Linear free energy relationships for metal-ligand complexation: Monodentate binding to negatively-charged oxygen donor atoms

The analysis presented below suggests that the following equation models monodentate binding to negatively-charged oxygen donor atoms with no distinction between phenolic, carboxylic or inorganic hydroxide functional groups: log K_ML = α_O log K_HL + β_O; where K_ML is the metal-ligand formation constant, K_HL is the corresponding proton-ligand formation constant, and α_O and β_O are termed the Irving-Rossotti slope and intercept, respectively. Linear free energy relationships (LFERs) of this type are presented for 24 different metal ions complexing to negatively-charged oxygen donor atoms. Ligands selected for use in LFERs meet the following criteria: (i) they contain negatively-charged oxygen donor atoms (e.g., carboxylic acids and phenols), (ii) they are capable of only monodentate binding to metal ions, (iii) steric hindrances are not expected to influence the extent of metal-ligand binding, and (iv) the negatively-charged oxygen donor atom is the only functional group that imparts charge. The intercept of all LFERs was nearly zero for all metal ions investigated (β_O ≈ 0). The magnitude of α_O indicates the relative preference of metal binding to negatively-charged oxygen donor atoms and to the proton. Values of α_O can be used in QSARs (quantitative structure activity relationships) to estimate metal-NOM (natural organic matter) binding constants employed in the Windermere Humic Aqueous Model (WHAM) version V.     

Monitoring and predicting channel change in a free‐evolving,small Alpine river: Ridanna Creek (North East Italy)

The recent (25 years) morphodynamics of a proglacial reach of the Ridanna Creek, North‐East Italy, evolving in the absence of human constraints, has been investigated by means of an intensive field activity and of the analysis of aerial photographs. The study reach mostly displays a braided morphology, with sharp downstream variations of valley gradient, sediment size and formative conditions within the main channel. These discontinuities are associated with different processes of channel adjustment at different timescales, which have been quantified by coupling hydrological with morphological information. Several processes of channel change and variations in braiding intensity have been documented along the whole reach and highlight how a regular, weakly meandering main channel may significantly affect the morphodynamics of the braided network. A first attempt to predict the morphological instability of this main channel at the observed spatial scales through existing linear theories of curved river channels shows a good agreement with field observations. Finally, the complete hydro‐morphodynamical characterization of such an undisturbed alpine river reach can provide a relevant contribution to the definition of reference conditions for Alpine rivers required by the EU Water Framework Directive. Copyright © 2007 John Wiley & Sons, Ltd.     

A physically-based method for removing pits in digital elevation models

Spurious pits in digital elevation models (DEMs) are traditionally removed by filling depressions, often creating flat regions that lead to inaccurate estimation of landscape flow directions. In this study, a physical approach based on a simple landscape evolution model is proposed for DEM pit removal. This method, an alternative to traditional geometrical procedures, enforces more realistic slopes and flow directions on topography. The procedure is compared with the method most commonly used in the literature and distributed with commercial GIS software where, generally, elevations of a depression are increased up to the lowest value among neighbouring cells. Several tests are performed and parameters sensitivity is carried out in order to demonstrate the performance of the proposed model as compared to traditional methods.     

Imposex levels and concentrations of organotin compounds (TBT and its metabolites) in Nassarius nitidus from the Lagoon of Venice

Specimens of Nassarius nitidus were collected in seven stations of the Venice Lagoon to assess the levels of tributyltin (TBT) and its metabolites monobutyltin and dibutyltin in the tissues and monitor their effect on organisms, in particular the phenomenon of imposex (superimposition of male sexual characteristics on females). The following values of population indices were found: vas deferens sequence: 1.2 ± 0.7–4.0 ± 0.5; relative penis length: 6–47%. The least impacted station was situated in the northern part of the Lagoon, where females without imposex were found and Butyltin (BuTs) concentrations in the organisms (average sum of BuTs = 43 ± 14 ng Sn g⁻¹ w.) were significantly lower than in the other stations (range of average sum of BuTs: 101 ± 22–217 ± 27 ng Sn g⁻¹ d.w.). Population indices were found to be related to the TBT content in the tissues. In particular VDSI had a significant logarithmic correlation: r = 0.95, n = 8, p < 0.05.     

雷击火灾现场痕迹物证的鉴识方法

对雷击火灾现场痕迹物证的提取方法及提取部位进行了论述.根据火灾现场雷击痕迹物证的特点,应采用剩磁检测和金相分析的方法进行雷击火灾的技术鉴定,结合实际火灾案例论述了对利用剩磁检测方法和应用金相分析方法鉴别雷击火灾痕迹物证的原理和判据;分析了雷电的种类及引发火灾的机理,归纳总结了雷击引发火灾的主要原因,并提出了预防雷击火灾的措施.     

Comment on “Neutrino oscillations in the early universe: how can large lepton asymmetry be generated?” [Astropart. Phys. 14 (2000) 79–90]

We comment on the recent paper by A.D. Dolgov, S.H. Hansen, S. Pastor and D.V. Semikoz (DHPS) [Astropart. Phys. 14 (2000) 79] on the generation of neutrino asymmetries from active–sterile neutrino oscillations. We demonstrate that the approximate asymmetry evolution equation obtained therein is an expansion, up to a minor discrepancy, of the well-established static approximation equation, valid only when the supposedly new higher order correction term is small. In the regime where this so-called “back-reaction” term is large and artificially terminates the asymmetry growth, their evolution equation ceases to be a faithful approximation to the quantum kinetic equations simply because pure Mikheyev–Smirnov–Wolfenstein (MSW) transitions have been neglected. At low temperatures the MSW effect is the dominant asymmetry amplifier. Neither the static nor the DHPS approach contains this important physics. Therefore we conclude that the DHPS results have sufficient veracity at the onset of explosive asymmetry generation, but are invalid in the ensuing low temperature epoch where MSW conversions are able to enhance the asymmetry to values of order 0.2–0.37. DHPS do claim to find a significant final asymmetry for very large δm² values. However, for this regime the effective potential they employed is not valid.     

Nutrients, sea level and tectonics: constrains for the facies architecture of a Miocene carbonate ramp in central Italy

ABSTRACT In the western part of the central Apennines, Lower–Middle Miocene carbonates were deposited on a tropical–subtropical carbonate ramp. They record two long-term cycles, the first of which is illustrated in this paper. Between 21 and 17.5 Ma, Miocene carbonates, paraconformably overlying the Cretaceous limestones, record a transgressive event during a time of global (2nd order) sea-level lowstand. It is postulated that this deviation is related to an increase in tectonic subsidence. Between 17.5 Ma and 16–15 Ma, with a progressive relative sea-level rise, the inner–middle ramp facies belt stepped back, whereas the bryozoan-dominated outer ramp facies belt stepped back but simultaneously prograded. This bloom of suspension-feeding organisms is interpreted to reflect an increased nutrient availability, hence a change from oligotrophic to eutrophic conditions. Strontium-isotope dates constrain correlation of the second phase with a eutrophic event possibly linked to the influence of the neighbouring Apenninic accretionary wedge and foredeep system.     

In-flight Performance of the Advanced Camera for Surveys CCDs

The Advanced Camera for Surveys (ACS), installed in the Hubble Space telescope in March 2002, will significantly extend HST's deep, survey imaging capabilities. ACS has met, or exceeded, all of its key performance specifications. In this paper we briefly review the in-flight performance of the instrument's CCD detectors and preview early ACS science observations. This revised version was published online in July 2006 with corrections to the Cover Date.     

Metal speciation and environmental impact on sandy beaches due to El Salvador copper mine, Chile

Several coastal rocky shores in northern Chile have been affected by the discharges of copper mine tailings. The present study aims to analyze the chemical speciation of heavy metals in relation to the diversity of sessile species in the rocky intertidal benthic community on the northern Chilean coast, which is influenced by the presence of copper mine tailings. In particular, the chemical forms of Cd, Cu, Fe, Mn, Ni, Pb and Zn in beach sediment samples collected in the area influenced by El Salvador mine tailings were studied using a sequential chemical extraction method. In general, all the elements present a maximum concentration in the area near the actual discharge point (Caleta Palito). With regard to Cu and Mn, the concentrations range between 7.2-985 and 746-22,739 microg/g respectively, being lower than background levels only in the control site of Caleta Zenteno. Moreover, the correlation coefficients highlight that Fe, Mn and Ni correlate significantly and positively in the studied area, showing a possible common, natural origin, whilst Cu shows a negative correlation with Fe, Mn and Ni. It could be possible that Cu has an anthropogenic origin, coming from mining activity in the area. Cd, Fe, Mn, Ni, Pb and Zn are mostly associated with the residual phase, whilst Cu presents a different speciation pattern, as resulted from selective extractions. In fact, Cu is highly associated with organic and exchangeable phases in contaminated localities, whilst it is mainly bound to the residual phase in control sites. Moreover, our results, compared to local biological diversity, showed that those sites characterized by the highest metal concentrations in bioavailable phase had the lowest biodiversity.     

Thermal expansion and phase transitions in åkermanite and gehlenite

Thermal expansion has been measured by laboratory and synchrotron X-ray powder diffraction for end-member åkermanite (ak, Ca₂MgSi₂O₇) and gehlenite (ge, Ca₂Al₂SiO₇) in the range 20–1,500 K. In ak in the range 340–390 K, there is a negative linear thermal expansion in [001] direction. This is related to the phase transition from an incommensurate modulated structure (IC) to a normal one (N). The volumetric mean thermal expansion coefficients for ak and ge, obtained with a linear fit of the experimental data in the temperature range 298–1,400 K, are respectively 32.1×10^–6 and 28.3×10^–6 K^–1 . The variation of the c/a ratio with temperature, due to different thermal expansion along the crystallographic axes, can be related to the different behaviour of the tetrahedral layers in the N and IC phases. Analysis of the variation of the superstructure peaks intensity across the phase transition confirms the tricritical behaviour of the IC/N transition in ak.