interpretation is based on monitoring data of the water level as well as the environmental tracers electrical conductivity and water temperature.

Die Messung der Bodenfeuchte und des Matrixpotenzials als zentrale bodenhydrologische Zustandsvariablen kann mit einer Vielzahl von Messgeraten und Technologien erfolgen. Ein Konsortium von 8 Institutionen hat eine Vergleichsstudie auf einer speziell homogenisierten Testflache eines schluffigen Sandes durchgefuhrt. Die Experimentalflache von ca. 60 m² war naturlichen meteorologischen Bedingungen ausgesetzt und wurde von Vegetation freigehalten. 57 Sensoren von 15 verschiedenen Systemen zur Messung der Bodenfeuchte und 50 Sensoren von 14 verschiedenen Systemen zur Messung des Matrixpotenzials wurden in einer gitterformigen Anordnung in 0,2 m Tiefe installiert. Die meisten Sensoren erfassten zusatzlich die Temperatur. Die Ergebnisse der Studie zeigten: (1) Die meisten Wassergehaltssensoren ergaben plausible Daten, jedoch bestanden erhebliche Abweichungen in Hinblick auf die gemessenen Absolutwerte. (2) Bei Matrixpotenzialsensoren konnte die schnelle Reaktion auf Niederschlagsereignisse nur von Tensiometern aufgezeichnet werden. Alle indirekten Verfahren reagierten langsamer, (3) ein Vergleich der im Freiland beobachteten Relation zwischen Bodenwassergehalt und Matrixpotenzial mit Labormessungen an ungestorten Stechzylinderproben zeigte systematische Abweichungen. Mit den Ergebnissen aus der Vergleichsstudie wollen wir zu einer kritischen Diskussion der intrinsischen Annahmen bodenhydrologischer Messungen und zur Entwicklung alternativer Techniken zur Beobachtung der Zustande und Prozesse im Boden beitragen.

Coastal wetlands like the nature reserve "Hutelmoor und Heiligensee" northeast of Rostock are characteristic elements of the landscapes along the southern Baltic Sea coastline. Under natural conditions, their hydrological peculiarities include exchange processes between the fens and the Baltic Sea. Due to human interventions, e.g. the construction of dunes and dikes, drainage systems and lately also renaturation measures, their hydrological regime has been repeatedly changed over the centuries.The nature reserve (German: Naturschutzgebiet, NSG)"Hijtelmoor und Heiligensee", formerly used for pasture, has recently been restored, which allows the investigation of past changes and the evaluation of possible and future developments. The present contribution is the first part of a double publication which aims at identifying the relevant hydrological processes that affect the water balance of the presented wetland area. The investigations are based on a monitoring network measuring groundwater levels and electric conductivity within the fen since 2009, as well as on measurements of the flow and of meteorological variables. The topic of this first publication part is the hydrological characterization of the area under study and the identification of its particular hydrological basic patterns. This is done on the basis of a principal water budget, i.e. balancing of the different water flows across the system's borders, such as precipitation, evapotranspiration, inflows from the neighbouring parts of the catchment area, subterranean exchange processes with the Baltic Sea and the area's surface discharge. Furthermore, the episodic input of salty water, in the rare cases of heavy storm tides causing dune overspilling or breaching, provides salt as a natural tracer. This tracer allows clearer distinction of the specific processes in this particular lowland (vertical fluxes due to precipitation, evaporation and rising groundwater levels, lateral transport processes, exchange with trenches).This concerns the temporal dynamics (both seasonality and trends) as well as the spatial patterns of salt concentration reflecting the water flows within the peat layers, which will be discussed in part II (SELLE et al. 2016).

Several trend studies have shown that hydrological conditions are changing considerably in the Alpine region. However, the reasons for these changes are only partially understood and trend analyses alone are not able to shed much light. Hydrological modelling is one possible way to identify the trend drivers, i.e., to attribute the detected streamflow trends, given that the model captures all important processes causing the trends. We modelled the hydrological conditions for two alpine catchments in western Austria (a large, mostly lower-altitude catchment with wide valley plains and a nested high-altitude, glaciated headwater catchment) with the distributed, physically-oriented WaSiM-ETH model, which includes a dynamical glacier module. The model was calibrated in a transient mode, i.e., not only on several standard goodness measures and glacier extents, but also in such a way that the simulated streamflow trends fit with the observed ones during the investigation period 1980 to 2007. With this approach, it was possible to separate streamflow components, identify the trends of flow components, and study their relation to trends in atmospheric variables. In addition to trends in annual averages, highly resolved trends for each Julian day were derived, since they proved powerful in an earlier, data-based attribution study. We were able to show that annual and highly resolved trends can be modelled sufficiently well. The results provide a holistic, year-round picture of the drivers of alpine streamflow changes: Higher-altitude catchments are strongly affected by earlier firn melt and snowmelt in spring and increased ice melt throughout the ablation season. Changes in lower-altitude areas are mostly caused by earlier and lower snowmelt volumes. All highly resolved trends in streamflow and its components show an explicit similarity to the local temperature trends. Finally, results indicate that evapotranspiration has been increasing in the lower altitudes during the study period.

Coastal fens like the nature reserve "Hutelmoor und Heiligensee" (north-eastern Germany) are important landscape elements along the southern Baltic coast, which exchange fresh water and brackish water with the Baltic Sea. These exchange processes can be understood as experiments with a natural tracer, which may be used to investigate the hydrologic behaviour of these fen systems. With the establishment of coastal protection measures such as dunes and dikes, the installation of surface drainage and, more recently, also nature conservation measures, the hydrologic regime of these coastal wetlands has constantly altered over the last centuries.The rehabilitated wetland "Hutelnnoor und Heiligensee" is suitable for an analysis of hydrologic change as it has been monitored over the time period since nature conservation measures started in the 1990s. Collected data sets included observation of groundwater levels and electrical conductivities, weather data as well as discharge at the outlet of the drainage catchment. In this article, as a second part of the dual publication, processes and quantified process magnitudes have been identified that govern the salt balance of the study area including its variability in space and time. It was detected that - over the period of rehabilitation - salt water entered the catchment with an episodic storm surge by wave overtopping of dunes in 1995. The intruded brackish water was then diluted, which was a slow process extending over decades. It was governed by local groundwater recharge from precipitation and the inflow of relatively fresh groundwater from the hinterland. It is concluded that salt inputs from the Baltic Sea provide a natural tracer of hydrological processes, which can be readily monitored via electrical conductivity measurements.