High strain rate constitutive modeling forhistorical structures subjected to blast loading

Doctoral Thesis Civil Engineering

Persistent organic chemicals of emerging environmental concern

The use of chemicals and chemical derivatives in agriculture and industry has contributed to their accumulation and persistence in the environment. Persistent organic pollutants (POPs) are among the environmental pollutants of most concern since, when improperly handled and disposed, they can persist in the environment, bioaccumulate through the food web, and may create serious public health and environmental problems. Development of an effective degradation process has become an area of intense research. The physical/chemical methods employed, such as volatilization, evaporation, photooxidation, adsorption, or hydrolysis, are not always effective, are very expensive, and, sometimes, lead to generation/disposal of other contaminants. Biodegradation is one of the major mechanisms by which organic contaminants are transformed, immobilized, or mineralized in the environment. A clear understanding of the major processes that affect the interactions between organic contaminants, microorganisms, and environmental matrix is, thus, important for determining persistence of the compounds, for predicting in situ transformation rates, and for developing site remediation. Information on their risks and impact and occurrence in the different environmental matrices is also important, in order to attenuate their impact and apply the appropriate remediation process. This chapter provides information on the fate of pesticides and polycyclic aromatic hydrocarbons (PAHs), their impact, bioavailability, and biodegradation. © Springer Science+Business Media Dordrecht 2014.

Preparació, estudi estructural i aplicabilitat de derivats de Poli-(4R)-hidroxi-L-prolina a la separació d’enantiòmers per tècniques cromatogràfiques o relacionades

La separació d’enantiòmers (isòmers òptics) és molt important en molts diversos camps, com les síntesis quirals, biologia, i en el camp de la farmacologia especialment. És per això, que es fa necessari de disposar de tècniques i mètodes analítics ràpids, fiables i sensibles per a la separació d’enantiòmers. La present tesi s’emmarca en el camp de la separació d’enantiòmers, concretament en la preparació de fases estacionàries quirals per al seu ús en cromatografia liquida. En aquest sentit, s’ha desenvolupat la síntesi i caracterització de molècules polimèriques quirals derivades de l’aminoàcid L-prolina que incorporades en matrius de gel de sílice poden constituïr columnes quirals per a la separació d’enantiòmers per cromatografia liquida. S’han estudiat les característiques enantioselectives d’aquests nous materials en la separació de molècules quirals, trobant-se ésser satisfactòriament enantioselectius. L’interès que suscita l’obtenció d’enantiòmers a gran escala fa que la recerca s’orienti a la recerca de materials amb elevada capacitat de càrrega, és a dir, que puguin donar lloc a la separació d’elevades quantitats d’enantiòmers. Amb aquesta finalitat s’han dut a terme assaigs de capacitat de càrrega, que han posat de manifest la possible aplicació d’aquests materials a la separació preparativa d’enantiòmers. També s’ha parat especial atenció a l’estudi de les característiques de la matriu de gel de sílice, assajant-se altres materials de sílice més porosos i que permeten així treballar amb fluxos més elevats tot reduint-ne el temps d’anàlisi i els costos associats a la separació preparativa d’enantiòmers. L'estudi conformacional d'aquests nous selectors també ha estat contemplat per tal d'explicar l'enantioselectivitat específica que s'observa en certs dissolvents orgànics en els qual es duu a terme la separació dels enantiòmers.

Bit loading for MIMO with statistical channel information at the transmitter and ZF receivers

For single-user MIMO communication with uncoded and coded QAM signals, we propose bit and power loading schemes that rely only on channel distribution information at the transmitter. To that end, we develop the relationship between the average bit error probability at the output of a ZF linear receiver and the bit rates and powers allocated at the transmitter. This relationship, and the fact that a ZF receiver decouples the MIMO parallel channels, allow leveraging bit loading algorithms already existing in the literature. We solve dual bit rate maximization and power minimization problems and present performance resultsthat illustrate the gains of the proposed scheme with respect toa non-optimized transmission.

Facilitation by serum albumin of renal tubular secretion of organic anions.

The role of albumin in tubular secretion of the organic anions p-aminohippurate (PAH, 21% albumin-bound at 1 microM) and methotrexate (MTX, 55% bound at 1 microM), and of the organic cation N1-methylnicotinamide (NMN, not bound), was investigated in isolated rabbit S2 proximal tubules. PAH or MTX secretory rates were low in the absence of colloids or in the presence of 1 g/dl dextran 40, and were reversibly two- to sevenfold stimulated by either 1 g/dl bovine (BSA, either regular, defatted, and/or dialyzed) or rabbit serum albumin, or by dialyzed native rabbit plasma. NMN secretion was not stimulated by either dextran or albumin. Luminal BSA had no effect, but stimulation of PAH secretion was observed when albumin was present in both lumen and bath. This secretion was BSA concentration-dependent up to a 1 g/dl BSA. Saturation experiments suggested that 1 g/dl BSA may increase PAH apparent affinity for secretion, with no change in its maximum velocity. Albumin appears therefore to facilitate organic anion proximal secretion by an effect unrelated to oncotic pressure or to the extent of organic anion binding.

SwissParam: a fast force field generation tool for small organic molecules.

The drug discovery process has been deeply transformed recently by the use of computational ligand-based or structure-based methods, helping the lead compounds identification and optimization, and finally the delivery of new drug candidates more quickly and at lower cost. Structure-based computational methods for drug discovery mainly involve ligand-protein docking and rapid binding free energy estimation, both of which require force field parameterization for many drug candidates. Here, we present a fast force field generation tool, called SwissParam, able to generate, for arbitrary small organic molecule, topologies, and parameters based on the Merck molecular force field, but in a functional form that is compatible with the CHARMM force field. Output files can be used with CHARMM or GROMACS. The topologies and parameters generated by SwissParam are used by the docking software EADock2 and EADock DSS to describe the small molecules to be docked, whereas the protein is described by the CHARMM force field, and allow them to reach success rates ranging from 56 to 78%. We have also developed a rapid binding free energy estimation approach, using SwissParam for ligands and CHARMM22/27 for proteins, which requires only a short minimization to reproduce the experimental binding free energy of 214 ligand-protein complexes involving 62 different proteins, with a standard error of 2.0 kcal mol(-1), and a correlation coefficient of 0.74. Together, these results demonstrate the relevance of using SwissParam topologies and parameters to describe small organic molecules in computer-aided drug design applications, together with a CHARMM22/27 description of the target protein. SwissParam is available free of charge for academic users at www.swissparam.ch.

Kinetics of K release from soils of Brazilian coffee regions: effect of organic acids

Kinetic studies on soil potassium release can contribute to a better understanding of K availability to plants. This study was conducted to evaluate K release rates from the whole soil, clay, silt, and sand fractions of B-horizon samples of a basalt-derived Oxisol and a sienite-derived Ultisol, both representative soils from coffee regions of Minas Gerais State, Brazil. Potassium was extracted from each fraction after eight different shaking time periods (0-665 h) with either 0.001 mol L-1 citrate or oxalate at a 1:10 solid:solution ratio. First-order, Elovich, zero-order, and parabolic diffusion equations were used to parameterize the time dependence of K release. For the Oxisol, the first-order equation fitted best to the experimental data of K release, with similar rates for all fractions and independent of the presence of citrate or oxalate in the extractant solution. For all studied Ultisol fractions, in which K release rates increased when extractions were performed with citrate solution, the Elovich model described K release kinetics most adequately. The highest potassium release rate of the Ultisol silt fraction was probably due to the transference of "non-exchangeable" K to the extractant solution, whereas in the Oxisol exchangeable potassium represented the main K source in all studied fractions.

Mobility of inorganic and organic phosphorus forms under different levels of phosphate and poultry litter fertilization in soils

The eutrophication of aquifers is strongly linked to the mobility of P in soils. Although P mobility was considered irrelevant in a more distant past, more recent studies have shown that P, both in organic (Po) and inorganic forms (Pi), can be lost by leaching and eluviation through the soil profile, particularly in less weathered and/or sandier soils with low P adsorption capacity. The purpose of this study was to determine losses of P forms by leaching and eluviation from soil columns. Each column consisted of five PVC rings (diameter 5 cm, height 10 cm), filled with two soil types: a clayey Red-Yellow Latosol and a sandy loam Red-Yellow Latosol, which were exposed to water percolation. The soils were previously treated with four P rates (as KH2PO4 ) to reach 0, 12.5, 25.0 and 50 % of the maximum P adsorption capacity (MPAC). The P source was homogenized with the whole soil volume and incubated for 60 days. After this period the soils were placed in the columns; the soil of the top ring was mixed with five poultry litter rates of 0, 20, 40, 80, and 160 t ha-1 (dry weight basis). Treatments consisted of a 4 x 5 x 2 factorial scheme corresponding to four MPAC levels, five poultry litter rates, two soils, with three replications, arranged in a completely randomized block design. Deionized water was percolated through the columns 10 times in 35 days to simulate about 1,200 mm rainfall. In the leachate of each column the inorganic P (reactive P, Pi) and organic P forms (unreactive P, Po) were determined. At the end of the experiment, the columns were disassembled and P was extracted with the extractants Mehlich-1 (HCl 0.05 mol L-1 and H2SO4 0.0125 mol L-1) and Olsen (NaHCO3 0.5 mol L-1; pH 8.5) from the soil of each ring. The Pi and Po fractions were measured by the Olsen extractant. It was found that under higher poultry litter rates the losses of unreactive P (Po) were 6.4 times higher than of reactive P (Pi). Both the previous P fertilization and increasing poultry litter rates caused a vertical movement of P down the soil columns, as verified by P concentrations extracted by Mehlich-1 and NaHCO3 (Olsen). The environmental critical level (ECL), i.e., the P soil concentration above which P leaching increases exponentially, was 100 and 150 mg dm-3 by Mehlich-1 and 40 and 60 mg dm-3 by Olsen, for the sandy loam and clay soils, respectively. In highly weathered soils, where residual P is accumulated by successive crops, P leaching through the profile can be significant, particularly when poultry litter is applied as fertilizer.

Influence of organic-mineral fertilization of an oxisol on soil chemical properties and Bracharia brizantha production

The use of organic-mineral fertilizer produced by the manufacturing industry of lysine and threonine amino acids can improve the fertility of tropical soils. The objective of this study was to evaluate the influence of different doses of the organic-mineral fertilizer named Ajifer L-14 on chemical properties and on the response with increased production of a forage on a Red Latosol in the northwestern region of São Paulo State, Brazil. A randomized block design was used with seven treatments and four replications. The treatments consisted of: T1- control (without application of Ajifer L-14); T2- control (natural vegetation); T3- mineral fertilization according to crop requirements and soil analysis (application of 1.35 kg plot-1 of urea, 2.20 single superphosphate, and 0.51 KCl, corresponding to 60 of N, 40 P2O5 and 30 kg ha-1 of K2O); T4- fertilization with Ajifer L-14 according to the recommendation resulting from the soil chemical analysis (40 L plot-1, corresponding to 60 kg ha-1 N); T5- fertilization with Ajifer L-14, at a rate of 150 % of the recommended values (60 L plot-1, corresponding to 90 kg ha-1 N); T6- fertilization with Ajifer L-14 at a rate of 50 % of the recommended values (20 L plot-1, corresponding to 30 kg ha-1 N); T7- fertilization with Ajifer L-14 at a rate of 125 % of the recommended values (50 L plot-1, corresponding to 75 kg ha-1 N); T8- fertilization with Ajifer L-14 at a rate of 75 % of the recommended values (30 L plot-1, corresponding to 45 kg ha-1 N). The following soil chemical properties were evaluated (layers 0.0-0.1 and 0.1-0.2 m): P, organic matter, pH, K+, Ca2+, Mg2+, cation exchange capacity, potential acidity, and base saturation. The application of this organic-mineral fertilizer does not influence the soil chemical properties. Regression analysis indicated a polynomial relationship between the application rates of organic-mineral fertilizer and the production of dry matter and crude protein of Bracharia Brizantha.

Effect of swine residue rates on corn, common bean, soybean and wheat yield

Swine residue (SR) applied as nutrient source of crops such as corn, bean, soybean and wheat, besides representing an environmental-friendly way of disposing of organic waste resulting from swine production, may significantly increase grain yields, replacing mineral fertilizer. The objective was to evaluate the effect of SR rates on corn, common bean, soybean and wheat yields from 2002 to 2007, in comparison with mineral fertilizer. The experiment was carried out at the Instituto Agronômico do Paraná - IAPAR, Pato Branco, PR and consisted of increasing SR rates (0, 15, 30, 45, and 60 m³ ha-1) and one treatment with mineral fertilizer (NPK 4-30-10), using 250 kg ha-1 for bean and 300 kg ha-1 for corn, soybean and wheat. Also, in the treatment with mineral fertilizer, 60, 120 and 90 kg ha-1 N was applied as topdressing to bean, corn and wheat, respectively. There were significant increases of grain yield in all evaluated years and crops with increasing SR rates, especially in the grass species under study. Also, with increasing SR rates applied every six months, K, P, Ca and Mg were accumulated in the soil and the pH increased. The application of 60 m³ ha-1 SR increased yields and exceeded the yield obtained with the recommended mineral fertilizer, indicating this amount as adequate for these crops.

Spectroscopic quantification of soil phosphorus forms by 31p-nmr after nine years of organic or mineral fertilization

Long-standing applications of mineral fertilizers or types of organic wastes such as manure can cause phosphorus (P) accumulation and changes in the accumulated P forms in the soil. The objective of this research was to evaluate the forms of P accumulated in soils treated with mineral fertilizer or different types of manure in a long-term experiment. Soil was sampled from the 0-5 cm layer of plots fertilized with five different nutrient sources for nine years: 1) control without fertilizer; 2) mineral fertilizer at recommended rates for local conditions; 3) 5 t ha-1 year-1 of moist poultry litter; 4) 60 m³ ha-1 year-1 of liquid cattle manure and 5) 40 m³ ha-1 year-1 of liquid swine manure. The 31P-NMR spectra of soil extracts detected the following P compounds: orthophosphate, pyrophosphate, inositol phosphate, glycerophosphate, and DNA. The use of organic or mineral fertilizer over nine years did not change the soil P forms but influenced their concentration. Fertilization with mineral or organic fertilizers stimulated P accumulation in inorganic forms. Highest inositol phosphate levels were observed after fertilization with any kind of manure and highest organic P concentration in glycerophosphate form in after mineral or no fertilization.

Organic acid adsorption and mineralization in oxisols with different textures

Organic acids play an important role in the nutritional conditions of plants. Their relevance is related to their formation dynamics, mineralization rate and adsorption by soil colloids. This study was carried out to evaluate the dynamics of mineralization and adsorption of organic acid (acetic acid - AA, citric acid - CA and humic acid - HA) applied to the soil. Samples of two Oxisols were used: Rhodic Haplustox (LV) and Typic Haplustox (LVA). The mineralization experiment was arranged in a 2 x 3 x 5 factorial design, based on the factors: two soils (LV and LVA) x three organic acid (OA) types (AA, CA and HA) x five OA rates (0, 1, 2, 4, and 8 mmol dm-3). Organic carbon mineralization in samples was measured by the C-CO2 efflux, produced by the microbial activity, in a 30-day (measurements after 4, 8, 12, 21, and 30 days) and in a 4-day experiment (measured after 24, 48, 72 and 96 h). Organic acid adsorption was tested in a 2 x 2 x 5 x 4 factorial design, with the factors and levels: two Oxisols; two organic acids (AA and CA); five OA rates (0, 1, 2, 4, and 8 mmol dm-3) and four adsorption periods (6, 24, 48, and 72 h). The C-CO2 production of soil treated with CA was highest. In the adsorption experiment, the affinity of CA to soil adsorption sites was greatest. The adsorption of organic acids to soils may be an important mechanism by which bioavailability and thus mineralization capacity by microbial activity are reduced.

Available content, surface runoff and leaching of phosphorus forms in a typic hapludalf treated with organic and mineral nutrient sources

The application of animal manure to soil can increase phosphorus availability to plants and enhance transfer of the nutrient solution drained from the soil surface or leached into the soil profile. The aim of this study was to evaluate the effect of successive applications of organic and mineral nutrient sources on the available content, surface runoff and leaching of P forms in a Typic Hapludalf in no-tillage systems. Experiment 1 was set up in 2004 in the experimental area of UFSM, in Santa Maria (RS, Brazil). The treatments consisted of: control (without nutrient application) and application of pig slurry (PS), pig deep-litter (PL), cattle slurry (CS), and mineral fertilizers (NPK). The rates were determined to meet the N crop requirements of no-tillage black oat and maize, grown in the 2010/2011 growing season. The soil solution was collected after each event (rain + runoff or leaching) and the soluble, particulate and total P contents were measured. In November 2008, soil was collected in 2 cm intervals to a depth of 20 cm, in 5 cm intervals to a depth of 40 cm, and in 10 cm intervals to a depth of 70 cm. The soil was dried and ground, and P determined after extraction by anion exchange resin (AER). In experiment 2, samples collected from the Typic Hapludalf near experiment 1 were incubated for 20, 35, 58, 73 and 123 days after applying the following treatments: soil, soil + PS, soil + PL, soil + CS and soil + NPK. Thereafter, the soil was sampled and P was analyzed by AER. The applications of nutrient sources over the years led to an increase in available P and its migration in the soil profile. This led to P transfer via surface runoff and leaching, with the largest transfer being observed in PS and PL treatments, in which most P was applied. The soil available P and P transfer via surface runoff were correlated with the amounts applied, regardless of the P source. However, P transfer by leaching was not correlated with the applied nutrient amount, but rather with the solution amount leached in the soil profile.

Crop response to organic fertilization with supplementary mineral nitrogen

Animal manure is applied to the soil as a nutrient source, especially of nitrogen, to plants. However, manure application rates can be reduced with the use of N fertilizer in topdressing. The aim of this study was to evaluate crop responses to different application rates of animal manure sources, used alone and supplemented with mineral N topdressing, in a no-tillage system. The study was carried out from 2005 to 2008 on a Hapludalf soil. The treatments consisted of rates of 10, 20 and 30 m³ ha-1 of pig slurry (PS), and of 1 and 2 t ha-1 of turkey manure (TM), applied alone and supplemented with topdressed N fertilizer (TNF), as well as two controls, mineral fertilization (NPK) and one control without fertilizer application. Grain yield in common bean and maize, and dry matter yield and nutrient accumulation in common bean, maize and black oat crops were evaluated. Nitrogen application in topdressing in maize and common bean, especially when PS was used at rates of 20 and 30 m³ ha-1, and TM, at 2 t ha-1, proved effective in increasing the crop grain yields, showing the viability of the combined use of organic and industrialized mineral sources. Nitrogen accumulation in maize and common bean tissues was the indicator most strongly related to grain yield, in contrast with the apparent nutrient recovery, which was not related to the N, P and K quantities applied in the organic sources. No clear residual effect of N topdressing of maize and common bean was observed on the dry matter yield of black oat grown in succession to the main crops with PS and TM applications.

ORGANIC NITROGEN IN A TYPIC HAPLUDOX FERTILIZED WITH PIG SLURRY

The application of pig slurry may have a different effect on nitrogen dynamics in soil compared to mineral fertilization. Thus, the aim of this study was to determine the different forms of organic N in a Latossolo Vermelho distroférrico (Typic Hapludox) and their relationship to N uptake by crops in response to 10 years of annual application of pig slurry and mineral fertilizer. The treatments were application rates of 0, 25, 50, 100, and 200 m3 ha-1 of pig slurry, in addition to mineral fertilizer, organized in a randomized block design with four replications. The N contents were determined in the plant tissue and in the forms of total N and acid hydrolyzed fractions: ammonium-N, hexosamine-N, α-amino-N, amide-N, and unidentified-N. Annual application of pig slurry or mineral fertilizer increased the total-N content in the 0-10 cm depth layer. The main fractions of organic N in the soil were α-amino-N when pig slurry was applied and unidentified-N in the case of mineral fertilizers. Pig slurry increased the N fractions considered as labile: α-amino-N, ammonium-N, and amide-N. The increase in these labile organic N fractions in the soil through pig slurry application allows greater N uptake by the maize and oat crops in a no-tillage system.