Chemical and textural equilibration of garnet during amphibolite facies metamorphism: The influence of coupled dissolution–reprecipitation

Metamorphic equilibration requires chemical communication between minerals and may be inhibited through sluggish volume diffusion and or slow rates of dissolution in a fluid phase. Relatively slow diffusion and the perceived robust nature of chemical growth zoning may preclude garnet porphyroblasts from readily participating in low‐temperature amphibolite facies metamorphic reactions. Garnet is widely assumed to be a reactant in staurolite‐isograd reactions, and the evidence for this has been assessed in the Late Proterozoic Dalradian pelitic schists of the Scottish Highlands. The 3D imaging of garnet porphyroblasts in staurolite‐bearing schists reveals a good crystal shape and little evidence of marginal dissolution; however, there is also lack of evidence for the involvement of either chlorite or chloritoid in the reaction. Staurolite forms directly adjacent to the garnet, and its nucleation is strongly associated with deformation of the muscovite‐rich fabrics around the porphyroblasts. “Cloudy” fluid inclusion‐rich garnet forms in both marginal and internal parts of the garnet porphyroblast and is linked both to the production of staurolite and to the introduction of abundant quartz inclusions within the garnet. Such cloudy garnet typically has a Mg‐rich, Mn‐poor composition and is interpreted to have formed during a coupled dissolution–reprecipitation process, triggered by a local influx of fluid. All garnet in the muscovite‐bearing schists present in this area is potentially reactive, irrespective of the garnet composition, but very few of the schists contain staurolite. The staurolite‐producing reaction appears to be substantially overstepped during the relatively high‐pressure Barrovian regional metamorphism reflecting the limited permeability of the schists in peak metamorphic conditions. Fluid influx and hence reaction progress appear to be strongly controlled by subtle differences in deformation history. The remaining garnet fails to achieve chemical equilibrium during the reaction creating distinctive patchy compositional zoning. Such zoning in metamorphic garnet created during coupled dissolution–reprecipitation reactions may be difficult to recognize in higher grade pelites due to subsequent diffusive re‐equilibration. Fundamental assumptions about metamorphic processes are questioned by the lack of chemical equilibrium during this reaction and the restricted permeability of the regional metamorphic pelitic schists. In addition, the partial loss of prograde chemical and textural information from the garnet porphyroblasts cautions against their routine use as a reliable monitor of metamorphic history. However, the partial re‐equilibration of the porphyroblasts during coupled dissolution–reprecipitation opens possibilities of mapping reaction progress in garnet as a means of assessing fluid access during peak metamorphic conditions.     

The response in floodplain respiration of an alpine river to experimental inundation under different temperature regimes

The respiratory potential [i.e. electron transport system activity (ETSA)] of soils and sediments from five floodplain habitats (channel, gravel, islands, riparian forest and grassland) of the Urbach River, Switzerland, and actual respiration rate (R) of the same samples exposed to experimental inundation were measured. Measurements were carried out at three incubation temperatures (4°C, 12°C and 20°C), and ETSA/R ratios (i.e. exploitation of the overall metabolic capacity) were investigated to better understand the effects of temperature and inundation on floodplain functional heterogeneity. Furthermore, ETSA/R ratios obtained during experimental inundation were compared with ETSA/R ratios from field measurements to investigate the exploitation in total metabolic potential at different conditions. Lowest ETSA and R were measured in samples from channel and gravel habitats, followed by those from islands. Substantially higher values were measured in soils from riparian forest and grassland. Both ETSA and R increased with increasing temperature in samples from all habitats, while the ETSA/R ratio decreased because of a rapid response in microbial community respiration to higher temperatures. The metabolic capacity exploitation (i.e. ETSA/R) during experimental inundation was lowest in predominantly terrestrial samples (riparian forest and grassland), indicating the weakest response to wetted conditions. Comparison of experimentally inundated and field conditions revealed that in rarely flooded soils, the metabolic capacity was less exploited during inundation than during non‐flooded conditions. The results suggest high sensitivity in floodplain respiration to changes in temperature and hydrological regime. ETSA/R ratios are considered good indicators of changes in metabolic activity of floodplain soils and sediments, and thus useful to estimate the impact of changes in hydrological regime or to evaluate success of floodplain restoration actions. Copyright © 2015 John Wiley & Sons, Ltd.     

Predicting the dependency of a degree of saturation on void ratio and suction using effective stress principle for unsaturated soils

The paper presents an approach to predicting variation of a degree of saturation in unsaturated soils with void ratio and suction. The approach is based on the effective stress principle for unsaturated soils and several underlying assumptions. It focuses on the main drying and wetting processes and does not incorporate the effects of hydraulic hysteresis. It leads to the dependency of water retention curve (WRC) on void ratio, which does not require any material parameters apart from the parameters specifying WRC for the reference void ratio. Its validity is demonstrated by comparing predictions with the experimental data on four different soils taken over from the literature. Good correlation between the measured and predicted behaviour indirectly supports applicability of the effective stress principle for unsaturated soils. Copyright © 2009 John Wiley & Sons, Ltd.     

Chemical and isotopic interpretation of major ion compositions from precipitation: a one-year temporal monitoring study in Wrocław,SW Poland

The chemical compositions (Na⁺, NH₄ ⁺, K⁺, Mg²⁺, Ca²⁺, Cl^?, NO₂ ^?, NO₃ ^?, SO₄ ^2?, HCO₃ ^?) of wet precipitation and nitrogen isotope compositions δ¹⁵N(NH₄ ⁺) were studied from January to December 2010 in Wroc?aw (SW Poland). Results of a principle component analysis show that 82 % of the data variability can be explained by three main factors: 1) F1 (40 %) observed during vegetative season (electrical conductivity, HCO₃ ^?, NO₃ ^?, NO₂ ^?, NH₄ ⁺ and SO₄ ^2?), mainly controlling rainwater mineralization; 2) F2 (26 %) observed during vegetative and heating seasons (K⁺, Ca²⁺ and Mg²⁺), probably representing a combination of two processes: anthropogenic dusts and fertilizers application in agricultural fields, and 3) F3 (16 %) reported mainly during heating season (Na⁺ and Cl^?) probably indicating the influence of marine aerosols. Variations of δ¹⁵N(NH₄ ⁺) from ?11.5 to 18.5?‰ identify three main pathways for the formation of NH₄ ⁺: 1) equilibrium fractionation between NH₃ and NH₄ ⁺; 2) kinetic exchange between NH₃ and NH₄ ⁺; 3) NH₄ ⁺ exchange between atmospheric salts particles and precipitation. The coupled chemical/statistical analysis and δ¹⁵N(NH₄ ⁺) approach shows that while fossil fuels burning is the main source of NH₄ ⁺ in precipitation during the heating season, during the vegetative season NH₄ ⁺ originates from local sewage irrigation fields in Osobowice or agricultural fertilizers.     

Root‐related rhodochrosite and concretionary siderite formation in oxygen‐deficient conditions induced by a ground‐water table rise

Sedimentological, mineralogical, stable carbon and oxygen isotope determinations and biomarker analyses were performed on siderite concretions occurring in terrestrial silts to understand their formation and to characterize the sedimentary and diagenetic conditions favouring their growth. High δ¹³C values (6·4‰ on average) indicate that siderite precipitated in an anoxic environment where bacterial methanogenesis operated. The development of anoxic conditions during shallow burial was induced by a change in sedimentary environment from flood plain to swamp, related to a rise of the ground‐water table. Large amounts of decaying plant debris led to efficient oxygen consumption within the pore‐water in the peat. Oxygen depletion, in combination with a decrease in sedimentation rate, promoted anoxic diagenetic conditions under the swamp and favoured abundant siderite precipitation. This shows how a change in sedimentary conditions can have a profound impact on the early‐diagenetic environment and carbonate authigenesis. The concretions contain numerous rhizoliths; they are cemented with calcium‐rhodochrosite, a feature which has not been reported before. The rhodochrosite cement has negative δ¹³C values (?16·5‰ on average) and precipitated in suboxic conditions due to microbial degradation of roots coupled to manganese reduction. The exceptional preservation of the epidermis/exodermis and xylem vessels of former root tissues indicates that the rhodochrosite formed shortly after the death of a root in water‐logged sediments. Rhodochrosite precipitated during the initial stages of concretionary growth in suboxic microenvironments within roots, while siderite cementation occurred simultaneously around them in anoxic conditions. These suboxic microenvironments developed because oxygen was transported from the overlying oxygenated soil into sediments saturated with anoxic water via roots acting as permeable conduits. This model explains how separate generations of carbonate cements having different mineralogy and isotopic compositions, which would conventionally be regarded as cements precipitated sequentially in different diagenetic zones during gradual burial, can form simultaneously in shallow burial settings where strong redox gradients exist around vertically oriented permeable root structures.     

Convective and stratiform precipitation characteristics in an ensemble of regional climate model simulations

We apply a recently proposed algorithm for disaggregating observed precipitation data into predominantly convective and stratiform, and evaluate biases in characteristics of parameterized convective (subgrid) and stratiform (large-scale) precipitation in an ensemble of 11 RCM simulations for recent climate in Central Europe. All RCMs have a resolution of 25 km and are driven by the ERA-40 reanalysis. We focus on mean annual cycle, proportion of convective precipitation, dependence on altitude, and extremes. The results show that characteristics of total precipitation are often better simulated than are those of convective and stratiform precipitation evaluated separately. While annual cycles of convective and stratiform precipitation are reproduced reasonably well in most RCMs, some of them consistently and substantially overestimate or underestimate the proportion of convective precipitation throughout the year. Intensity of convective precipitation is underestimated in all RCMs. Dependence on altitude is also simulated better for stratiform and total precipitation than for convective precipitation, for which several RCMs produce unrealistic slopes. Extremes are underestimated for convective precipitation while they tend to be slightly overestimated for stratiform precipitation, thus resulting in a relatively good reproduction of extremes in total precipitation amounts. The results suggest that the examined ensemble of RCMs suffers from substantial deficiencies in reproducing precipitation processes and support previous findings that climate models’ errors in precipitation characteristics are mainly related to deficiencies in the representation of convection.