Rigorous characterization of oxygen vacancies in ionic oxides

Charged and neutral oxygen vacancies in the bulk and on perfect and defective surfaces of MgO are characterized as quantum-mechanical subsystems chemically bonded to the host lattice and containing most of the charge left by the removed oxygens. Attractors of the electron density appear inside the vacancy, a necessary condition for the existence of a subsystem according to the atoms in molecules theory. The analysis of the electron localization function also shows attractors at the vacancy sites, which are associated to a localization basin shared with the valence domain of the nearest oxygens. This polyatomic superanion exhibits chemical trends guided by the formal charge and the coordination of the vacancy. The topological approach is shown to be essential to understand and predict the nature and chemical reactivity of these objects. There is not a vacancy but a coreless pseudoanion that behaves as an activated host oxygen.

First principles LDA+U and GGA+U study of cerium oxides: Dependence on the effective U-parameter

The electronic structure and properties of cerium oxides (CeO2 and Ce2O3) have been studied in the framework of the LDA+U and GGA(PW91)+U implementations of density functional theory. The dependence of selected observables of these materials on the effective U parameter has been investigated in detail. The examined properties include lattice constants, bulk moduli, density of states, and formation energies of CeO2 and Ce2O3. For CeO2, the LDA+U results are in better agreement with experiment than the GGA+U results whereas for the computationally more demanding Ce2O3 both approaches give comparable accuracy. Furthermore, as expected, Ce2O3 is much more sensitive to the choice of the U value. Generally, the PW91 functional provides an optimal agreement with experiment at lower U energies than LDA does. In order to achieve a balanced description of both kinds of materials, and also of nonstoichiometric CeO2¿x phases, an appropriate choice of U is suggested for LDA+U and GGA+U schemes. Nevertheless, an optimum value appears to be property dependent, especially for Ce2O3. Optimum U values are found to be, in general, larger than values determined previously in a self-consistent way.

Ionic-covalent transition in titanium oxides

The nature of the chemical bond in three titanium oxides of different crystal structure and different formal oxidation state has been studied by means of the ab initio cluster-model approach. The covalent and ionic contributions to the bond have been measured from different theoretical techniques. All the analysis is consistent with an increasing of covalence in the TiO, Ti2O3, and TiO2 series as expected from chemical intuition. Moreover, the use of the ab initio cluster-model approach combined with different theoretical techniques has permitted us to quantify the degree of ionic character, showing that while TiO can approximately be described as an ionic compound, TiO2 is better viewed as a rather covalent oxide.

Estimation of soil nitrate in the spring as a basis for adjustment of nitrogen fertiliser rates

Selostus: Maassa olevan nitraattitypen arviointi simulointimallin avulla

Effects of riparian vegetation removal on nutrient retention in a Mediterranean stream

We examined the effects of riparian vegetation removal on algal dynamics and stream nutrient retention efficiency by comparing NH4-N and PO4-P uptake lengths from a logged and an unlogged reach in Riera Major, a forested Mediterranean stream in northeastern Spain. From June to September 1995, we executed 6 short-term additions of N (as NH4Cl) and P (as Na2HPO4) in a 200-m section to measure nutrient uptake lengths. The study site included 2 clearly differentiated reaches in terms of canopy cover by riparian trees: the first 100 m were completely logged (i.e., the logged reach) and the remaining 100 m were left intact (i.e., the shaded reach). Trees were removed from the banks of the logged reach in the winter previous to our sampling. In the shaded reach, riparian vegetation was dominated by alders (Alnus glutinosa). The study was conducted during summer and fall months when differences in light availability between the 2 reaches were greatest because of forest canopy conditions. Algal biomass and % of stream surface covered by algae were higher in the logged than in the shaded reach, indicating that logging had a stimulatory effect on algae in the stream. Overall, nutrient retention efficiency was higher (i.e., shorter uptake lengths) in the logged than in the shaded reach, especially for PO4-P. Despite a greater increase in PO4-P retention efficiency relative to that of NH4-N following logging, retention efficiency for NH4-N was higher than for PO4-P in both study reaches. The PO4-P mass-transfer coefficient was correlated with primary production in both study reaches, indicating that algal activity plays an important role in controlling PO4-P dynamics in this stream. In contrast, the NH4-N mass-transfer coefficient showed a positive relation-ship only with % of algal coverage in the logged reach, and was not correlated with any algal-related parameter in the shaded reach. The lack of correlation with algal production suggests that mechanisms other than algal activity (i.e., microbial heterotrophic processes or abiotic mechanisms) may also influence NH4-N retention in this stream. Overall, this study shows that logging disturbances in small shaded streams may alter in-stream ecological features that lead to changes in stream nutrient retention efficiency. Moreover, it emphasizes that alteration of the tight linkage between the stream channel and the adjacent riparian zone may directly and indirectly impact biogeochemical processes with implications for stream ecosystem functioning.

Undersowing Italian ryegrass diminishes nitrogen leaching from spring barley

Selostus: Italian raiheinä aluskasvina vähentää typen huuhtoutumista ohranviljelyssä

DNA extraction using the QIAsymphony: Evaluation of PCR inhibitor removal

The goal of this study was to compare the quantity and purity of DNA extracted from biological tracesusing the QIAsymphony robot with that of the manual QIAamp DNA mini kit currently in use in ourlaboratory. We found that the DNA yield of robot was 1.6-3.5 times lower than that of the manualprotocol. This resulted in a loss of 8% and 29% of the alleles correctly scored when analyzing 1/400 and 1/800 diluted saliva samples, respectively. Specific tests showed that the QIAsymphony was at least 2-16times more efficient at removing PCR inhibitors. The higher purity of the DNA may therefore partlycompensate for the lower DNA yield obtained. No case of cross-contamination was observed amongsamples. After purification with the robot, DNA extracts can be automatically transferred in 96-wellsplates, which is an ideal format for subsequent RT-qPCR quantification and DNA amplification. Lesshands-on time and reduced risk of operational errors represent additional advantages of the robotic platform.

Carbohydrate and nitrogen stores in Festuca paniculata under mowing explain dominance in subalpine grasslands

Cessation of traditional management threatens semi-natural grassland diversity through the colonisation or increase of competitive species adapted to nutrient-poor conditions. Regular mowing is one practice that controls their abundance. This study evaluated the ecophysiological mechanisms limiting short- and long-term recovery after mowing for Festuca paniculata, a competitive grass that takes over subalpine grasslands in the Alps following cessation of mowing. We quantified temporal variations in carbon (C) and nitrogen (N) content, starch, fructan and total soluble sugars in leaves, stem bases and roots of F. paniculata during one growth cycle in mown and unmown fields and related them to the dynamics of soil mineral N concentration and soil moisture. Short-term results suggest that the regrowth of F. paniculata following mowing might be N-limited, first because of N dilution by C increments in the plant tissue, and second, due to low soil mineral N and soil moisture at this time of year. However, despite short-term effects of mowing on plant growth, C and N content and concentration at the beginning of the following growing season were not affected. Nevertheless, total biomass accumulation at peak standing biomass was largely reduced compared to unmown fields. Moreover, lower C storage capacity at the end of the growing season impacted C allocation to vegetative reproduction during winter, thereby dramatically limiting the horizontal growth of F. paniculata tussocks in the long term. We conclude that mowing reduces the growth of F. paniculata tussocks through both C and N limitation. Such results will help understanding how plant responses to defoliation regulate competitive interactions within plant communities.

Response of P, K, Mg and NO‚́ƒ-N contents of carrots to irrigation, soil compaction, and nitrogen fertilisation

Selostus: Maan tiiviyden, sadetuksen ja typpilannoituksen vaikutus porkkanan kivennäisainepitoisuuteen ja ravinteiden ottoon sekä nitraatin kertymiseen

Field Measurements of Plow Loads During Ice Removal Operations, HR-334, 1993

One of the more severe winter hazards is ice or compacted snow on roadways. While three methods are typically used to combat ice (salting, sanding and scraping), relatively little effort has been applied to improve methods of scraping ice from roads. In this project, a new test facility has been developed, comprising a truck with an underbody blade, which has been instrumented such that the forces to scrape ice from a pavement can be measured. A test site has been used, which is not accessible to the public, and ice covers have been sprayed onto the pavement and subsequently scraped from it, while the scraping loads have been recorded. Three different cutting edges have been tested for their ice scraping efficiency. Two of the blades are standard (one with a carbide insert, the other without) while the third blade was designed under the SHRP H-204A project. Results from the tests allowed two parameters to be identified. The first is the scraping efficiency which is the ratio of vertical to horizontal force. The lower this ratio, the more efficiently ice is being removed. The second parameter is the scraping effectiveness, which is related (in some as yet unspecified manner) to the horizontal load. The higher the horizontal load, the more ice is being scraped. The ideal case is thus to have as high a horizontal load as possible, combined with the lowest possible vertical load. Results indicate that the SHRP blade removed ice more effectively than the other two blades under equivalent conditions, and furthermore, did so with greater efficiency and thus more control. Furthermore, blade angles close to 0 deg provide for the most efficient scraping for all three blades. The study has shown that field testing of plow blades is possible in controlled situations, and that blades can be evaluated using this system. The system is available for further tests as are deemed appropriate.