Factors controlling carbonate dissolution rates quantified in a field test in the Austrian alps

Carbonate dissolution rates were investigated by measuring the mass difference of carbonate tablets exposed to natural dissolution for 1 year. 70 tablets were distributed over 13 test sites on the north slope of the Hochschwab Massif in the Austrian Alps. The influences of altitude, subsoil vs. sub-aerial exposure, vegetation, karst morphology, soil humidity, sample lithology, and sample surface morphology were investigated. The observed dissolution rates varied between 13 and 40 μm/a for subcutaneous samples and about 11 μm/a for sub-aerial exposure. Outstandingly high rates of 48 μm/a were observed in a doline and nearly zero rates were measured at a site influenced by seeping spring water.A mass balance, using high-resolution hydrological data, was calculated for the Kläffer Spring, which has an average outflow of 4.8 m³/s. It indicated a loss of 21×10⁶ kg of carbonate rock per year which gives an average dissolution rate of 95 μm/a for the catchment area of 83 km². The dissolution rates of 10 μm/a from the sub-aerially exposed samples are comparable to values from limestone pedestals, which were protected from dissolution by glacial erratics for the past 15 ka.     

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.     

Statistically Extrapolated Nowcasting of Summertime Precipitation over the Eastern Alps

This paper presents a new multiple linear regression(MLR) approach to updating the hourly, extrapolated precipitation forecasts generated by the INCA(Integrated Nowcasting through Comprehensive Analysis) system for the Eastern Alps.The generalized form of the model approximates the updated precipitation forecast as a linear response to combinations of predictors selected through a backward elimination algorithm from a pool of predictors. The predictors comprise the raw output of the extrapolated precipitation forecast, the latest radar observations, the convective analysis, and the precipitation analysis. For every MLR model, bias and distribution correction procedures are designed to further correct the systematic regression errors. Applications of the MLR models to a verification dataset containing two months of qualified samples,and to one-month gridded data, are performed and evaluated. Generally, MLR yields slight, but definite, improvements in the intensity accuracy of forecasts during the late evening to morning period, and significantly improves the forecasts for large thresholds. The structure–amplitude–location scores, used to evaluate the performance of the MLR approach,based on its simulation of morphological features, indicate that MLR typically reduces the overestimation of amplitudes and generates similar horizontal structures in precipitation patterns and slightly degraded location forecasts, when compared with the extrapolated nowcasting.     

Multi-Century Tree-Ring Reconstructions of Colorado Streamflow for Water Resource Planning

Water resource management requires knowledge of the natural variability in streamflow over multiple time scales. Reconstructions of streamflow derived from moisture-sensitive trees extend, in both time and magnitude, the variability provided by relatively short gage records. In this study, we present a network of 14 annual streamflow reconstructions, 300–600 years long, for gages in the Upper Colorado and South Platte River basins in Colorado generated from new and existing tree-ring chronologies. Gages for the reconstruction were selected on the basis of their importance to two of the largest Colorado Front Range water providers, who provided the natural flow data for the calibration with tree-ring data. The reconstruction models explain 63–76% of the variance in the gage records and capture low flows particularly well. Analyses of the reconstructions indicate that the 20th century gage record does not fully represent the range of streamflow characteristics seen in the prior two to five centuries. Multi-year drought events more severe than the 1950s drought have occurred, notably in the 19th century, and the distribution of extreme low flow years is markedly uneven over the past three centuries. When the 14 reconstructions are grouped into Upper Colorado, northern South Platte, and southern South Platte regional flow reconstructions, the three time series show a high degree of coherence, but also time-varying divergences that may reflect the differential influence of climatic features operating in the western U.S. These reconstructions are currently being used by water managers to assess the reliability of water supply systems under a broader range of conditions than indicated by the gage records alone.     

Drought 2002 in Colorado: An Unprecedented Drought or a Routine Drought?

The 2002 drought in Colorado was reported by the media and by public figures, and even by a national drought-monitoring agency, as an exceptionally severe drought. In this paper we examine evidence for this claim. Our study shows that, while the impacts of water shortages were exceptional everywhere, the observed precipitation deficit was less than extreme over a good fraction of the state. A likely explanation of this discrepancy is the imbalance between water supply and water demand over time. For a given level of water supply, water shortages become intensified as water demands increase over time. The sobering conclusion is that Colorado is more vulnerable to drought today than under similar precipitation deficits in the past.     

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.     

Component mobility at 900 °C and 18 kbar from experimentally grown coronas in a natural gabbro

Several approximately 100-μm-wide reaction zones were grown under experimental conditions of 900 °C and 18 kbar along former olivine-plagioclase contacts in a natural gabbro. The reaction zone comprises two distinct domains: (i) an irregularly bounded zone with idiomorphic grains of zoisite and minor corundum and kyanite immersed in a melt developed at the plagioclase side and (ii) a well-defined reaction band comprising a succession of mineral layers forming a corona structure around olivine. Between the olivine and the plagioclase reactant phases we observe the following layer sequence: olivine|pyroxene|garnet|partially molten domain|plagioclase. Within the pyroxene layer two micro-structurally distinct layers comprising enstatite and clinopyroxene can be discerned. Chemical potential gradients persisted for the CaO, Al₂O₃, SiO₂, MgO and FeO components, which drove diffusion of Ca, Al and Si bearing species from the garnet-matrix interface to the pyroxene-olivine interface and diffusion of Mg- and Fe-bearing species in the opposite direction. The systematic mineralogical organization and chemical zoning across the corona suggest that the olivine corona was formed by a “diffusion-controlled” reaction. We estimate a set of diffusion coefficients and conclude that L_AlAl < L_CaCa < (L_SiSi, L_FeFe) < L_MgMg during reaction rim growth.     

The behavior of Mg, Fe, and Ni during the replacement of olivine by orthopyroxene: experiments relevant to mantle metasomatism

Replacement of olivine by orthopyroxene is a frequently observed phenomenon in mantle metasomatism. In order to study element redistribution in SiO₂ metasomatism we synthesised orthopyroxene reaction rims at the contacts between forsterite-rich olivine and quartz. The orthopyroxene rims grew from the original quartz-olivine interface into both directions implying counterdiffusion of iron/magnesium and silicon. Following local equilibrium partitioning the X_Fe is lower in the orthopyroxene than in the reactant olivine at the olivine-orthopyroxene replacement front. The resulting local iron excess is compensated by formation of orthopyroxene with a higher X_Fe at the quartz-orthopyroxene interface, which is out of equilibrium with the reactant olivine. This is facilitated through short circuit diffusion along grain boundaries within the orthopyroxene rim. Due to the low capacity of orthopyroxene to accommodate Ni, this component is forced to diffuse back into the olivine producing a Ni enriched zone ahead of the replacement front. This leads to Ni contents in the orthopyroxene rim, which are higher than what is expected in equilibrium with the unaltered olivine. Taking quartz as a proxy for a silica rich fluid or liquid metasomatising agent, we conclude that the overall element fractionation between olivine and the silica rich phase may deviate from equilibrium partitioning so that the Fe and Ni concentrations in the orthopyroxene which is in contact with quartz are higher than in equilibrium with the reactant olivine. This indicates that kinetic fractionation is important for the chemical evolution of both the mantle rocks and the metasomatising agents.     

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.     

pH changes in peralkaline late-magmatic fluids

The 1.15-Ga-old Ilimaussaq intrusive complex in South Greenland shows an extensive fractionation trend from alkaline augite syenite to various varieties of strongly peralkaline, agpaitic nepheline syenites. The peralkaline nepheline-bearing syenites crystallized between ca. 900 and 450 °C at 1 kbar and they are cut by late-magmatic hydrothermal veins with nepheline-absent assemblages of albite + aegirine + analcime - sodalite - Na-Be-silicates (tugtupite, chkalovite, sørensenite) - ussingite (NaAlSi₃O₈*NaOH). Based on fluid inclusions and phase equilibria, these veins crystallized between 300 and 500 °C at 1 kbar. Textures indicate that the hydrothermal veins at least partly replaced earlier Ilimaussaq rocks. The occurrence of ussingite and tugtupite suggests that the late-magmatic fluids had strongly basic pH values. Speciation calculations show that the pH in fluids of the system Na-Al-Si-O-H-Cl mainly depends on the Na/Cl ratio and, to a lesser degree, on salinity and temperature. If the Na/Cl ratio is greater than 1, pH (at 400 °C and 1 kbar, where neutrality is about at pH 5) lies between 7 and 12. Because Na/Cl tends to decrease in the final stages of magmatism and during crystallization of the vein assemblage, pH of late-magmatic fluids generally should become more acidic, and only two processes can increase Na/Cl and, thus, pH: dissolution of a Cl-poor or Cl-free Na silicate or unmixing of an HCl-enriched vapour phase. Field observations and microtextures suggest that replacement reactions are responsible for the change to basic pH at least in some alteration assemblages. While replacement of 1 mol nepheline by 1 mol analcime would not alter the pH, the volume-conserving reaction 1.85  Ne + 2.3  H₂ O + 0.19  H₄ SiO₄ = 1.02  Anl + 0.83   Na⁺ + 0.83  Al(OH)₄^-1.85\;{\rm Ne} + 2.3\;{\rm H}_{\rm 2} {\rm O} + 0.19\;{\rm H}_{\rm 4} {\rm SiO}_4 = 1.02\;{\rm Anl} + 0.83\,\;{\rm Na}^ + + 0.83\;{\rm Al(OH)}_4^ - can be used to model the replacement process quantitatively, provided it occurred in a more or less closed system. Progress of this reaction leads to successively increasing pH of the fluid during fluid-rock interaction and stabilizes minerals such as ussingite and tugtupite. Transferring the two processes to a larger scale, it is proposed that the extreme 'hyper-agpaitic' assemblages at Ilimaussaq or at the Kola peninsula, which include copious amounts of very basic, water-soluble minerals such as trona, villiaumite or thermonatrite, are formed either in this way by autometasomatic reactions of late-magmatic fluids or melts (or supercritical fluid-melt-mixtures) with earlier crystallized rocks of the same plutonic complex or by large-scale vapour unmixing in the very final stages of magmatism.