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.     

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.     

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.     

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.     

Solubility of the assemblage albite+K-feldspar+andalusite+quartz in supercritical aqueous chloride solutions at 650 °C and 2 kbar

The solubility of the high grade pelite assemblage albite+K-feldspar+andalusite+quartz at 650 °C and 2 kbar was determined in aqueous solutions over a total chloride range of 0.01–3 m_Cl^tot using rapid-quench hydrothermal technique. The concentration of Na, K, Si, and Al was determined in the fluid phase after quench. The K/Na ratio was determined by approaching the equilibrium from below and above. It is 0.34 at low chloride concentrations and decreases slightly to 0.31 with increasing total chloride. Silica and aluminum concentrations were determined only from undersaturation. The silica solubility is found to be independent of chloride concentration and is 0.13 molal. Aluminum is nearly independent of chloride concentration decreasing only slightly from 0.0015 to 0.0007 molal. Comparison of the experimental data with thermodynamic model calculations demonstrates that the silica concentrations are well predicted, while significant differences exist between individual databases for Al speciation and its total concentration. Al concentrations are underestimated by up to 10 to 15 orders of magnitude using the SUPCRT92 database. Predicted K/Na ratios are underestimated by up to 30%. The best predictions achieved for this simplified high-grade pelite assemblage are those using the SUPCRT92 database with revised thermodynamic data for feldspars and K- and Na-species (J. Phys. Chem. Ref. Data 24 (1995) 1401) and additional Al-species (Am. J. Sci. 295 (1995) 1255; Geochim. Cosmochim. Acta 61 (1997) 2175). The use of ideal mixing for neutral complexes in combination with the extended Debye–Hückel activity model for the charged species yields the most compatible speciation model.     

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.     

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.     

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.