Structural characterization of new malvidin 3-glucoside-catechin aryl/alkyl-linked pigments

The condensation reaction between malvidin 3-glucoside and catechin mediated by isobutyraldehyde, benzaldehyde, and isovaleraldehyde was conducted in model solutions at two pH values (1.5 and 3.2). The formation of new alkyl/aryl-linked adducts corresponding to the structures malvidin 3-glucoside-isobutylcatechin, malvidin 3-glucoside-benzylcatechin, and malvidin 3-glucoside-3-methylbutylcatechin was respectively observed from each aldehyde. The structural characterization of these new structures has been elucidated by 1D and 2D NMR, mass spectrometry, and UV-vis techniques. These new adducts showed the same lambda(max) in the visible region at 540 nm, which is bathochromically shifted 15 nm when compared with the original anthocyanin (lambda(max) = 525 nm).     

Higher taxa surrogates of spider (Araneae) diversity and their efficiency in conservation

A number of alternative approaches have been suggested during recent years to predict species richness of a given taxa, while retaining information on the identities of the observed individuals. Such information can be extremely useful for choosing conservation priority areas, either by using simple richness values or, preferentially, by considering the complementarity of potential sites. Among the most popular approaches is the use of higher taxa surrogates. Both family and genus richness are here tested in their ability to predict the number of spider (Araneae) species independently of sampling effort, geographical location and type of habitat. We use data from three Portuguese protected areas as a test case. Genus richness is considered a good surrogate of species richness, despite some caution being needed regarding the comparison of sites with considerably different sampling effort, the same not happening with families. Only genera are also found to be reliable either for ranking sites according to taxa richness or for determining near-minimum sets of sites for conservation. We therefore recommend surrogacy at this taxonomic level as a promising approach for the prediction of spider species richness or evaluation and ranking of areas according to their conservation importance. The reached conclusions should uphold for Portugal and the entire Mediterranean region.     

Differential Complexation between Zn2+ and Cd2+ with Fulvic Acid: A Computational Chemistry Study

Fulvic (FA) and humic acids (HA) from the solubilization of organic matter are significant agents of the complex of metallic ions in soil and water. Cadmium ions are important natural water pollutants which are discharged along with electroplating and zinc metallurgy liquid wastes, zinc and cadmium being always associated with isomorphic substitution. In this paper we study the complexes formed by Zn²⁺ and Cd²⁺ with fulvic acids, using computational chemistry. We carried out relative free energy calculations using a thermodynamic cycle and Free Energy Pertubation (FEP) and Density Functional Theory (DFT-B3LYP/6-31G**) methods. We also computed the interaction energies between orbitals from Natural Bond Order (NBO) calculations. Cd-FA complexes, octahedral with four water molecules in the coordination sphere are more stable than Zn-FA complexes, tetrahedral with two water molecules. This means that FA should be a better ligand for Cd²⁺ bioavailability and toxicity in natural aquatic environments.     

Effects of phenolic propyl esters on the oxidative stability of refined sunflower oil

The oxidative stability of refined sunflower oil in the presence and in the absence of propyl caffeate (PC), propyl hydrocaffeate (PHC), propyl ferulate (PF), and propyl isoferulate (PI) has been evaluated according to the Rancimat method. The antioxidant activity of the phenolic derivatives was compared with that obtained with native [alpha-tocopherol (alpha-TOH)] and synthetic [propyl gallate (PG)] antioxidants. The results allow the establishment of a decreasing order of antioxidant power: PG > PHC > PC > alpha-TOH > PI > PF. The oxidative stability was improved neither by the addition of PF nor by a supplement of alpha-TOH. Moreover, a positive antioxidant effect was obtained for PC that was placed between those of alpha-TOH and PG. The antioxidant activity of PHC was higher than that of its analogue (PC). A dose-dependent effect was observed for PG, PHC, and PC. A chain-breaking mechanism was proposed for the antioxidant activity of propyl phenolic esters because the same ranking order of efficacy was obtained for their antiradical activities evaluated by using the 2,2-diphenyl-1-picrylhydrazyl radical method.     

Soil pH on mobility of imazaquin in oxisols with positive balance of charges

The influence of soil pH on the leaching potential of the ionizable herbicide imazaquin was assessed on the profile of two highly weathered soils having a net positive charge in the B horizon, in contrast to a soil having a net negative charge in the whole profile, using packed soil column experiments. Imazaquin leached to a large extent and faster at Kd values lower than 1.0 L kg(-1), a much more lenient limit than usually proposed for pesticides in the literature (Kd < 5.0 L kg(-1)). The amount of imazaquin leached increased with soil pH. As the soil pH increased, the percentage of imazaquin in the anionic forms, the negative surface potential of the soils, as well as imazaquin water solubility also increased, thus reducing sorption because of repulsive electrostatic forces (hydrophilic interactions). For all surface samples (0-0.2 m), imazaquin did not leach at soil pH values lower than pKa (3.8) and more than 80% of the applied amount was leached at pH values higher than 5.5. For subsurface samples from the acric soils, imazaquin only began to leach at soil pH values > zero point of salt effects (ZPSE > 5.7). In conclusion, the use of surface K(oc) values to predict the amount of imazaquin leached within soil profiles having a positive balance of charges may greatly overestimate its actual leaching potential.     

Effects of short-term conservation management practices on soil organic carbon fractions and microbial community composition under a rice-wheat rotation system

The objective of this study was to investigate the effects of short-term (less than 2 years) conservation managements [no-tillage (NT) and crop residue returning] on top soil (0–5 cm) microbial community composition and soil organic C (SOC) fractions under a rice-wheat rotation at Junchuan town of Hubei Province, China. Treatments were established following a split-plot design of a randomized complete block with tillage practices [conventional tillage (CT) and NT] as the main plot and residue returning level [no residue returning (0) and all residues returned to fields from the preceding crop (S, 2,146 kg C ha^?1)] as the subplots. The four treatments were CT with or without residue returning (CT0 and CTS) and NT with or without residue returning (NT0 and NTS). The abundances of microbial groups [total FLFAs, fungal biomass, bacterial biomass, fungal biomass/bacterial biomass (F/B), monounsaturated fatty acids/saturated fatty acids (MUFA/STFA), and microbial stress] were determined by phospholipid fatty acid (PLFA) analysis of soil. The ratio of MUFA/STFA reflects aeration of soil and greater MUFA/STFA means better aeration condition of soil. Moreover, the microbial stress, the ratio of cy19:0 to 18:1ω7, was regarded as an indicator of physiological or nutritional stress of microbial community. PLFA profiles were dominated by the fatty acids iC15:0 (9.8 %), C16:0 (16.5 %), 10Me17:0 (9.9 %), and Cyc19:0 (8.3 %), together accounting for 44.6 % of the total PLFAs. Compared with CT, NT significantly increased microbial biomass C (MBC) by 20.0 % but did not affect concentrations of total organic C (TOC), dissolved organic C (DOC), easily oxidizable C (EOC), and SOC of aggregates. Residue returning significantly increased MBC by 18.3 % and SOC content of 2–1-mm aggregate by 9.4 %. NT significantly increased total PLFAs by 9.8 % and fungal biomass by 40.8 % but decreased MUFA/STFA by 15.5 %. Residue returning significantly enhanced total PLFAs, bacterial biomass, fungal biomass, F/B, and MUFA/STFA by 31.1, 36.0, 95.9, 42.5, and 58.8 %, respectively, but decreased microbial stress by 45.9 %. Multivariate analysis (redundancy analysis and partial correlation analysis) indicated that SOC of 2–1-mm aggregate was related to changes in the composition of soil microbial groups, suggesting that SOC of 2–1-mm aggregate was sensitive to changes in soil microbial community composition affected by short-term conservation management practices in our study.     

Soil compressibility and penetrability of an Oxisol from southern Brazil, as affected by long-term tillage systems

The precompression stress value defines the transition from the reloading curve to the virgin compression line in the stress–strain curve, which can be used to quantify the highest load or the most intense predrying previously applied to the soil. Thus, in soils with well-defined structured soil horizons, each layer can be characterized by such mechanical strength. Penetration resistance measurements, on the other hand, can be used to determine total soil strength profiles in the field. The effect of long-term tillage systems on physical and mechanical properties was determined in undisturbed and remolded samples collected at 5 and 15 cm depth, 6 months after applying no-till (NT), chisel plow (CP), and conventional tillage (CT) treatments, along with the application of mineral fertilizer and poultry litter. The compressibility tests were performed under confined conditions, with normal loads varying from 10 to 400 kPa after a defined predrying to −6 or −30 kPa. Penetration resistance was determined in the field, after seeding, in three positions: seeding row (SR), untrafficked interrow (UI), and recently trafficked interrow (TI). No-till system showed greater soil resistance to deformation than tilled treatments, as determined by the higher precompression stress and lower coefficient of compressibility. When original soil structure was destroyed (remolded samples), smaller differences were found. The application of extra organic matter (poultry litter) resulted in a reduction of precompression stress in undisturbed samples. Penetration resistance profiles showed greater differences among tillage treatments in the upper layer of the untrafficked interrow, where NT system showed the higher values. Smaller differences were found in the seeding row (with lower values) and in recently trafficked interrow (with higher values), showing that even traffic with a light tractor after soil tillage reduced drastically the effect of previous tillage by loosening up the soil. On the other hand, the tool used to cut the soil and to open the furrow for seeding, incorporated in the direct seeding machine, was sufficient to realleviate surface soil compaction.     

Tantalum Dissolution Rate in Simulant Lung Fluid

The aim of this study is to determine the solubility rate of tantalum contained in pyrochlore, columbite–tantalite and columbite in simulant lung fluid. The International Commission on Radiological Protection (ICRP), in its recommendation for limiting intakes of radionuclide by workers, has consistently recognized that the biological behavior of any specific material after incorporation can significantly diverge from model prevision. Model parameters should be adjusted to adapt the model for each specific substance material in order to estimate the dose due to this element intake. The most recent ICRP publication 66, respiratory tract dosimetry model, point out that information as data like particle size, aerosols solubility and the material chemical compounds are important parameters in the dose coefficients calculation. This paper studies the solubility in Simulant Lung Fluid (SLF) of Ta present in mineral dust particles. For this study 3 minerals were selected: pyrochlore, columbite–tantalite and columbite. Tantalum dissolution in vitro samples were obtained using the Gamble solution and PIXE (Particle Induced X-ray Emission) as analytical technique. In order to characterize the worker exposure to Ta bearing particles, one Brazilian niobium mine was selected. The mineral dust particles were collected using a six-stage cascade impactor and the elemental mass concentrations and the MMAD (Mass Median Aerodynamic Diameter) were determined. Concentrations of radionuclides from natural series of thorium and uranium were also determined. The results show that the workers are exposed to Ta bearing particles in the respirable fraction of aerosols (aerodynamic diameter (d _aer) <2.5 μm) during the mineral processing to obtain Fe–Nb alloy. The solubility in Simulant Lung Fluid (SLF) of Ta present in mineral dust particles depends on the mineral characteristics. The solubility half-time varies between 34 and 62 h depending on the associated mineral.     

Sediment Dynamics and Pollutant Mobility in Rivers (SEDYMO): Assessing Catchment-Wide Emission-Immission Relationships from Sediment Studies. BMBF Coordinated Research Project SEDYMO (2002–2006)

-  DOI: http://dx.doi.org/10.1065/jss2005.11.002 Background and Scope. Apart from their function as indicator or memory for local pollutant inputs, sediments, and especially sediment cores, can be used as a tool for assessing emissionimmission relationships of contaminants on a river-basin scale. Methods. In the framework of the SEDYMO program, source effects, i.e. intensity of sediment erosion under different shear stress, were investigated using a combination of core profile or sampling box studies in laboratory flumes and a mobile in-situ testing device for sediment stability. Results. Calculations of immission risks on downstream areas, e.g., from a three-step approach (substances of concern, areas of concern, areas of risk; Heise et al. 2004), may be directly confirmed from sediment core data, specifically from flood layers, at the target site.