Targeting European R&D for accidental marine pollution

Accidental marine pollution can have major ecological and economic consequences at national and trans-national levels, and there is a need to achieve a better integration of science into actual decision-making systems to support prevention measures, response systems and management activities.. Effective linking mechanisms between R&D and end-users/policy stakeholders are required to ensure the relevance of R&D, effective uptake of R&D outputs, and suitable policy development. Different issues and barriers to effectively link accidental marine pollution R&D effort to end-users concerns and needs and to develop a trans-national strategic approach are identified, analysed, and further developed into recommendations.     

Aragonite–calcite veins of the ‘Erzberg’ iron ore deposit (Austria): Environmental implications from young fractures

The well‐known Erzberg site represents the largest siderite (FeCO₃) deposit in the world. It consists of various carbonates accounting for the formation of prominent CaCO₃ (dominantly aragonite) precipitates filling vertical fractures of different width (centimetres to decimetres) and length (tens of metres). These commonly laminated precipitates are known as ‘erzbergite’. This study focuses on the growth dynamics and environmental dependencies of these vein fillings. Samples recovered on‐site and from mineral collections were analyzed, and these analyses were further complemented by modern water analyses from different Erzberg sections. Isotopic signatures support meteoric water infiltration and sulphide oxidation as the principal hydrogeochemical mechanism of (Ca, Mg and Fe) carbonate host rock dissolution, mobilization and vein mineralization. Clumped isotope measurements revealed cool formation temperatures of ca 0 to 10°C for the aragonite, i.e. reflecting the elevated altitude Alpine setting, but unexpectedly low for aragonite nucleation. The ²³⁸U–²³⁴U–²³⁰Th dating yielded ages from 285·1 ± 3·9 to 1·03 ± 0·04 kyr bp and all samples collected on‐site formed after the Last Glacial Maximum. The observed CaCO₃ polymorphism is primarily controlled by the high aqueous Mg/Ca ratios resulting from dissolution of Mg‐rich host rocks, with Mg/Ca further evolving during prior CaCO₃ precipitation and CO₂ outgassing in the fissured aquifer. Aragonite represents the ‘normal’ mode of erzbergite formation and most of the calcite is of diagenetic (replacing aragonite) origin. The characteristic lamination (millimetre‐scale) is an original growth feature and mostly associated with the deposition of stained (Fe‐rich) detrital particle layers. Broader zonations (centimetre‐scale) are commonly of diagenetic origin. Petrographic observations and radiometric dating support an irregular nature for most of the layering. Open fractures resulting from fault tectonics or gravitational mass movements provide water flow routes and fresh chemical reaction surfaces of the host rock carbonates and accessory sulphides. If these prerequisites are considered, including the hydrogeochemical mechanism, modern water compositions, young U‐Th ages and calculated precipitation rates, it seems unlikely that the fractures had stayed open over extended time intervals. Therefore, it is most likely that they are geologically young.     

Preservation of Fe isotope heterogeneities during diagenesis and metamorphism of banded iron formation

We present the iron isotope composition of primary, diagenetic and metamorphic minerals in five samples from the contact metamorphosed Biwabik Iron Formation. These samples attained peak metamorphic temperatures of <200, <340, ∼500, <550, and <740°C respectively. δ⁵⁶Fe of bulk layers ranges from −0.8 to +0.8‰; in some samples the layers may differ by >1‰ on the millimeter scale. Minerals in the lowest grade samples consistently show a sequence in which δ⁵⁶Fe of magnetite > silicate ≥ carbonate. The inter-mineral Fe isotope differences vary in a fashion that cannot be reconciled with theoretical temperature-dependent fractionation factors. Textural evidence reveals that most, if not all, magnetite in the Biwabik Formation is diagenetic, not primary, and that there was tremendous element mobility during diagenesis. The short duration of contact metamorphism allowed diagenetic magnetite compositions to be preserved throughout prograde metamorphism until at least the appearance of olivine. Magnetite compositions therefore act as an isotope record of the environment in which these sediments formed. Larger-scale fluid flow and longer timescales may allow equilibration of Fe isotopes in regionally metamorphosed rocks to lower temperatures than in contact metamorphic environments, but weakly regionally metamorphosed rocks may preserve small-scale Fe isotopic heterogeneities like those observed in the Biwabik Iron Formation. Importantly, Fe isotope compositions that are characteristic of chemical sedimentation or hydrothermal processes are preserved at low grade in the form of large inter-mineral variations, and at high grade in the form of unique bulk rock compositions. This observation confirms earlier work that has suggested that Fe isotopes can be used to identify sedimentary processes in the Precambrian rock record. An erratum to this article can be found at     

Sorption kinetics of naphthalene and phenanthrene in loess soils

A laboratory study was executed to investigate the effect of surfactants to enhance sorption of polycyclic aromatic hydrocarbon (PAH) contaminants in loess soil. Phenanthrene and naphthalene were chosen as organic contaminant indicators in loess soil modified by the cation surfactant hexadecyltrimethylammonium (HDTMA) bromide. The kinetic behavior of sorption during transport in natural and modified loess soil was studied. The results indicated that sorption rate in the cation surfactant modified loess soils was at least 3 times faster than that of the natural soil. A first-order kinetics model fitted the sorption data well for both soils. The sorption rates of the two organic compounds were related to their primary residual quantity on the soils. The experiments showed that sorption amounts approached constant values approximately within 30 and 90 min for naphthalene and phenanthrene at 298–318 K, respectively. The rate constants, however, displayed negative correlation with increasing temperature. With changing temperature, the activation energy was calculated at –6.196–1.172 kJ/mol for naphthalene and –28.86–15.70 kJ/mol for phenanthrene at 298–318 K. The results can be used to predict the sorption kinetics of phenanthrene and naphthalene in loess soils, and in a wider perspective, be used to better understand the transport of petroleum contaminants in the soil environment.     

Iron and lithium isotope systematics of the Hekla volcano,Iceland — Evidence for Fe isotope fractionation during magma differentiation

In this study potential iron isotope fractionation by magmatic processes in the Earth's crust was systematically investigated. High precision iron isotope analyses by MC-ICP-MS were performed on a suite of rock samples representative for the volcanic evolution of the Hekla volcano, Iceland. The whole series of Hekla's rocks results from several processes. (i) Basaltic magmas rise and induce partial melting of meta-basalts in the lower part of the Icelandic crust. The resulting dacitic magma evolves to rhyolitic composition through crystal fractionation. During this differentiation the δ^56/54Fe_IRMM-014 values increase successively from 0.051 ± 0.021‰ for the primitive dacites to 0.168 ± 0.021‰ for the rhyolites. This increase can be described by a Rayleigh fractionation model using a constant bulk fractionation factor between all mineral phases (M) and the silicate liquid (L) of Δ^56/54Fe_M–L = ? 0.1‰. (ii) The basaltic magma itself differentiates by crystal fractionation to basaltic andesite composition. No Fe isotope fractionation was found in this series. All basalts and basaltic andesites have an average δ^56/54Fe_IRMM-014 value of 0.062 ± 0.042‰ (2SD, n = 9), identical to mean terrestrial basaltic values reported in previous studies. This observation is consistent with the limited removal of iron from the remaining silicate melt through crystal fractionation and small mineral-melt Fe isotope fractionation factors expected at temperatures in excess of 1050 °C. (iii) Andesites are produced by mixing of basaltic andesite with dacitic melts. The iron isotope composition of the andesites is matching that of the basaltic andesites and the less evolved dacites, in agreement with a mixing process. In the Hekla volcanic suite Li concentrations are positively correlated with indicators of magma differentiation. All Hekla rocks have δ⁷Li values typical for the upper mantle and demonstrate the absence of resolvable Li isotope fractionation during crystal fractionation. As a fluid-mobile trace element, Li concentrations and isotopes are a potential tracer of magma/fluid interaction. At Hekla, Li concentrations and isotope compositions do not indicate any extensive fluid exsolution. Hence, the heavy Fe isotope composition of the dacites and rhyolites can be predominately attributed to fractional crystallisation. Iron isotope analyses on single samples from other Icelandic volcanoes (Torfajökull, Vestmannaeyjar) confirm heavy Fe isotope enrichment in evolving magmas. Our results suggest that the iron isotope composition of highly evolved crust can be slightly modified by magmatic processes.     

Regionalization of precipitation characteristics in Iran’s Lake Urmia basin

Theoretical and Applied Climatology - Lake Urmia in northwest Iran, once one of the largest hypersaline lakes in the world, has shrunk by almost 90% in area and 80% in volume during the last four...     

Technical paper: FluMo—a mobile fluid–chemical monitoring unit for geothermal plants

A versatile fluid–chemical monitoring unit has been developed in the framework of the geothermal research platform Groß Schönebeck, Germany. It enables selective online and in situ measurements of various physico-chemical parameters at different surface locations of a geothermal fluid loop. Sensors are provided for pressure, temperature, volumetric flow rate, density, pH-value, redox potential, oxygen content, and electrical conductivity. In addition, the apparatus features two fluid samplers to manually collect fluid under in situ conditions and ultimately analyze the solution composition. All devices are mounted on a rack allowing easy transfer of the apparatus to other geothermal plants. The maximum operating pressure and temperature of the unit are 15 bar and 150 °C, respectively. The scientific and technical purpose of the system is to monitor a compositional variability of the produced fluid and chemical processes potentially occurring within the plant. These may result from reactions between the fluid and the surrounding materials, e.g., corrosion. Also, mineral precipitation as a consequence of temperature and/or pressure decrease or oxygen contamination may occur. This information is of paramount importance as so induced reactions might lead to failure of plant components or may damage the geothermal reservoir upon fluid reinjection and thus decrease injectivity.     

Nanochemo-mechanical signature of organic-rich shales: a coupled indentation–EDX analysis

The organic–inorganic nature of organic-rich source rocks poses several challenges for the development of functional relations that link mechanical properties with geochemical composition. With this focus in mind, we herein propose a method that enables chemo-mechanical characterization of this highly heterogeneous source rock at the micron and submicron length scale through a statistical analysis of a large array of energy-dispersive X-ray spectroscopy (EDX) data coupled with nanoindentation data. The ability to include elemental composition to the indentation probe via EDX is shown to provide a means to identify pure material phases, mixture phases, and interfaces between different phases. Employed over a large array, the statistical clustering of this set of chemo-mechanical data provides access to the properties of the fundamental building blocks of clay-dominated organic-rich source rocks. The versatility of the approach is illustrated through the application to a large number of source rocks of different origin, chemical composition, and organic content. We find that the identified properties exhibit a unique scaling relation between stiffness and hardness. This suggests that organic-rich shale properties can be reduced to their elementary constituents, with several implications for the development of predictive functional relations between chemical composition and mechanical properties of organic-rich source rocks such as the intimate interplay between clay-packing, organic maturity, and mechanical properties of porous clay/organic phase.     

High-resolution isotope records of early Holocene rapid climate change from two coeval stalagmites of Katerloch Cave,Austria

Two coeval stalagmites from Katerloch Cave show pronounced intervals of low δ¹⁸O values around 8.2, 9.1, and 10.0 kyr (all ages are reported before the year 2000 AD) and represent an inorganic U–Th dated climate archive from the southeast of the European Alps, a region where only very few well-dated climate records exist. The O isotope curves, providing near-annual resolution, allow a direct comparison to the Greenland ice core records, as temperature was the primary factor controlling the O isotopic composition of Katerloch speleothems.The 8.2 kyr climate anomaly lasted about one century, from 8196 to 8100 yr, with a maximum amplitude of 1.1‰ at 8175 yr. The event is characterized by a rapid onset and a more gradual demise and U–Th data as well as annual lamina counting support a rapid climate change towards cooler conditions within 10–20 yr. There is no strong evidence that the 8.2 kyr anomaly was superimposed on a pronounced longer-term cooling episode, nor do the new data support two separate cooling events within the 8.2 kyr event as reported by other studies. Our record also shows a distinct climate anomaly around 9.1 kyr, which lasted 70–110 yr and showed a maximum amplitude of 1.0‰, i.e. it had a similar duration and amplitude as the (central) 8.2 kyr event. Compared to the 8.2 kyr event, the 9.1 kyr anomaly shows a more symmetrical structure, but onset and demise still occurred within a few decades only. The different progression of the 8.2 (asymmetrical) and 9.1 kyr anomaly (symmetrical) suggests a fundamental difference in the trigger and/or the response of the climate system. Moreover, both stalagmites show evidence of a climate anomaly around 10.0 kyr, which was of comparable magnitude to the two subsequent events.Using a well constrained modern calibration between air temperature and δ¹⁸O of precipitation for the study area and cave monitoring data (confirming speleothem deposition in Katerloch reflecting cave air temperature), a maximum cooling by ca 3 °C can be inferred at 8.2 and 9.1 kyr, which is similar to other estimates, e.g., from Lake Ammersee north of the Alps. The O isotopic composition of meteoric precipitation, however, is a complex tracer of the hydrological cycle and these temperature estimates do not take into account additional effects such as changes in the source area or synoptic shifts. Apart from that, the relative thickness of the seasonally controlled lamina types in the Katerloch stalagmites remains rather constant across the intervals comprising the isotopic anomalies, i.e. the stalagmite petrography argues against major shifts in seasonality during the early Holocene climate excursions.