Hydrothermal alteration and zeolitization of the Fohberg phonolite,Kaiserstuhl Volcanic Complex,Germany

The subvolcanic Fohberg phonolite (Kaiserstuhl Volcanic Complex, Germany) is an economic zeolite deposit, formed by hydrothermal alteration of primary magmatic minerals. It is mined due to the high (>40 wt%) zeolite content, which accounts for the remarkable zeolitic physicochemical properties of the ground rock. New mineralogical and geochemical studies are carried out (a) to evaluate the manifestation of hydrothermal alteration, and (b) to constrain the physical and chemical properties of the fluids, which promoted hydrothermal replacement. The alkaline intrusion is characterized by the primary mineralogy: feldspathoid minerals, K-feldspar, aegirine–augite, wollastonite, and andradite. The rare-earth elements-phase götzenite is formed during the late-stage magmatic crystallization. Fluid-induced re-equilibration of feldspathoid minerals and wollastonite caused breakdown to a set of secondary phases. Feldspathoid minerals are totally replaced by various zeolite species, calcite, and barite. Wollastonite breakdown results in the formation of various zeolites, calcite, pectolite, sepiolite, and quartz. Zeolites are formed during subsolidus hydrothermal alteration (<150 °C) under alkaline conditions. A sequence of Ca–Na-dominated zeolite species (gonnardite, thomsonite, mesolite) is followed by natrolite. The sequence reflects an increase in \(\log [(a_{{{\text{Na}}^{ + } }} )/(a_{{{\text{H}}^{ + } }} )]\) and decrease in \(\log [(a_{{{\text{Ca}}^{2 + } }} )/(a_{{{\text{H}}^{ + } }}^{2} )]\) of the precipitating fluid. Low radiogenic ⁸⁷Sr/⁸⁶Sr values indicate a local origin of the elements necessary for secondary mineral formation from primary igneous phases. In addition, fractures cut the intrusive body, which contain zeolites, followed by calcite and a variety of other silicates, carbonates, and sulfates as younger generations. Stable isotope analysis of late-fracture calcite indicates very late circulation of meteoric fluids and mobilization of organic matter from surrounding sedimentary units.     

Zircon M127 – A Homogeneous Reference Material for SIMS U–Pb Geochronology Combined with Hafnium,Oxygen and,Potentially, Lithium Isotope Analysis

In this article, we document a detailed analytical characterisation of zircon M127, a homogeneous 12.7 carat gemstone from Ratnapura, Sri Lanka. Zircon M127 has TIMS‐determined mean U–Pb radiogenic isotopic ratios of 0.084743 ± 0.000027 for ²⁰⁶Pb/²³⁸U and 0.67676 ± 0.00023 for ²⁰⁷Pb/²³⁵U (weighted means, 2s uncertainties). Its ²⁰⁶Pb/²³⁸U age of 524.36 ± 0.16 Ma (95% confidence uncertainty) is concordant within the uncertainties of decay constants. The δ¹⁸O value (determined by laser fluorination) is 8.26 ± 0.06‰ VSMOW (2s), and the mean ¹⁷⁶Hf/¹⁷⁷Hf ratio (determined by solution ICP‐MS) is 0.282396 ± 0.000004 (2s). The SIMS‐determined δ⁷Li value is ?0.6 ± 0.9‰ (2s), with a mean mass fraction of 1.0 ± 0.1 μg g^?1 Li (2s). Zircon M127 contains ~ 923 μg g^?1 U. The moderate degree of radiation damage corresponds well with the time‐integrated self‐irradiation dose of 1.82 × 10¹⁸ alpha events per gram. This observation, and the (U–Th)/He age of 426 ± 7 Ma (2s), which is typical of unheated Sri Lankan zircon, enable us to exclude any thermal treatment. Zircon M127 is proposed as a reference material for the determination of zircon U–Pb ages by means of SIMS in combination with hafnium and stable isotope (oxygen and potentially also lithium) determination.     

The BEAM-project: prediction and assessment of mixture toxicities in the aquatic environment

Freshwater and marine ecosystems are exposed to various multi-component mixtures of pollutants. Nevertheless, most ecotoxicological research and chemicals regulation focus on hazard and exposure assessment of individual substances only, the problem of chemical mixtures in the environment is ignored to a large extent. In contrast, the assessment of combination effects has a long tradition in pharmacology, where mixtures of chemicals are specifically designed to develop new products, e.g. human and veterinary drugs or agricultural and non-agricultural pesticides. In this area, two concepts are frequently used and are thought to describe fundamental relationships between single substance and mixture effects: Independent Action (Response Addition) and Concentration Addition. The question, to what extent these concepts may also be applied in an ecotoxicological and regulatory context may be considered a research topic of major importance, as the concepts would allow to make use of already existing single substance toxicity data for the predictive assessment of mixture toxicities. Two critical knowledge gaps are identified: (a) There is a lack of environmental realism, as a huge part of our current knowledge about the applicability of the concepts is restricted to artificial situations with respect to mixture composition or biological effect assessment. (b) The knowledge on what exactly is needed for using the concepts as tools for the predictive mixture toxicity assessment is insufficient. Both gaps seriously hamper the necessary, scientifically sound consideration of mixture toxicities in a regulatory context.In this paper, the two concepts will be briefly introduced, the necessity of considering the toxicities of chemical mixtures in the environment will be demonstrated and the applicability of Independent Action and Concentration Addition as tools for the prediction and assessment of mixture toxicities will be discussed. An overview of the specific aims and approaches of the BEAM project to fill in the identified knowledge gaps is given and first results are outlined.     

Reply to Discussion of “Perceptual models of uncertainty for socio-hydrological systems: a flood risk change example”*

ABSTRACT

Ertsen discusses the representation of reality and uncertainty in our paper, raising three critical points. In response to the first, we agree that discussion of different interpretations of the concept of uncertainty is important when developing perceptual models – making different uncertainty interpretations explicit was a key motivation behind our method. Secondly, we do not, as Ertsen suggests, deny anyone who is not a “certified” scientist to have relevant knowledge. The elicitation of diverse views by discussing perceptual models is a basis for open discussion and decision making. Thirdly, Ertsen suggests that it is not useful to treat socio-hydrological systems as if they exist. We argue that we act as “pragmatic realists” in most practical applications by treating socio-hydrological systems as an external reality that can be known. But the uncertainty that arises from our knowledge limitations needs to be recognized, as it may impact on practical decision making and associated costs.     

Military Emissions, Armed Conflicts, Border Changes and the Kyoto Protocol

The impacts of military activities in peacetime, military action and territorial changes on greenhouse gas emission commitments of nations under the Kyoto Protocol are analysed. We propose rules and institutional responsibilities to deal with the repercussions of such changes on markets in emission permits and national commitments aiming at prevention of serious distortions.     

Comparison of environmental tracers including organic micropollutants as groundwater exfiltration indicators into a small river of a karstic catchment

Understanding groundwater–surface water (GW–SW) interactions is vital for water management in karstic catchments due to its impact on water quality. The objective of this study was to evaluate and compare the applicability of seven environmental tracers to quantify and localize groundwater exfiltration into a small, human-impacted karstic river system. Tracers were selected based on their emission source to the surface water either as (a) dissolved, predominantly geogenic compounds (radon-222, sulphate and electrical conductivity) or (b) anthropogenic compounds (predominantly) originating from wastewater treatment plant (WWTP) effluents (carbamazepine, tramadol, sodium, chloride). Two contrasting sampling approaches were compared (a) assuming steady-state flow conditions and (b) considering the travel time of the water parcels (Lagrangian sampling) through the catchment to account for diurnal changes in inflow from the WWTP. Spatial variability of the concentrations of all tracers indicated sections of preferential groundwater inflow. Lagrangian sampling techniques seem highly relevant for capturing dynamic concentration patterns of WWTP-derived compounds. Quantification of GW inflow with the finite element model FINIFLUX, based on observed in-stream Rn activities led to plausible fluxes along the investigated river reaches (0.265 m³ s⁻¹), while observations of other natural or anthropogenic environmental tracers produced less plausible water fluxes. Important point sources of groundwater exfiltration can be ascribed to locations where the river crosses geological fault lines. This indicates that commonly applied concepts describing groundwater–surface water interactions assuming diffuse flow in porous media are difficult to transfer to karstic river systems whereas concepts from fractured aquifers may be more applicable. In general, this study helps selecting the best suited hydrological tracer for GW exfiltration and leads to a better understanding of processes controlling groundwater inflow into karstic river systems.     

Polar organic micropollutants in the coastal environment of different marine systems

Polar anthropogenic organic micropollutants are frequently detected in freshwater and discharged on large scale into marine systems. In this work the results of 153 samples collected from the shorelines of the Baltic Sea (Germany), Northern Adriatic Sea (Italy), Aegean Sea and Dardanelles (Greece & Turkey), San Francisco Bay (USA), Pacific Ocean (USA), Mediterranean Sea (Israel), and Balearic Sea (Spain) are presented. The samples were analyzed for various classes of micropollutants such as pharmaceuticals, corrosion inhibitors, biocides, and stimulants. Caffeine, paraxanthine, theobromine, tolyltriazole, 1H-benzotriazole, and atrazine were detected in >50% of all samples. The detection frequencies of carbamazepine, iopamidol, diuron, sulfamethoxazole, paracetamol, theophylline, and atenolol were between 20% and 32%. As caffeine is linked to untreated wastewater, the widespread occurrence of raw sewage in marine environments and thus potentially elevated nutrient concentrations and risk for the presence of wastewater-related pathogens is remarkable.