A statistical analysis of climate variability and ecosystem response in the German Bight

We compiled homogeneous long-term time series comprising 39 variables representing the German Bight and for the period 1975–2004. A diverse set of variables was selected to cover multiple trophic levels and different environmental forcing thus to examine long-term changes in this coastal region. Previous studies have hypothesised the presence of regime shifts in observations extending over the entire North Sea. Focusing on a smaller spatial scale, and closer to the coast, we investigated the major modes of variability in the compiled time series using principal component analysis. The results obtained confirm a previously identified regime shift in the North Sea in 1987/1988 and suggest that the German Bight is dominantly characterised by long-term modes of variability. In the German Bight, the shift of 1987/1988 is driven primarily by temperature, Gulf Stream index, frost days and Secchi depth. Changes in some of the ecosystem variables (plankton and fish) appear to be related to changes in these driving variables. In particular, we documented strong positive correlations between the long-term trend showed by the first principal component and herring, Noctiluca scintillans, and, to a lesser extent, Pleurobrachia pileus. Two gadoids, namely cod and saithe, showed negative correlations with the observed long-term mode of variability. Changes in the sum of five small calanoid copepods were, however, less marked. Phosphate and ammonium exhibited a decreasing trend over the last 30 years. Diatoms and Calanus helgolandicus did not show evidence of changes in concert to this trend. Specific analyses of the data divided into three different subsets (biological, climatic and chemical) characterise the climate of the German Bight as highly dynamic also on short timescales (a few years) as compared to much smoother biological and chemical components. The dynamic regime of the German Bight taken together with a low correlation between the major mode of variability and phytoplankton and zooplankton data suggests that the lower trophic levels of this ecosystem are remarkably resilient.     

Fate of Benzalkonium Chloride in a Sewage Sludge Low Temperature Conversion Process Investigated by LC‐LC/ESI‐MS/MS

Thermocatalytic low temperature conversion (LTC) is a new method for the disposal of sewage sludge. Using this method, sludge is converted into a residual solid (coal) along with reaction water, oil, and non‐condensable gases. The oil can be used as an energy source and the coal as a substitute for charcoal. To this end, it is important to determine whether there are any easily available contaminants present in the coal generated by the process. Contaminants that can be strongly sorbed by sewage sludge solids are, e. g., pharmaceuticals and disinfectants. As an example the fate of the persistent and strong adsorbing disinfectant benzalkonium chloride (BAC) has been investigated within the LTC process. The sewage sludge was spiked with BAC and then subjected to the LTC process. The resulting coal was extracted and analyzed using LC‐LC/ESI‐MS/MS (ion trap). BAC could not be detected in the LTC coal, although it could be extracted from the spiked sludge before the LTC treatment. It can thus be concluded that the investigated compound is not easily available in the coal, and hence that its use does not present a risk.     

Mobilisation and transport of dissolved organic carbon and iron in peat catchments—Insights from the Lehstenbach stream in Germany using generalised additive models

During the last decades, increasing exports of both dissolved organic carbon (DOC) and iron were observed from peat catchments in North America and Europe with potential consequences for water quality of streamwater and carbon storages of soils. As mobilisation and transport processes of DOC and iron in peat catchments are only partly understood, the purpose of this study was to elucidate these processes in an intensively monitored and studied system. Specifically, it was hypothesised that dissimilatory iron reduction in riparian peatland soils mobilises DOC initially adsorbed to iron minerals. During stormflow conditions, both DOC and iron will be transported into the stream network. Ferrous iron may be reoxidised at redox interfaces on its way to the stream, and subsequently, ferric iron could be transported together with DOC as complexes. To test these hypotheses, generalised additive models (GAMs) were applied to 14 years of weekly time series of discharge and concentrations of selected solutes measured in a German headwater stream called Lehstenbach. This stream drains a 4.19‐km² forested mountain catchment; one third of which is covered by riparian peatland soils. We interpreted results of different types of GAM in the way that (a) iron reduction drove the mobilisation of DOC from peatland soils and that (b) both iron and DOC were transported as complexes after their joint mobilisation to and within the steam. It was speculated that low nitrate availability in the uppermost wetland soil layer, particularly during the growing season, promoted iron reduction and thus the mobilisation of DOC. However, the influence of nitrate on the DOC mobilisation remains relatively uncertain. This influence could be further investigated using methods similar to the GAM analysis conducted here for other catchments with long‐term data as well as detailed measurements of the relevant species in riparian wetland soils and the adjacent stream network.     

Attenuation mechanisms in fractured fluid-saturated porous rocks: a numerical modelling study

Seismic attenuation mechanisms receive increasing attention for the characterization of fractured formations because of their inherent sensitivity to the hydraulic and elastic properties of the probed media. Attenuation has been successfully inferred from seismic data in the past, but linking these estimates to intrinsic rock physical properties remains challenging. A reason for these difficulties in fluid-saturated fractured porous media is that several mechanisms can cause attenuation and may interfere with each other. These mechanisms notably comprise pressure diffusion phenomena and dynamic effects, such as scattering, as well as Biot's so-called intrinsic attenuation mechanism. Understanding the interplay between these mechanisms is therefore an essential step for estimating fracture properties from seismic measurements. In order to do this, we perform a comparative study involving wave propagation modelling in a transmission set-up based on Biot's low-frequency dynamic equations and numerical upscaling based on Biot's consolidation equations. The former captures all aforementioned attenuation mechanisms and their interference, whereas the latter only accounts for pressure diffusion phenomena. A comparison of the results from both methods therefore allows to distinguish between dynamic and pressure diffusion phenomena and to shed light on their interference. To this end, we consider a range of canonical models with randomly distributed vertical and/or horizontal fractures. We observe that scattering attenuation strongly interferes with pressure diffusion phenomena, since the latter affect the elastic contrasts between fractures and their embedding background. Our results also demonstrate that it is essential to account for amplitude reductions due to transmission losses to allow for an adequate estimation of the intrinsic attenuation of fractured media. The effects of Biot's intrinsic mechanism are rather small for the models considered in this study.     

In situ and high frequency monitoring of suspended sediment properties using a spectrophotometric sensor

It is well known that sediment properties, including sediment‐associated chemical constituents and sediment physical properties, can exhibit significant variations within and between storm runoff events. However, the number of samples included in suspended sediment studies is often limited by time‐consuming and expensive laboratory procedures after stream water sampling. This restricts high frequency sampling campaigns to a limited number of events and reduces accuracy when aiming to estimate fluxes and loads of sediment‐associated chemical constituents. In this study, we address the potential of a portable ultraviolet–visible spectrophotometer (220–730 nm) to estimate suspended sediment properties in a resource efficient way. Several field deployable spectrophotometers are currently available for in‐stream measurements of environmental variables at high temporal resolution. These instruments have primarily been developed and used to quantify solute concentrations (e.g. dissolved organic carbon and NO₃‐N), total concentrations of dissolved and particulate forms (e.g. total organic carbon) and turbidity. Here we argue that light absorbance values can be calibrated to estimate sediment properties. We present light absorbance data collected at 15‐min intervals in the Weierbach catchment (NW Luxembourg, 0.45 km²) from December 2013 to January 2015. In this proof‐of‐concept study, we performed a local calibration using suspended sediment loss‐on‐ignition (LOI) measurements as an example of suspended sediment property. We assessed the performance of several regression models that relate light absorbance measurements with the percentage weight LOI. The MM‐robust regression method presented the lowest standard error of prediction (0.48%) and was selected for calibration (adjusted r² = 0.76 between observed and predicted values). The model was then used to predict LOI during a storm runoff event in December 2014. This study demonstrates that spectrophotometers can be used to estimate suspended sediment properties at high temporal resolution and for long‐time spans in a simple, non‐destructive and affordable manner. Copyright © 2016 John Wiley & Sons, Ltd.     

Aquifer Vulnerability Assessment Based on Sequence Stratigraphic and 39Ar Transport Modeling

A large‐scale groundwater flow and transport model is developed for a deep‐seated (100 to 300 m below ground surface) sedimentary aquifer system. The model is based on a three‐dimensional (3D) hydrostratigraphic model, building on a sequence stratigraphic approach. The flow model is calibrated against observations of hydraulic head and stream discharge while the credibility of the transport model is evaluated against measurements of ³⁹Ar from deep wells using alternative parameterizations of dispersivity and effective porosity. The directly simulated 3D mean age distributions and vertical fluxes are used to visualize the two‐dimensional (2D)/3D age and flux distribution along transects and at the top plane of individual aquifers. The simulation results are used to assess the vulnerability of the aquifer system that generally has been assumed to be protected by thick overlaying clayey units and therefore proposed as future reservoirs for drinking water supply. The results indicate that on a regional scale these deep‐seated aquifers are not as protected from modern surface water contamination as expected because significant leakage to the deeper aquifers occurs. The complex distribution of local and intermediate groundwater flow systems controlled by the distribution of the river network as well as the topographical variation (Tóth 1963) provides the possibility for modern water to be found in even the deepest aquifers.     

Numerical simulation of three-dimensional saltwater–freshwater fingering instabilities observed in a porous medium

We consider saltwater–freshwater fingering instabilities in a saturated porous medium. In the first part, we present three-dimensional results obtained from a laboratory experiment using non-invasive imaging. In the second part, we define a set of model problems in which the performed laboratory experiments can be ranged in. Due to its highly non-linear behavior and inevitable modeling errors, a detailed numerical reproduction of the physical concentration measurements cannot be expected. Nevertheless, four criteria have been identified, two quantitative and two qualitative, which facilitate a substantiated comparison of the physical experiment and the numerical simulation. With respect to these criteria a high degree of similarity could be observed. The use of these features allows a deeper understanding of the physical processes and the influence of the initial conditions.     

Microfabric analyses applied to the Witwatersrand gold- and uranium-bearing conglomerates: constraints on the provenance and post-depositional modification of rock and ore components

Microfabrics of detrital quartz grains and quartz cement of four gold- and uranium-bearing conglomerates of various goldfields of the Witwatersrand Basin, South Africa, were investigated by optical and cathodoluminescence microscopy. The study revealed that the vast majority of quartz grains (<5 mm) originate from felsic magmatic source rocks. Cherts and polymineralic mineral grains, pointing to greenschist to amphibolite facies metasedimentary rocks, follow in abundance, whereas diagenetic to weakly metamorphosed quartzites are subordinate. Material from hydrothermal vein quartz is almost completely lacking, both in the sand and in the pebble fraction. No obvious relationships are discernible between the varying proportions of detrital siliciclastic components of the different reefs and their ore grades. Assuming a sedimentological control of gold distribution, this finding supports multiple sources for the detrital components, which were thoroughly mixed during transport. The post-depositional history of the sediments is characterized by a complex polyphase succession of deformation, cementation and hydrothermal alteration events. Both fragmentation and pressure solution features within detrital quartz, quartz cement and round grains of pyrite, zircon, chromite and uraninite demonstrate that these materials were present in the conglomerates during diagenesis, and, thus, are true detrital grains with abraded, rounded grain morphologies. By analogy, it is assumed that gold is also a detrital component, although most of the gold grains display characteristics of hydrothermal overprinting. During subsequent metamorphism, micro-shear zones are developed, and brittle-ductile crystal-plastic deformation and limited quartz recrystallization occur. Maximum temperatures of about 350 °C were reached on the prograde metamorphic path. Recrystallization and redistribution of detrital siliciclastic and ore minerals took place, and various hydrothermal/metamorphic minerals including chlorite, sericite, pyrophyllite and chloritoid were formed. These redistribution processes involved existing detrital minerals only and were generally isochemical because little evidence exists for the development of a secondary porosity and permeability that would allow major external inputs into the Witwatersrand conglomerates. Most of the gold grains have hydrothermal characteristics, as evidenced by their authigenic, crystalline shapes and their chemical compositions. However, these features are regarded to result from overprinting. Most likely, the gold grains experienced more drastic modifications relative to other ore components because of the ductile and mobile nature of gold. The retrograde metamorphic path is characterized by percolating radioactive fluids at T<300 °C, recorded by radiation damage indicated by cathodoluminescence alteration rims along quartz grain boundaries and microcracks. The degrees of radiation damage observed are proportional to the uranium contents of the conglomerate ores. The collective evidence of our study supports the modified placer model for the genesis of the Witwatersrand ores. This model explains most of the observations on the detrital mineral assemblage and its post-depositional modification elegantly and in a satisfactory manner.     

Schwankungen im Wasserhaushalt der Ostsee

Zusammenfassung Durch die gleichzeitige Berücksichtigung aller Komponenten des Wasserhaushaltes der Ostsee wird das Zusammenwirken von Süßwasserzufuhr, Wasserstandsänderungen und Wasseraustausch mit der Nordsee einer Analyse unterzogen. Dabei wird der Einfluß der atmosphärischen Zirkulation und der Gang des Wasserstandes erklärt. Die Behandlung der vollständigen monatlichen Bilanz durch fünf Jahre zeigt, daß die Abweichungen von diesem Jahresgang erheblich sind. Der Wasseraustausch wird durch die Wasserbewegungen an der Oberfläche in den Belten und dem Sund repräsentativ wiedergegeben. Der Wasseraustausch ist intensiver als bisher angenommen. Die langjährigen Schwankungen der Haushaltsgrößen werden untersucht. Es wird gezeigt, daß die atmosphärische Zirkulation auf dem Wege über die Niederschläge und die Süßwasserzufuhr Schwankungen des Ausstroms bewirkt. Andererseits wirkt sie direkt auf den Wasserstand und durch Veränderungen der Intensität des Wasseraustausches auf den Salzgehalt ein. Eine Abschätzung des Salzhaushaltes der Ostsee wird gegeben.

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On fluctuations of the water volume of the Baltic

Summary The combined effects of fresh water influx, variations of sea level, and water exchange with the North Sea are analysed by simultaneously taking into account all components of the water volume of the Baltic Sea. The influence of the atmospheric circulation and of the variations of sea level are explained. The diseussion of the complete monthly water balance over a five years' period shows considerable departures from the annual variation of sea level. The surface currents in the Great and the Little Belt and in the Sound give a representative picture of the water exchange with the North Sea which is revealed to be more intensive than it was hitherto supposed to be. The secular fluctuations of the water volume are studied. Through the medium of precipitation and influx of fresh water the atmospheric circulation causes fluctuations in the outflow from the Baltic. On the other hand, the atmospheric circulation exercises a direct influence on the sea level and — owing to variations in the intensity of water exchange — an indirect one on the salinity. The salinity balance of the Baltic is evaluated.

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Sur les fluctuations du volume d'eau de la mer Baltique

Résumé En tenant compte de toutes les composantes du volume d'eau de la mer Baltique on fait l'analyse des effets réunis des affluences d'eau douce, des variations du niveau de la mer et le l'échange d'eau avec la mer du Nord. On explique l'influence de la circulation atmosphérique et de la variation du niveau de la mer. L'étude du bilan mensuel complet portant sur cinq années montre que les déviations de la marche annuelle sont considérables. Les courants de surface dans le Grand et le Petit Belt et le Sund donnent une image représentative de l'échange d'eau qui est plus intensif qu'on ne l'a supposé jusqu'ici. Les fluctuations séculaires des composantes du volume d'eau sont étudiées. On montre que par l'inter-médiaire des précipitations et de l'affluence d'eau douce la circulation atmosphérique donne lieu à des variations de l'écoulement de la mer Baltique. D'autre part, la circulation atmosphérique exerce une influence directe sur le niveau de la mer et, par suite des variations de l'intensité de l'échange d'eau, elle a une influence indirecte sur la salinité. Le bilan de la salinité est évalué.