Limitations of the potentiometric titration technique in determining the proton active site density of goethite surfaces

Density of proton active surface sites at mineral surfaces is a property of fundamental importance in equilibrium modeling of surface complexation reactions. In this article, methods for an experimental determination of these sites at the surface of α-FeOOH (goethite) are explored. It is shown that previously obtained saturation data of goethite with respect to protons do not yield a site density that can be considered as an intrinsic sorbent property: the results are below crystallographically expected values and values for different ionic media in terms of composition and concentration yield different numbers—for example, chloride would yield higher values than nitrate at the same concentration, and higher electrolyte concentration would favor higher apparent maxima. Although site saturation might be explained by electrostatic repulsion, which is more efficient at high electrolyte concentration or for certain ions, further independent experimental results show that no saturation occurs on goethite down to ph ≡ −log[H⁺] = 2.2 and possibly to ph = 1.0 in 0.6 M NaCl. For those very low pH values, the experimental charging curve was obtained by coulometric back titration (using the Gran plot) or titrations with tris (hydroxymethyl)-aminomethane of the supernatant of acidified goethite suspension. These experimental data are to our knowledge the first high quality data at such low pHs. However, small errors in the determination of proton concentrations (1%) are shown to strongly affect the shape of the charging curve for ph < 2. Furthermore, goethite dissolution (proton consumption and iron reduction in coulometric titrations) and liquid junction effects interfere at low ph, hampering the straightforward application of coulometric Gran titrations over the whole pH range. From these experiments, it can nonetheless be ascertained that a minimum of 2.5 protons/nm² can be adsorbed at the goethite surface from the point of zero charge (ph 9.4) to pH 0.9. Although these studies are restricted to goethite, those studies in which titrations with excess acid and base have been used for the determination of proton active site concentrations of sorbents should be reconsidered.     

Rapid and rhythmic ice sheet fluctuations in western Scandinavia 15-40 Kya–a review

The onshore record of Middle to Late Weichselian sediments and glacial history in Norway indicates a succession of four major ice advances alternating with rapid, considerable ice recessions and interstadial conditions. During all the glacial advances the ice sheet expanded from onshore/inland positions to the shelf areas. The basis for visualizing these variations in glaciation curves constructed along nine transects from inland to shelf, and for interpretation of the palaeoclimatic history, is the regional Quaternary stratigraphy, more than 300 datings, fossil content and some palaeomagnetic data. The methods applied in recent years for AMS radiocarbon dating of glacial sediments with low organic carbon content have given promising results with respect to accuracy and precision, and the results of such datings were an important tool for our reconstructions and for timing of the ice oscillations. The rapid and rhythmic ice fluctuations, as reconstructed in our new model, have been fairly synchronous in most parts of Norway. Ice advances commenced and culminated at 40, 30-28, 24-21 and 18-15 (¹⁴C) Kya. We describe three intervening interstadials from inland sites: Hattfjelldal I, Hattfjelldal II and Trofors. Our stratigraphical record also includes many indications of high, pre-Holocene, relative sea levels, suggesting a considerable glacioisostatic depression of western Scandinavia during the interstadials. In our glaciation model we suggest that, in addition to precipitation, the mountainous fjord and valley topography, glacial isostasy and relative sea level changes were probably more important for the size of the glacial fluctuations than were air temperature changes.     

Moving Code in Spatial Data Infrastructures – Web Service Based Deployment of Geoprocessing Algorithms

This article proposes a concept for offering complex geoprocessing functionality in service‐based Spatial Data Infrastructures (SDI). Today, geoprocessing in SDI is typically realized in a data driven manner. Applying the suggested “moving code” approach in a case study in the field of Spatial Decision Support proves its applicability. The proposed solution is analyzed and assessed in terms of gained efficiency, performance behavior and support for distributed development of geoprocessing functionality. In data and computation intensive SDI applications the deployment of moving code proves to be beneficial.     

An evaluation of measures for quantifying map information

A real-time map must not contain too much information. Therefore, we need measures of map information that could be guidelines for the selection of data layers and the real-time generalisation process. In this paper we evaluate measures of the amount of information and the distribution of information. The evaluation is performed by (1) defining measures, (2) implementing the measures, (3) computing the measures for some test maps, and finally (4) comparing the values of the measures with human judgement of the map information. For amount of information, we found that the measures number of objects, number of points and object line length had better correspondence with human judgement than object area. We also found that measures based on the size of Voronoi regions of objects (respectively points) can be used for identifying the distribution of information. The results are based on the testing of only building objects. Future work should extend the test, using all object types.     

Spatial variability of soil water content in the covered catchment at Gårdsjön,Sweden

The spatial variability of soil water content was investigated for a 6300 m² covered catchment on the Swedish west coast. The catchment podzol soil is developed in a sandy—silty till with a mean depth of 43 cm and the dominant vegetation is Norway spruce. The acid precipitation is removed by a plastic roof and replaced with lake water irrigated under the tree canopies. On two occasions, in April and May 1993, TDR measurements were made at 57–73 points in the catchment using 15 and 30 cm long vertically installed probes. The water content pattern at the two dates, which occurred during a relatively dry period, were similar. The range of water content was large, from 5 to 60%. In May 1993 measurements also were made in areas of 10 × 10 m, 1 × 1 m and 0·2 × 0·2 m. The range and standard deviation for the 10 × 10 m area, which apart from a small-scale variability in soil hydraulic properties and fine root distribution also had a heterogeneous micro- and macro-topography, was similar to the range and standard deviation for the catchment. The 1 × 1 m and 0·2 × 0·2 m areas had considerably lower variability. Semi-variogram models for the water content had a range of influence of about 20 m. If data were paired in the east-–west direction the semi-variance reflected the topography of the central valley and had a maximum for data pairs with internal distances of 20–40 m. The correlation between soil water content and topographic index, especially when averaged for the eight topographically homogeneous subareas, indicated the macro-topography as the cause of a large part of the water content variability.     

Phase transitions of α-quartz at elevated temperatures under dynamic compression using a membrane-driven diamond anvil cell: Clues to impact cratering?

Coesite and stishovite are high-pressure silica polymorphs known to have been formed at several terrestrial impact structures. They have been used to assess pressure and temperature conditions that deviate from equilibrium formation conditions. Here we investigate the effects of nonhydrostatic, dynamic stresses on the formation of high-pressure polymorphs and the amorphization of α-quartz at elevated temperatures. The obtained disequilibrium states are compared with those predicted by phase diagrams derived from static experiments under equilibrium conditions. We analyzed phase transformations starting with α-quartz in situ under dynamic loading utilizing a membrane-driven diamond anvil cell. Using synchrotron powder X-ray diffraction, the phase transitions of SiO₂ are identified up to 77.2 GPa and temperatures of 1160 K at compression rates ranging between 0.10 and 0.37 GPa s⁻¹. Coesite starts forming above 760 K in the pressure range between 2 and 11 GPa. At 1000 K, coesite starts to transform to stishovite. This phase transition is not completed at 1160 K in the same pressure range. Therefore, the temperature initiates the phase transition from α-quartz to coesite, and the transition from coesite to stishovite. Below 1000 K and during compression, α-quartz becomes amorphous and partially converts to stishovite. This phase transition occurs between 25 and 35 GPa. Above 1000 K, no amorphization of α-quartz is observed. High temperature experiments reveal the strong thermal dependence of the formation of coesite and stishovite under nonhydrostatic and disequilibrium conditions.     

Oxidative damage in rainbow trout caged in a polluted river

Sewage treatment works (STWs) are a common source of chemicals entering into the aquatic environment. In order to assess effects of these effluents on oxidative stress parameters in aquatic organisms, we caged rainbow trout at five sites: upstream, near an STW effluent, and three sites downstream in the river Viskan in western Sweden for 14 days during autumn, 2006. We then measured protein carbonyls in plasma as well as 20S proteosome activity and lipid peroxidation products, i.e. MDA and 4-HNE, in liver samples. Levels of both lipid and protein oxidative damage products were elevated in fish caged near the STW effluent while 20S activity showed no differences. This argues that complex mixtures of chemicals entering into the aquatic environment do have deleterious effects on fish. Additionally, oxidative stress parameters can serve as a biomarker in aquatic organisms.     

Black-body temperature of a closed Universe

In a closed gravitationally-bound Universe we are subject to an inward accelerationa ₀. One consequence of this acceleration is that matter will radiate and create a black-body spectrum throughout the Universe. Using the valuea ₀=7.623×10^–12 ms^–2 and a radiation formula from a previously-described cosmological model (Wåhlin, 1981), we obtain a black-body temperature of 2.766 K.