In situ Raman observation of the crystallization in NaNO3–Na2SO4–H2O solution droplets

Several double salts have been detected in building materials and most of these salts are incongruently soluble compounds. In contrast to single salts, however, no systematic investigations of the crystallization behavior and deleterious effects of incongruently soluble double salts exist. To assess the damage potential of these salts, a systematic investigation of their highly complex behavior is desirable. This paper deals with the crystallization behavior of various solids in the ternary mixed NaNO₃–Na₂SO₄ system including the formation of the double salt darapskite, Na₃NO₃SO₄·H₂O. The crystallization sequence during droplet evaporation experiments at room conditions was determined using Raman and polarization microscopy. The basic idea of this research is to use deviations of the crystallization sequence of a salt or a mixed salt solution from the equilibrium pathway as an indicator to detect the degree of supersaturation. The observed crystallization pathway includes the formation of the metastable phases Na₂SO₄(III), Na₂SO₄(V) and darapskite. The experimental observations are discussed on the basis of the NaNO₃–Na₂SO₄–H₂O phase diagram and the results provide evidence for crystal growth from highly supersaturated solutions in both systems. If the crystals growing under these conditions are confined, these supersaturations result in substantial crystallization pressures.     

Oxygen and hydrogen isotope fractionation in serpentine-water and talc-water systems from 250 to 450 °C, 50 MPa

Oxygen and hydrogen isotope fractionation factors in the talc-water and serpentine-water systems have been determined by laboratory experiment from 250 to 450 °C at 50 MPa using the partial exchange technique. Talc was synthesized from brucite + quartz, resulting in nearly 100% exchange during reaction at 350 and 450 °C. For serpentine, D-H exchange was much more rapid than ¹⁸O-¹⁶O exchange when natural chrysotile fibers were employed in the initial charge. In experiments with lizardite as the starting charge, recrystallization to chrysotile enhanced the rate of ¹⁸O-¹⁶O exchange with the coexisting aqueous phase. Oxygen isotope fractionation factors in both the talc-water and serpentine-water systems decrease with increasing temperature and can be described from 250 to 450 °C by the relationships: 1000 ln  = 11.70 × 10⁶/T² − 25.49 × 10³/T + 12.48 and 1000 ln  = 3.49 × 10⁶/T² − 9.48 where T is temperature in Kelvin. Over the same temperature interval at 50 MPa, talc-water D-H fractionation is only weakly dependent on temperature, similar to brucite and chlorite, and can be described by the equation: 1000 ln = 10.88 × 10⁶/T² − 41.52 × 10³/T + 5.61 where T is temperature in Kelvin. Our D-H serpentine-water fractionation factors calibrated by experiment decrease with temperature and form a consistent trend with fractionation factors derived from lower temperature field calibrations. By regression of these data, we have refined and extended the D-H fractionation curve from 25 to 450 °C, 50 MPa as follows: 1000 ln  = 3.436 × 10⁶/T² − 34.736 × 10³/T + 21.67 where T is temperature in Kelvin. These new data should improve the application of D-H and ¹⁸O-¹⁶O isotopes to constrain the temperature and origin of hydrothermal fluids responsible for serpentine formation in a variety of geologic settings.     

N and O isotope effects during nitrate assimilation by unicellular prokaryotic and eukaryotic plankton cultures

In order to provide biological systematics from which to interpret nitrogen (N) and oxygen (O) isotope ratios of nitrate (¹⁵N/¹⁴N, ¹⁸O/¹⁶O, respectively) in the environment, we previously investigated the isotopic fractionation of nitrate during its assimilation by mono-cultures of eukaryotic algae (Granger et al., 2004). In this study, we extended our analysis to investigate nitrate assimilation by strains of prokaryotic plankton. We measured the N and O isotope effects, ¹⁵ε and ¹⁸ε, during nitrate consumption by cultures of prokaryotic strains and by additional eukaryotic phytoplankton strains (where ε is the ratio of reaction rate constants of the light vs. heavy isotopologues, ^lightk and ^heavyk; ε = ^lightk/^heavyk − 1 × 1000, expressed in per mil). The observed ¹⁵ε ranged from 5‰ to 8‰ among eukaryotes, whereas it did not exceed 5‰ for three cyanobacterial strains, and was as low as 0.4‰ for a heterotrophic α-protoeobacterium. Eukaryotic phytoplankton fractionated the N and O isotopes of nitrate to the same extent (i.e., ¹⁸ε ∼ ¹⁵ε). The ¹⁸ε:¹⁵ε among the cyanobacteria was also ∼1, whereas the heterotrophic α-proteobacterial strain, which showed the lowest ¹⁵ε, between 0.4‰ and 1‰, had a distinct ¹⁸ε:¹⁵ε of ∼2, unlike any plankton strain observed previously. Equivalent N vs. O isotope discrimination is thought to occur during internal nitrate reduction by nitrate reductase, such that the cellular efflux of the fractionated nitrate into the medium drives the typically observed ¹⁸ε:¹⁵ε of ∼1. We hypothesize that the higher in the ¹⁸ε:¹⁵ε of the α-proteobacterium may result from isotope discrimination by nitrate transport, which is evident only at low amplitude of ε. These observations warrant investigating whether heterotrophic bacterial assimilation of nitrate decreases the community isotope effects at the surface ocean.     

Tsunamis as geological agents

When a tsunami wave series approaches and interacts with a coast, the consequent passage shorewards of great volumes of water and their invasion of the land, especially within bays and up river valleys, results in the disturbance of existing sediment and the removal seawards of land debris and coastal and shallow‐water marine sediments. Tsunami action builds up sequences of peculiar sediments in shallow water; it at least assists in the formation and maintenance of submarine canyons and, through them, produces turbidity currents of a particularly powerful kind. Tsunami action may explain many puzzling sedimentary phenomena, for example, sudden and drastic changes in near‐shore bathymetry; the formation of chaotic sediments such as some paraconglomerates and edgewise conglomerates. It offers solutions to problems arising from the study of turbiditic sequences, both modern and ancient.     

The Upper Middle Rhine Valley as a risk area

The Upper Middle Rhine Valley, granted the status of a World Heritage site, is well known for its unique inner narrow valley of Quaternary age with its historical legacy of numerous medieval castles and old towns. Less known is that this has always been a risk area of floods and gravitative mass movements. Up to the recent past, mainly ice floods caused enormous damage. The inhabitants of the valley were well aware that they lived in a risk area, but they had learned to handle the flood hazard. With the demise of ice floods over the last 40 years, due to climate change and because of the additional heating of the river water by power plants, the awareness of flood hazards has been much diminished, in contrast to that of potential damage by rockfalls and landslides which were also much feared in the past, though at the local level only. Still in the people’s memory is the Kaub catastrophe of March 10, 1876, when 28 persons were killed by a landslide. Nowadays, even minor rockfalls are a major threat, as they will affect the much-used traffic lines on both banks of the river, in particular the railroads. Therefore, since 2002, on behalf of German Rail (Deutsche Bahn, DB), all problematic slopes have been protected by costly steel-ring nets, although they are an aesthetic problem by UNESCO standards. The feeling of absolute safety created among the public is only subjective, though, as planners are well aware of. Moreover, the impact of modern climate change on slope stability is nearly unknown. Therefore, it is still necessary to develop a risk map for the narrow valley, with emphasis on gravitational hazards.     

The role of prior model calibration on predictions with ensemble Kalman filter

This paper, based on a real world case study (Limmat aquifer, Switzerland), compares inverse groundwater flow models calibrated with specified numbers of monitoring head locations. These models are updated in real time with the ensemble Kalman filter (EnKF) and the prediction improvement is assessed in relation to the amount of monitoring locations used for calibration and updating. The prediction errors of the models calibrated in transient state are smaller if the amount of monitoring locations used for the calibration is larger. For highly dynamic groundwater flow systems a transient calibration is recommended as a model calibrated in steady state can lead to worse results than a noncalibrated model with a well-chosen uniform conductivity. The model predictions can be improved further with the assimilation of new measurement data from on-line sensors with the EnKF. Within all the studied models the reduction of 1-day hydraulic head prediction error (in terms of mean absolute error [MAE]) with EnKF lies between 31% (assimilation of head data from 5 locations) and 72% (assimilation of head data from 85 locations). The largest prediction improvements are expected for models that were calibrated with only a limited amount of historical information. It is worthwhile to update the model even with few monitoring locations as it seems that the error reduction with EnKF decreases exponentially with the amount of monitoring locations used. These results prove the feasibility of data assimilation with EnKF also for a real world case and show that improved predictions of groundwater levels can be obtained.     

Meteorological excitation of the annual polar motion

Summary. Numerous studies have indicated that the annual term in the polar motion cannot be explained in any detail by meteorological/hydrological excitation and no reasonable alternative excitations have been put forward. Part of the problem has been that the hydrostatic adjustment of the oceans to the atmospheric pressure changes has traditionally been computed using the inverse barometer approach. This approach does not properly model the gravitational interaction between the atmosphere and oceans, and the inverse barometer theory is modified in this paper to account for this properly. The information necessary to compute the ocean tide and polar excitation caused by any change in the atmospheric pressure pattern is presented. The results of the application of this theory to two global atmospheric pressure data sets are examined and compared to results of other workers.
It is concluded that the atmosphere is observed well enough to answer the question of the annual excitation of polar motion and it is argued that the ground water excitation is the component with the largest error and remains the chief obstacle to the successful solution of this problem.