An innovative rapid method for analysis of 10 organophosphorus pesticide residues in wheat by HS-SPME-GC-FPD/MSD

Reduced models of chemical reaction in chaotic flows

We describe and evaluate two reduced models for nonlinear chemical reactions in a chaotic laminar flow. Each model involves two separate steps to compute the chemical composition at a given location and time. The “manifold tracking model” first tracks backwards in time a segment of the stable manifold of the requisite point. This then provides a sample of the initial conditions appropriate for the second step, which requires solving one-dimensional problems for the reaction in Lagrangian coordinates. By contrast, the first step of the “branching trajectories model” simulates both the advection and diffusion of fluid particles that terminate at the appropriate point; the chemical reaction equations are then solved along each of the branched trajectories in a second step. Results from each model are compared with full numerical simulations of the reaction processes in a chaotic laminar flow.

Monitoring of glyphosate residues in herbicide tolerant soybeans from eight production areas of Brazil - 2005/2006 and 2006/2007 harvest seasons.

2008

Flutuação populacional de Anastrepha fraterculus (Wiedemann, 1830) (Diptera, Tephritidae) na Região Oeste de Santa Catarina, Brasil

Fruit flies are the major pests in fruit orchards and require a frequent insecticide aplication control, which increases production cost and chemical residues in fruits. Adults of Anastrepha fraterculus were sampled from twelve peach, plum, orange, tangerine and acid lime orchards in four counties in the Western Region of Santa Catarina. Modified McPhail plastic traps, baited with glucose 10%, were used to collect the flies from October 1998 to September 2000. Trap monitoring, bait replacement and fruit flies sorting by species and sex were done weekly. A total of 4,164 specimens of A. fraterculus was collected and highest population was registered in the county of Chapecó (64,8% of all sampled flies). Adults were collected all year long, with the highest population peaks occurring from December and January, although the fluctuation was different for each fruit species due to their particular phenology and in different years. Positive correlation among temperature, atmospheric humidity and population levels of adults of A. fraterculus was observed. According to the degree days obtained for each year, 4851.9, 4632.9 and 4983.7, respectively in 1998, 1999 and 2000, it was established that A. fraterculus could present an average of 11.2 generations a year.

Determinação do ponto de névoa em surfactantes não iônicos por espectroscopia de impedância elétrica

In this paper, we analyze the use of electrical impedance spectroscopy applied to determination of cloud point. The slope of admittance measured at 100 kHz is reduced to temperature above the critical value which characterizes the phase transition, in a strong indication that this process is activated during the clouding. Additionally to this study we explored the influence of parameters such as additives and temperature on the performance of phase separation of residues (silver nanoparticles) by cloud point extraction. The interaction with salt maximizes the separation of chemical residues in a progressively reduced temperature.

Residues of zeta-cypermethrin in bovine tissues and milk following pour-on and spray application

The depletion of zeta-cypermethrin residues in bovine tissues and milk was studied. Beef cattle were treated three times at 3-week intervals with 1 ml 10 kg(-1) body weight of a 25 g litre(-1) or 50 g litre(-1) pour-on formulation (2.5 and 5.0 mg zeta-cypermethrin kg(-1) body weight) or 100 mg kg(-1) spray to simulate a likely worst-case treatment regime. Friesian and Jersey dairy cows were treated once with 2.5 mg zeta-cypermethrin kg(-1) in a pour-on formulation. Muscle, liver and kidney residue concentrations were generally less than the limit of detection (LOD = 0.01 mg kg(-1)). Residues in renal-fat and back-fat samples from animals treated with 2.5 mg kg(-1) all exceeded the limit of quantitation (LOQ = 0.05 mg kg(-1)), peaking at 10 days after treatment. Only two of five kidney fat samples were above the LOQ after 34 days, but none of the back-fat samples exceeded the LOQ at 28 days after treatment. Following spray treatments, fat residues were detectable in some animals but were below the LOQ at all sampling intervals. Zeta-cypermethrin was quantifiable (LOQ = 0.01 mg kg(-1)) in only one whole-milk sample from the Friesian cows (0.015 mg kg(-1), 2 days after treatment). In whole milk from Jersey cows, the mean concentration of zeta-cypermethrin peaked 1 day after treatment, at 0.015 mg kg(-1), and the highest individual sample concentration was 0.025 mg kg(-1) at 3 days after treatment. Residues in milk were not quantifiable beginning 4 days after treatment. The mean concentrations of zeta-cypermethrin in milk fat from Friesian and Jersey cows peaked two days after treatment at 0.197 mg kg(-1) and 0.377 mg kg(-1), respectively, and the highest individual sample concentrations were 2 days after treatment at 0.47 mg kg(-1) and 0.98 mg kg(-1), respectively. (C) 2001 Society of Chemical Industry.

Electrodialytic remediation of two types of air pollution control residues and their applicability in construction materials

Dissertação para obtenção do Grau de Mestre em Engenharia do Ambiente Perfil de Engenharia de Sistemas Ambientais

Chemical and physical properties of organic residues

Due to human activity, large amounts of organic residue are generated daily. Therefore, an adequate use in agricultural activities requires the characterization of the main properties. The chemical and physical characterization is important when planning the use and management of organic residue. In this study, chemical and physical properties of charcoal, coffee husk, pine-bark, cattle manure, chicken manure, coconut fiber, sewage sludge, peat, and vermiculite were determined. The following properties were analyzed: N-NH4+, N-N0(3)-, and total concentrations of N, P, S, K, Ca, Mg, Mn, Zn, Cu, and B, as well as pH, Electrical Conductivity (EC) and bulk density. Coffee husk, sewage sludge, chicken manure and cattle manure were generally richer in nutrients. The EC values of these residues were also the highest (0.08 - 40.6 dS m-1). Peat and sewage sludge had the highest bulky density. Sodium contents varied from 0 to 4.75 g kg-1, with the highest levels in chicken manure, cattle manure and sewage sludge. Great care must be taken when establishing proportions of organic residues in the production of substrates with coffee husk, cattle or chicken manure or sewage sludge in the calculation of the applied fertilizer quantity in crop fertilization programs.

Biomass decomposition and nutrient release from black oat and hairy vetch residues deposited in a vineyard

A significant quantity of nutrients in vineyards may return to the soil each year through decomposition of residues from cover plants. This study aimed to evaluate biomass decomposition and nutrient release from residues of black oats and hairy vetch deposited in the vines rows, with and without plastic shelter, and in the between-row areas throughout the vegetative and productive cycle of the plants. The study was conducted in a commercial vineyard in Bento Gonçalves, RS, Brazil, from October 2008 to February 2009. Black oat (Avena strigosa) and hairy vetch (Vicia villosa) residues were collected, subjected to chemical (C, N, P, K, Ca, and Mg) and biochemical (cellulose - Cel, hemicellulose - Hem, and lignin - Lig content) analyses, and placed in litter bags, which were deposited in vines rows without plastic shelter (VPRWS), in vines rows with plastic shelter (VPRS), and in the between-row areas (BR). We collected the residues at 0, 33, 58, 76, and 110 days after deposition of the litter bags, prepared the material, and subjected it to analysis of total N, P, K, Ca, and Mg content. The VPRS contained the largest quantities and percentages of dry matter and residual nutrients (except for Ca) in black oat residues from October to February, which coincides with the period from flowering up to grape harvest. This practice led to greater protection of the soil surface, avoiding surface runoff of the solution derived from between the rows, but it retarded nutrient cycling. The rate of biomass decomposition and nutrient release from hairy vetch residues from October to February was not affected by the position of deposition of the residues in the vineyard, which may especially be attributed to the lower values of the C/N and Lig/N ratios. Regardless of the type of residue, black oat or hairy vetch, the greatest decomposition and nutrient release mainly occurred up to 33 days after deposition of the residues on the soil surface, which coincided with the flowering of the grapevines, which is one of the phenological stages of greatest demand for nutrients.

A combined computational and functional approach identifies new residues involved in pH-dependent gating of ASIC1a.

Acid-sensing ion channels (ASICs) are key receptors for extracellular protons. These neuronal nonvoltage-gated Na(+) channels are involved in learning, the expression of fear, neurodegeneration after ischemia, and pain sensation. We have applied a systematic approach to identify potential pH sensors in ASIC1a and to elucidate the mechanisms by which pH variations govern ASIC gating. We first calculated the pK(a) value of all extracellular His, Glu, and Asp residues using a Poisson-Boltzmann continuum approach, based on the ASIC three-dimensional structure, to identify candidate pH-sensing residues. The role of these residues was then assessed by site-directed mutagenesis and chemical modification, combined with functional analysis. The localization of putative pH-sensing residues suggests that pH changes control ASIC gating by protonation/deprotonation of many residues per subunit in different channel domains. Analysis of the function of residues in the palm domain close to the central vertical axis of the channel allowed for prediction of conformational changes of this region during gating. Our study provides a basis for the intrinsic ASIC pH dependence and describes an approach that can also be applied to the investigation of the mechanisms of the pH dependence of other proteins.

Rapid analysis of multiclass antibiotic residues and some of their metabolites in hospital, urban wastewater and river water by ultra-highperformance liquid chromatography coupled to quadrupole-linear ion trap tandem mass spectrometry

The present work describes the development of a fast and robust analytical method for the determination of 53 antibiotic residues, covering various chemical groups and some of their metabolites, in environmental matrices that are considered important sources of antibiotic pollution, namely hospital and urban wastewaters, as well as in river waters. The method is based on automated off-line solid phase extraction (SPE) followed by ultra-high-performance liquid chromatography coupled to quadrupole linear ion trap tandem mass spectrometry (UHPLC–QqLIT). For unequivocal identification and confirmation, and in order to fulfill EU guidelines, two selected reaction monitoring (SRM) transitions per compound are monitored (the most intense one is used for quantification and the second one for confirmation). Quantification of target antibiotics is performed by the internal standard approach, using one isotopically labeled compound for each chemical group, in order to correct matrix effects. The main advantages of the method are automation and speed-up of sample preparation, by the reduction of extraction volumes for all matrices, the fast separation of a wide spectrum of antibiotics by using ultra-high-performance liquid chromatography, its sensitivity (limits of detection in the low ng/L range) and selectivity (due to the use of tandem mass spectrometry) The inclusion of β-lactam antibiotics (penicillins and cephalosporins), which are compounds difficult to analyze in multi-residue methods due to their instability in water matrices, and some antibiotics metabolites are other important benefits of the method developed. As part of the validation procedure, the method developed was applied to the analysis of antibiotics residues in hospital, urban influent and effluent wastewaters as well as in river water samples

Effect of heated solutions on decay control and residues of imazalil in lemons

Freshly harvested lemons [(Citrus limon (L.) Burm)] were dipped 3 min in water with and without imazalil (IMZ) at 50, 100, and 200 ppm at 50 degrees C and at 1000 ppm IMZ at 20 degrees C. Following treatments fruit were kept at 9 degrees C and 90%-95% relative humidity (RH) for 13 weeks and an additional week at 21 degrees C and ca. 75% RH, to simulate a marketing period (SMP). No decay control was observed with fruit dipped in water at 50 degrees C. In contrast, IMZ treatments provided 90%-96% control of Penicillium rots during cold storage and SMP. Fungi other than Penicillium spp. were also found in all samples as differences among treatments were negligible. IMZ treatment caused some external damage to the fruit (peel browning), and the percentage of damaged fruit was related to the amount of active ingredient (AI) present in it. Dipping in 200 or 1000 ppm IMZ promoted off-flavor development after 10 weeks of storage, and fruit were judged to be unacceptable for consumption after 13 weeks of cold storage. After 1000 ppm IMZ dipping at 20 degrees C, residue concentration in fruit was 8.20 ppm; this value doubled that found in a previous investigation on lemons treated with comparable IMZ levels. Residue concentrations in fruit after treatment at 50 degrees C was strictly related to the amount of fungicide employed. After 13 weeks Al residues in fruit decreased to average ca. 35% of the initial values. During the 1 week SMP, residue levels decreased by a further ca. 25%. It was concluded that it is possible to achieve significant control of decay in lemons during longterm storage by dipping fruit in 50 ppm IMZ mixtures at 50 degrees C. Such treatment should be advised to remarkably reduce potential pollution in the environment due to packinghouse wastewater disposal.

Towars a chemical reagents and residues management at the teaching laboratories of the Chemistry School of the Universidad Nacional

The academic activities carried out at the School of Chemistry make indispensable to develop actions oriented toward the consolidation of a reagent and residue management system, especially in the teaching laboratories. The project “Management of reagents and residues in the teaching laboratories of the School of Chemistry” works under the Green Chemistry values which designs products and chemical processes that reduce or eliminate the use and production of dangerous substances, to benefit the environment. With a preventive vision, a change from the  laboratory practices is looked to select those with less environmental impact. Additionally, residue quantification is made and its management protocols are developed for each practice. The project has several stages: diagnose, action implementation, student, teacher and administration personnel training and evaluation during the process and at the end of it. The article describes methodological aspects of the project operation emphasizing on reagent and residue quantification through flow diagrams.

Energy and amino acid content in phase 1 nursery diet: piglet performance and body chemical composition

It was evaluated the effects of metabolizable energy (ME) and digestible lysine (dLYS) densities on performance and body composition of weaned piglets. The study used 114 piglets weaned at 7.4 ± 0.80 kg, out of which 108 were allotted in the nursery and 6 were slaughtered on the weaning day to determine comparative data of body chemical composition. Six nutrients densities were stipulated from a previous study based on the highest nitrogen retention, maintaining the following ME:LYS relationship in the experimental diets: 3,390:1.291; 3,450:1.409; 3,650:1.411; 3,780:1.461; 3,940:1.507; and 4,109 kcal/kg ME:1.564% dLYS. The experimental diets were offered for 13 days when the piglets reached 12.986 ± 1.449 kg of body weight. The probable residual effects of nutritional density on the subsequent performance of the piglets were evaluated. At the end of initial phase 1, six piglets from each density were slaughtered to determine their chemical composition in body fractions and empty body. There was no significant influence of nutritional levels on the performance of the piglets at the end of the evaluation. The results of food conversion and body composition confirm the level indicated in the previous study, 4 g dLYS/Mcal of ME. The increase of energy and lysine densities confirms the need for a correct relationship among both of them to assure better performance of the piglets at the beginning of the growing phase.

Relevance of leaf surface contamination for assessing chemical composition of bromeliads in a restinga forest

Resuspended soil and other airborne particles adhered to the leaf surface affect the chemical composition of the plant. A well-defined cleaning procedure is necessary to avoid this problem, providing a correct assessment of the inherent chemical composition of bromeliads. To evaluate the influence of a washing procedure, INAA was applied for determining chemical elements in the leaves of bromeliads from Vriesea carinata species, both non-washed and washed with Alconox, EDTA and bi-distilled water. Br, Ce, Hg, La, Sc, Se, Sm and Th showed higher mass fractions in non-washed leaves. The washing procedure removed the exogenous material without leaching chemical elements from inside the tissues.