Ca2Mg(NO3)6×12H2O–structural investigations on a new compound retrieved from chimney deposits of a combined heat and power plant

Phase analysis of incrustations retrieved from chimney deposits of a combined heat and power plant in Malchow/Germany by X-ray powder diffraction gave evidence for the existence of a previously unknown hydrous calcium magnesium nitrate. Optical investigations of the sample showed the presence of colorless platy crystals with a maximum diameter of about 250 μm embedded in a partly polycrystalline and partly glassy matrix. Aided by EDX-analysis and Raman spectroscopy, a single-crystal diffraction study performed at ambient conditions demonstrated that the material represents a phase with composition Ca₂Mg(NO₃)₆×12H₂O. Basic crystallographic data are as follows: trigonal symmetry, space group type R \( \overline{3} \) , a?=?10.5583(5) Å, c?=?19.5351(10) Å, V?=?1885.97(16) ų, Z?=?3, (R(|F|) = 0.0248). The magnesium ions are coordinated by water molecules to form distorted Mg(H₂O)₆-octahedra. The calcium atoms are surrounded by nine ligands. The resulting CaO₉ tricapped trigonal prisms involve oxygen atoms from additional water moieties as well as from three different bidentate nitrate groups, respectively. Hydrogen bonds link one octahedron with two adjacent prisms into trimers. The trimers in turn are stacked in columns running parallel to [001]. Further hydrogen bonding between neighboring columns results in the formation of a three-dimensional network. To our best knowledge, Ca₂Mg(NO₃)₆×12H₂O represents a new structure type. However, column-like topologies with rods consisting of different types of polyhedra have been also observed in other trigonal hydrous nitrates. The structural relationships between these compounds are discussed. It is interesting to note that in previous phase equilibrium studies on the ternary system Ca(NO₃)₂-Mg(NO₃)₂-H₂O no other hydrous double salt has been described. Finally, the results of the structure analysis allowed a qualitative and quantitative phase analysis of the crystalline part of the chimney deposit by the Rietveld method.     

Reaction rim growth in the system MgO-Al2O3-SiO2 under uniaxial stress

We synthesize reaction rims between thermodynamically incompatible phases in the system MgO-Al₂O₃-SiO₂ applying uniaxial load using a creep apparatus. Synthesis experiments are done in the MgO-SiO₂ and in the MgO-Al₂O₃ subsystems at temperatures ranging from 1150 to 1350 °C imposing vertical stresses of 1.2 to 29 MPa at ambient pressure and under a constant flow of dry argon. Single crystals of synthetic and natural quartz and forsterite, synthetic periclase and synthetic corundum polycrystals are used as starting materials. We produce enstatite rims at forsterite-quartz contacts, enstatite-forsterite double rims at periclase-quartz contacts and spinel rims at periclase-corundum contacts. We find that rim growth under the “dry” conditions of our experiments is sluggish compared to what has been found previously in nominally “dry” piston cylinder experiments. We further observe that the nature of starting material, synthetic or natural, has a major influence on rim growth rates, where natural samples are more reactive than synthetic ones. At a given temperature the effect of stress variation is larger than what is anticipated from the modification of the thermodynamic driving force for reaction due to the storage of elastic strain energy in the reactant phases. We speculate that this may be due to modification of the physical properties of the polycrystals that constitute the reaction rims or by deformation under the imposed load. In our experiments rim growth is very sluggish at forsterite-quartz interfaces. Rim growth is more rapid at periclase-quartz contacts. The spinel rims that are produced at periclase-corundum interfaces show parabolic growth indicating that reaction rim growth is essentially diffusion controlled. From the analysis of time series done in the MgO-Al₂O₃ subsystem we derive effective diffusivities for the Al₂O₃ and the MgO components in a spinel polycrystal as ${\rm D}_{MgO} = 1.4 \pm 0.2 \cdot 10^{-15}$  m²/s and ${\rm D}_{Al_2O_3} = 3.7 \pm 0.6 \cdot 10^{-16}$  m²/s for T?=?1350 °C and a vertical stress of 2.9 MPa.     

UNFCCC before and after Paris – what's necessary for an effective climate regime?

What can reasonably be expected from the UNFCCC process and the climate conference in Paris 2015? To achieve transformative change, prevailing unsustainable routines embedded in socio-economic systems have to be translated into new and sustainable ones. This article conceptualizes the UNFCCC and the associated policy processes as a catalyst for this translation by applying a structurational regime model. This model provides an analytical distinction of rules (norms and shared meaning) and resources (economic resources as well as authoritative and allocative power) and allows us to conceptualize agency on various levels, including beyond nation states. The analysis concludes that the UNFCCC's narrow focus on emission targets, which essentially is a focus on resources, has proven ineffective. In addition, the static division of industrialized and developing countries in the Convention's annexes and the consensus-based decision-making rules have impeded ambitious climate protection. The article concludes that the UNFCCC is much better equipped to provide rules for climate protection activities and should consciously expand this feature to improve its impact.

Policy relevance

The international community is negotiating a new global climate agreement, to be adopted at the Conference of the Parties (COP 21) in December 2015 in Paris and to be applicable from 2020. This article analyses the successes and limitations the UNFCCC has had so far in combating climate change and it develops recommendations on how to enhance efforts within and beyond the framework of the Convention. From our analysis we derive two main recommendations for an effective and structurationally balanced treaty: First, multidimensional mitigation contributions going beyond emission targets could strongly improve countries’ abilities to tailor their contributions around national political discourses. Second, the UNFCCC regime should be complemented with another treaty outside of the UNFCCC framework. This ‘Alliance of the Ambitious’ would allow the pioneers of climate protection to move ahead and enjoy the benefits of cooperation. The dynamics generated through such a club approach could be fed back into the UNFCCC, leading to increased ambition by others in future commitment cycles.     

Growth mechanism of snowball garnets from the Lukmanier Pass area (Central Alps,Switzerland): a combined μCT/EPMA/EBSD study

For two decades, considerable efforts have been made to explain the formation of snowball garnets by either the rotational or non‐rotational models. On the basis of morphological, chemical and crystallographic evidence, this paper presents new data on snowball garnets showing that the formation of these microstructures can be explained by the combination of the two previously proposed mechanisms operating consecutively during garnet growth. The crystallization sequence of garnet revealed by Mn contouring and the distribution of crystallographic orientations within the spiral indicate that the final stages of garnet growth are controlled by post‐kinematic crystallization. However, some microstructural arguments plead for a rotational contribution during the first stages of growth. In this view, the overall spiral geometry is thought to overestimate the true amount of rotation experienced by the garnets. Results also reveal the existence of complex snowball garnets consisting of several grains formed from distinct nucleation sites.     

Hydrothermal alteration in the core of the Yaxcopoil‐1 borehole,Chicxulub impact structure,Mexico

Abstract Petrographic, electron microprobe, and Raman spectrometric analyses of Yaxcopoil‐1 core samples from the Chicxulub crater indicate that the impact generated a hydrothermal system. Relative textural and vein crosscutting relations and systematic distribution of alteration products reveal a progression of the hydrothermal event in space and time and provide constraints on the nature of the fluids. The earliest calcite, halite, and gaylussite suggest that the impactite sequence was initially permeated by a low temperature saline brine. Subsequent development of a higher temperature hydrothermal regime is indicated by thermal metamorphic diopside‐hedenbergite (Aeg₃Fs_18‐33En_32‐11Wo_47‐53) after primary augite and widespread Na‐K for Ca metasomatic alkali exchange in plagioclase. Hydrothermal sphene, apatite, magnetite + (bornite), as well as early calcite (combined 3 to 8 vol%) were introduced with metasomatic feldspar. A lower temperature regime characterized by smectite after probable primary glass, secondary chlorite, and other pre‐existing mafic minerals, as well as very abundant calcite veins and open‐space fillings, extensively overprinted the early hydrothermal stage. The composition of early and late hydrothermal minerals show that the solution was chlorine‐rich (Cl/F >10) and that its Fe/Mg ratio and oxidation state increased substantially (4 to 5 logfO₂ units) as temperature decreased through time. The most altered zone in the impactite sequence occurs 30 m above the impact melt. The lack of mineralogical zoning about the impact melt and convective modeling constraints suggest that this unit was too thin at Yaxcopoil‐1 to provide the necessary heat to drive fluids and implies that the hydrothermal system resulted from the combined effects of a pre‐existing saline brine and heat that traveled to the Yaxcopoil‐1 site from adjacent areas where the melt sheet was thicker. Limonite after iron oxides is more common toward the top of the sequence and suggests that the impactite section was subjected to weathering before deposition of the Tertiary marine cover. In addition, scarce latest anatase stringers, chalcopyrite, and barite in vugs, francolite after apatite, and recrystallized halite are the likely products of limited post‐hydrothermal ambient‐temperature diagenesis, or ocean and/or meteoric water circulation.     

Formation of garnet clusters during polyphase metamorphism

Pre‐Alpine garnets of Variscan age from metapelitic basement units in Northern Italy were strongly retrogressed at near‐surface conditions prior to Alpine contact metamorphism. The replacement by sheet silicates caused a significant volume increase during retrogression, producing pervasive fracturing. Up to several hundreds of angular fragments formed from each crystal. Electron backscatter diffraction analysis documents a maximum misorientation of ~22° of some fragments as a result of local rotation during fracturing. New garnet growth is observed on the garnet fragments during contact metamorphic overprinting, resulting in garnet clusters. Fragments can be identified due to calcium‐rich domains. Fragment orientations were inherited, and only minor new nucleation occurred. These garnets develop features typically associated with multiple nucleation models, but here they reflect multiple metamorphic events. We propose that clusters can be indicative of multiple metamorphic events, which were separated by a period of intense retrograde alteration.     

Basin modelling of a lignite‐bearing salt rim syncline: insights into rim syncline evolution and salt diapirism in NW Germany

The Helmstedt‐Staßfurt salt wall is 70 km long, 6–8 km wide and one of the most important diapiric structures in northern Germany, based on the economically significant lignite‐bearing rim synclines. The analysed Schöningen rim syncline, located on the southwestern side of the Helmstedt‐Staßfurt structure, is 8 km long and 3 km wide. The basin‐fill is up to 366 m thick and characterized by 13 major lignite seams with thicknesses between 0.1 and 30 m. The key objectives of this article were to expand on the classical cross‐section based rim syncline analysis by the use of 3D models and basin simulations. Cross‐sections perpendicular to the basin axis indicate that the basin‐fill has a pronounced lenticular shape. This shape varies from more symmetric in the NW to clearly asymmetric in the SE. Isopach maps imply a two‐fold depocentre evolution. The depocentre migrated over time towards the salt wall and also showed some distinct shifts parallel to the salt wall. The basin modelling part of the study was carried out with the software PetroMod^®, which focused on the burial history of the rim syncline. Modelling results also show the progressive migration of the rim syncline depocentre towards the salt wall. The present‐day asymmetry of the basin‐fill was already developed in the early phases of rim syncline evolution. The extracted geohistory curve shows initial rapid subsidence between 57 and 50 Ma and more moderate subsidence from 50 to 34 Ma. This pattern is interpreted to reflect salt evacuation from the source layer into the salt wall. The initial salt‐withdrawal rate was rapid, but later decreased probably due to depletion of the source layer.     

Karst morphology and groundwater vulnerability of high alpine karst plateaus

High alpine karst plateaus are recharge areas for major drinking water resources in the Alps and many other regions. Well-established methods for the vulnerability mapping of groundwater to contamination have not been applied to such areas yet. The paper characterises this karst type and shows that two common vulnerability assessment methods (COP and PI) classify most of the areas with high vulnerability classes. In the test site on the Hochschwab plateau (Northern Calcareous Alps, Austria), overlying layers are mostly absent, not protective or even enhance point recharge, where they have aquiclude character. The COP method classifies 82% of the area as highly or extremely vulnerable. The resulting maps are reasonable, but do not differentiate vulnerabilities to the extent that the results can be used for protective measures. An extension for the upper end of the vulnerability scale is presented that allows identifying ultra vulnerable areas. The proposed enhancement of the conventional approach points out that infiltration conditions are of key importance for vulnerability. The method accounts for karst genetical and hydrologic processes using qualitative and quantitative properties of karst depressions and sinking streams including parameters calculated from digital elevations models. The method is tested on the Hochschwab plateau where 1.7% of the area is delineated as ultra vulnerable. This differentiation could not be reached by the COP and PI methods. The resulting vulnerability map highlights spots of maximum vulnerability and the combination with a hazard map enables protective measures for a manageable area and number of sites.     

Quartz Reference Materials for Oxygen Isotope Analysis by SIMS

Two quartz samples of igneous origin, UNIL‐Q1 (Torres del Paine Intrusion, Chile) and BGI‐Q1 (Shandong province, China), were calibrated for their oxygen isotope composition for SIMS measurements. UNIL‐Q1 and BGI‐Q1 were evaluated for homogeneity using SIMS. Their reference δ¹⁸O values were determined by CO₂ laser fluorination. The average δ¹⁸O value found for UNIL‐Q1 is 9.8 ± 0.06‰ and that for BGI‐Q1 is 7.7 ± 0.11‰ (1s). The intermediate measurement precision of SIMS oxygen isotope measurements was 0.32–0.41‰ (2s; UNIL‐Q1) and 0.40–0.48‰ (2s; BGI‐Q1), respectively. While less homogeneous in its oxygen isotope composition, BGI‐Q1 is also suitable for SIMS trace element measurements.