Reactivity of sandstone and siltstone samples from the Ketzin pilot CO2 storage site-Laboratory experiments and reactive geochemical modeling

To evaluate mineralogical-geochemical changes within the reservoir of the Ketzin pilot CO₂ storage site in Brandenburg, Germany, two sets of laboratory experiments on sandstone and siltstone samples from the Stuttgart Formation have been performed. Samples were exposed to synthetic brine and pure CO₂ at experimental conditions and run durations of 5.5 MPa/40 °C/40 months for sandstone and 7.5 MPa/40 °C/6 months for siltstone samples, respectively. Mineralogical changes in both sets of experiments are generally minor making it difficult to differentiate natural variability of the whole rock samples from CO₂-induced alterations. Results of sandstone experiments suggest dissolution of the anorthite component of plagioclase, anhydrite, K-feldspar, analcime, hematite and chlorite + biotite. Dissolution of the anorthite component of plagioclase, anhydrite and K-feldspars is also observed in siltstone experiments. In an inverse modeling approach, an extensive set of equilibrium simulations was set up in order to reproduce the experimental observations of the sandstone experiments. Simulations generally show fairly good matches with the experimental observations. Best matches with measured brine data are obtained from mineral combinations of albite, analcime, anhydrite, dolomite, hematite, illite, and kaolinite. The major discrepancies during equilibrium modeling, however, are reactions involving Fe²⁺ and Al³⁺. The best matching subsets of the equilibrium models were finally run including kinetic rate laws. These simulations reveal that experimentally determined brine data was well matched, but reactions involving K⁺ and Fe²⁺ are not fully covered. The modeling results identified key primary minerals as well as key chemical processes, but also showed that the models are not capable of covering all possible contingencies.     

Thermal microstructural changes of grain-supported limestones

The microstructure of grainstone, grain-supported limestone, samples representing different geographic and stratigraphic intervals in Egypt were examined before and after calcination at 950°C for 0.25, 0.5, 1 and 2?h. The examination utilized are X-ray diffraction (XRD), X-ray fluorescence (XRF), transmitted light microscopy (TLM), scanning electron microscopy (SEM) and X-ray micro tomography (??-CT). Both the free lime content and reactivity of the produced quicklime were measured. The quicklime produced at 950°C for 0.25 and 0.5?h is un-reactive (R_DIN < 10) due to its low content of free lime. However, quicklime produced at 1 and 2?h conditions is highly reactive (R_DIN > 30) with variable reactivity due to the differences in the lime microfabric. The grainstones enriched in nummulites resulted in quicklime of higher reactivity than those dominated by foraminifera, peloids and miliolids. This is mainly attributed to the preservation of the intraparticle pores of the original limestone and the development of pinhole and fracture micropores. The shape of pores and not their amount is the main controlling variable in the quicklime reactivity. The grainstones enriched in fracture pores showed more reactive lime, whereas those with compact structures are less reactive post calcination.     

Sensing with boots and trousers — qualitative field observations of shallow soil moisture patterns

While soil moisture patterns can be interesting traits to investigate spatio‐temporal heterogeneity of catchments relevant for various physical processes of soil–atmosphere interaction and soil water redistribution, many of the existing methods to capture spatial patterns are time consuming, expensive or need site‐specific calibration. In this study we present a quick and inexpensive supplementary field method for classifying soil wetness in wet environments. The seven wetness classes are based on qualitative indicators, which one can touch, hear or see on the soil surface. To counter critics that such qualitative methods are considerably affected by subjectivity, we performed systematic testing of the method by taking qualitative measurements in the field with 20 non‐expert raters. We then analyzed these in terms of degree of agreement and assessed the results against gravimetric sampling and time domain reflectometry measurements. In 70% of all classifications raters agreed on the wetness class assigned to the marked sampling locations and in 95% they were not off by more than one wetness class. The seven quantitative wetness classes agreed with gravimetric and time domain reflectometry measurements, although intermediate to wet classes showed an overlap of their range whereas the driest classes showed considerable spread. Despite some potential to optimize the method, it has been shown to be a reliable supplement to existing quantitative techniques for assessing soil moisture patterns in wet environments. Copyright © 2012 John Wiley & Sons, Ltd.     

Future changes in daily summer temperature variability: driving processes and role for temperature extremes

Anthropogenic greenhouse gas emissions are expected to lead to more frequent and intense summer temperature extremes, not only due to the mean warming itself, but also due to changes in temperature variability. To test this hypothesis, we analyse daily output of ten PRUDENCE regional climate model scenarios over Europe for the 2071–2100 period. The models project more frequent temperature extremes particularly over the Mediterranean and the transitional climate zone (TCZ, between the Mediterranean to the south and the Baltic Sea to the north). The projected warming of the uppermost percentiles of daily summer temperatures is found to be largest over France (in the region of maximum variability increase) rather than the Mediterranean (where the mean warming is largest). The underlying changes in temperature variability may arise from changes in (1) interannual temperature variability, (2) intraseasonal variability, and (3) the seasonal cycle. We present a methodology to decompose the total daily variability into these three components. Over France and depending upon the model, the total daily summer temperature variability is projected to significantly increase by 20–40% as a result of increases in all three components: interannual variability (30–95%), seasonal variability (35–105%), and intraseasonal variability (10–30%). Variability changes in northern and southern Europe are substantially smaller. Over France and parts of the TCZ, the models simulate a progressive warming within the summer season (corresponding to an increase in seasonal variability), with the projected temperature change in August exceeding that in June by 2–3 K. Thus, the most distinct warming is superimposed upon the maximum of the current seasonal cycle, leading to a higher intensity of extremes and an extension of the summer period (enabling extreme temperatures and heat waves even in September). The processes driving the variability changes are different for the three components but generally relate to enhanced land–atmosphere coupling and/or increased variability of surface net radiation, accompanied by a strong reduction of cloudiness, atmospheric circulation changes and a progressive depletion of soil moisture within the summer season. The relative contribution of these processes differs substantially between models.     

CELIAS - Charge, Element and Isotope Analysis System for SOHO

The CELIAS experiment on SOHO is designed to measure the mass, ionic charge and energy of the low and high speed solar wind, of suprathermal ions, and of low energy flare particles. Through analysis of the elemental and isotopic abundances, the ionic charge state, and the velocity distributions of ions originating in the solar atmosphere, the investigation focuses on the plasma processes on various temporal and spatial scales in the solar chromosphere, transition zone, and corona. CELIAS includes 3 mass- and charge-discriminating sensors based on the time-of-flight technique: CTOF for the elemental, charge and velocity distribution of the solar wind, MTOF for the elemental and isotopic composition of the solar wind, and STOF for the mass, charge and energy distribution of suprathermal ions. The instrument will provide detailed in situ diagnostics of the solar wind and of accelerated particles, which will complement the optical and spectroscopic investigations of the solar atmosphere on SOHO. CELIAS also contains a Solar Extreme Ultraviolet Monitor, SEM, which continously measures the EUV flux in a wide band of 17 – 70 nm, and a narrow band around the 30.4 nm He II line.Principal-InvestigatorPrincipal-Investigator for data phase     

Quantifying uncertainties in projections of extremes��a perturbed land surface parameter experiment

Uncertainties in the climate response to a doubling of atmospheric CO₂ concentrations are quantified in a perturbed land surface parameter experiment. The ensemble of 108 members is constructed by systematically perturbing five poorly constrained land surface parameters of global climate model individually and in all possible combinations. The land surface parameters induce small uncertainties at global scale, substantial uncertainties at regional and seasonal scale and very large uncertainties in the tails of the distribution, the climate extremes. Climate sensitivity varies across the ensemble mainly due to the perturbation of the snow albedo parameterization, which controls the snow albedo feedback strength. The uncertainty range in the global response is small relative to perturbed physics experiments focusing on atmospheric parameters. However, land surface parameters are revealed to control the response not only of the mean but also of the variability of temperature. Major uncertainties are identified in the response of climate extremes to a doubling of CO₂. During winter the response both of temperature mean and daily variability relates to fractional snow cover. Cold extremes over high latitudes warm disproportionately in ensemble members with strong snow albedo feedback and large snow cover reduction. Reduced snow cover leads to more winter warming and stronger variability decrease. As a result uncertainties in mean and variability response line up, with some members showing weak and others very strong warming of the cold tail of the distribution, depending on the snow albedo parametrization. The uncertainty across the ensemble regionally exceeds the CMIP3 multi-model range. Regarding summer hot extremes, the uncertainties are larger than for mean summer warming but smaller than in multi-model experiments. The summer precipitation response to a doubling of CO₂ is not robust over many regions. Land surface parameter perturbations and natural variability alter the sign of the response even over subtropical regions.     

An experimental determination of chlorine isotope fractionation in acid systems and applications to volcanic fumaroles

The δ³⁷Cl values of volcanic fumarole gases and bubbling springs were measured from the Central American and the Kurile arcs. Low temperature gas samples from the Central American arc have δ³⁷Cl values generally between −2 and 2‰, whereas high-temperature fumaroles (>100 °C) range from 4 to 12‰, with several outliers. This is in contrast to the high-temperature fumaroles from the Kurile island Kudryavy which have slightly positive δ³⁷Cl values, averaging 0.8‰ (±0.6, 1σ), and from our previous work on Izu and Mariana arc samples in which the δ³⁷Cl values of fumarole and ash samples are similar to each other and negative. Assuming that the source for the high-T Central American fumaroles has typical subduction δ³⁷Cl values (−2.5 to 1‰), then there must be a large Cl isotope fractionation in the near-surface fumarolic system. The most likely fractionation mechanism for the high δ³⁷Cl values is between Cl⁻_aq − HCl(g), but published theoretical fractionation for this pair is only ∼1.5‰, insufficient to explain the large range of values observed in the fumaroles. Three experiments were undertaken in order to identify a process that could cause the wide range of δ³⁷Cl values observed in the high-temperature fumaroles. Results are the following: (1) A sub-boiling equilibration experiment between aqueous chloride and HCl gas had , in agreement with the theoretical calculations. (2) Evaporation of HCl(g) from hydrochloric acid at room temperature had fractionation in the opposite sense, with a . (3) A ‘synthetic fumarole’ gave large positive fractionations up to 9‰, with ³⁷Cl strongly partitioned into the vapor phase. The ‘fumarole’ experiments were made by bubbling dry air through boiling hydrochloric acid in an Erlenmeyer flask, and collecting the evolved HCl(g) in a second ‘downstream’ flask filled with distilled water. This extreme enrichment is likely due to a distillation process in which ³⁷Cl-enriched HCl(g) is stripped from the hydrochloric acid followed by a significant fraction of the light HCl(g) redissolving into the constantly condensing water vapor on the walls of the first flask. This distillation experiment creates a Cl isotope fractionation that is the same order of magnitude as observed in the high-temperature fumaroles in Central America. These results suggest that there must be a H₂O liquid-vapor region in the sub-surface fumarole conduit where light Cl is stripped from the HCl gas as it passes through the fumarole. Similar ³⁷Cl enrichments are expected in fossil epithermal boiling systems.     

Numerical analysis of the groundwater regime in the western Dead Sea escarpment, Israel + West Bank

Water is scarce in the semi-arid to arid regions around the Dead Sea, where water supply mostly relies on restricted groundwater resources. Due to increasing population in this region, the regional aquifer system is exposed to additional stress. This results in the continuous decrease in water level of the adjacent Dead Sea. The interaction of an increasing demand for water due to population growth and the decrease of groundwater resources will intensify in the near future. Thus, the water supply situation could worsen significantly unless sustainable water resource management is conducted. In this study, we develop a regional groundwater flow model of the eastern and southern Judea Group Aquifer to investigate the groundwater regime in the western Dead Sea drainage basin of Israel and the West Bank. An extensive geological database was developed and consequently a high-resolution structural model was derived. This structural model was the basis for various groundwater flow scenarios. The objective was to capture the spatial heterogeneity of the aquifer system and to apply these results to the southern part of the study area, which has not been studied in detail until now. As a result we analyzed quantitatively the flow regime, the groundwater mass balance and the hydraulic characteristics (hydraulic conductivity and hydraulic head) of the cretaceous aquifer system and calibrated them with PEST. The calibrated groundwater flow model can be used for integrated groundwater water management purposes in the Dead Sea area, especially within the framework of the SUMAR-Project.     

Robust flood statistics: comparison of peak over threshold approaches based on monthly maxima and TL-moments

ABSTRACT

Flood quantile estimation based on partial duration series (peak over threshold, POT) represents a noteworthy alternative to the classical annual maximum approach since it enlarges the available information spectrum. Here the POT approach is discussed with reference to its benefits in increasing the robustness of flood quantile estimations. The classical POT approach is based on a Poisson distribution for the annual number of exceedences, although this can be questionable in some cases. Therefore, the Poisson distribution is compared with two other distributions (binomial and Gumbel-Schelling). The results show that only rarely is there a difference from the Poisson distribution. In the second part we investigate the robustness of flood quantiles derived from different approaches in the sense of their temporal stability against the occurrence of extreme events. Besides the classical approach using annual maxima series (AMS) with the generalized extreme value distribution and different parameter estimation methods, two different applications of POT are tested. Both are based on monthly maxima above a threshold, but one also uses trimmed L-moments (TL-moments). It is shown how quantile estimations based on this “robust” POT approach (rPOT) become more robust than AMS-based methods, even in the case of occasional extraordinary extreme events.

Editor M.C. Acreman Associate editor A. Viglione