Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP): linking condensation, evaporation and chemical reactions of organics, oxidants and water

We present a novel kinetic multi-layer model for gas-particle interactions in aerosols and clouds (KMGAP) that treats explicitly all steps of mass transport and chemical reaction of semi-volatile species partitioning between gas phase, particle surface and particle bulk. KMGAP is based on the PRA model framework (P¨oschl-Rudich- Ammann, 2007), and it includes gas phase diffusion, reversible adsorption, surface reactions, bulk diffusion and reaction, as well as condensation, evaporation and heat transfer. The size change of atmospheric particles and the temporal evolution and spatial profile of the concentration of individual chemical species can be modeled along with gas uptake and accommodation coefficients. Depending on the complexity of the investigated system and the computational constraints, unlimited numbers of semi-volatile species, chemical reactions, and physical processes can be treated, and the model shall help to bridge gaps in the understanding and quantification of multiphase chemistry and microphysics in atmospheric aerosols and clouds. In this study we demonstrate how KM-GAP can be used to analyze, interpret and design experimental investigations of changes in particle size and chemical composition in response to condensation, evaporation, and chemical reaction. For the condensational growth of water droplets, our kinetic model results provide a direct link between laboratory observations and molecular dynamic simulations, confirming that the accommodation coefficient of water at 270K is close to unity (Winkler et al., 2006). Literature data on the evaporation of dioctyl phthalate as a function of particle size and time can be reproduced, and the model results suggest that changes in the experimental conditions like aerosol particle concentration and chamber geometry may influence the evaporation kinetics and can be optimized for efficient probing of specific physical effects and parameters. With regard to oxidative aging of organic aerosol particles, we illustrate how the formation and evaporation of volatile reaction products like nonanal can cause a decrease in the size of oleic acid particles exposed to ozone.

In situ preservation of wetland heritage: hydrological and chemical change in the burial environment of the Somerset Levels, UK.

In Situ preservation is a core strategy for the conservation and management of waterlogged remains at wetland sites. Inorganic and organic remains can, however, quickly become degraded, or lost entirely, as a result of chemical or hydrological changes. Monitoring is therefore crucial in identifying baseline data for a site, the extent of spatial and or temporal variability, and in evaluating the potential impacts of these variables on current and future In Situ preservation potential. Since August 2009, monthly monitoring has taken place at the internationally important Iron Age site of Glastonbury Lake Village in the Somerset Levels, UK. A spatial, stratigraphic, and analytical approach to the analysis of sediment horizons and monitoring of groundwater chemistry, redox potential, water table depth and soil moisture (using TDR) was used to characterize the site. Significant spatial and temporal variability has been identified, with results from water-table monitoring and some initial chemical analysis from Glastonbury presented here. It appears that during dry periods parts of this site are at risk from desiccation. Analysis of the chemical data, in addition to integrating the results from the other parameters, is ongoing, with the aim of clarifying the risk to the entire site.

PLANETARY NEBULAE AND THE CHEMICAL EVOLUTION OF THE MAGELLANIC CLOUDS

The determination of accurate chemical abundances of planetary nebulae (PN) in different galaxies allows us to obtain important constraints on chemical evolution models for these systems. We have a long-term program to derive abundances in the galaxies of the Local Group, particularly the Large and Small Magellanic Clouds. In this work, we present our new results on these objects and discuss their implications in view of recent abundance determinations in the literature. In particular, we obtain distance-independent correlations involving He, N, O, Ne, S, and Ar, and compare the results with data from our own Galaxy and other galaxies in the Local Group. As a result of our observational program, we have a large database of PN in the Galaxy and the Magellanic Clouds, so that we can obtain reliable constraints on the nucleosynthesis processes in the progenitor stars in galaxies of different metallicities.

Electronic structure and chemical bonding in the ground states of Tc(2) and Re(2)

Multiconfiguration second-order perturbation theory, including relativistic effects and spin-orbit coupling, has been employed to investigate the nature of the chemical bonding in the ground state of Tc(2) and Re(2). The Tc(2) ground state is found to be a 0(g)(+) state, with an effective bond order (EBO) of 4.4, and a dissociation energy of 3.25 eV. The Re(2) ground state is a 1(g) state, with EBO = 4.3. Almost degenerate to it, is a 0(g)(+) state (T(e) = 77 cm(-1)), with EBO = 4.1. Experimental evidence also indicates that the ground state is of 1(g) nature. The dissociation energy is computed to be 5.0 eV in agreement with an experimental estimate of 4 +/- 1 eV.

Space dependency of chemical attributes in an area with sugarcane plantation in Pereira Barreto, SP

The behavior of the chemical attributes is directly influenced by superficial flow and water movement inside the soil. This work aimed to study the space dependency of chemical attributes in an area with sugarcane plantation in Pereira Barreto, SP. An area of 530.67 hectares was mapped using an equipment of Global Positioning System and obtaining a Digital Elevation Model. A set of 134 soil samples were collected every seven hectares in the depths of 0-0.25 m and 0.80-1.00 m. The pH, organic matter (OM), Ca, Mg, K, BS, CEC and base saturation (BS) were analyzed. All the chemical attributes presented similar behavior in the superficial and subsuperficial layer of the soil, which provided better visualization and definition of the homogeneous tillage zones.

Predicting the chemical composition of the body and the carcass of 3/4Boer x 1/4Saanen kids using body components

The determination of the chemical composition of body and carcass is important in nutritional and growth regulation studies. The purpose of this study was to develop equations to predict the chemical composition of body and carcass using chemical composition of body components. Twenty 3/4Boer x 1/4Saanen crossbred male kids, weighing from 20 to 35 kg, were used in this study. The empty body chemical composition was measured by grinding all body components and sampling for chemical analyses. The body components used to estimate body and carcass composition were: neck, fore leg, ribs, loin, hind leg, 9-11 th rib section, non-carcass components (head plus feet, organs plus blood, and hide), visceral fat, and kidney fat. The chemical composition of organs plus blood and 9-11 th rib section had the highest precision to estimate percentage of fat, protein, and water in the body (r(2) of 0.94, 0.82, and 0.90, respectively). For carcass composition, the chemical composition of ribs was the best component to predict all carcass chemical components; however, the equations to estimate the percentages of protein and ash showed a low precision (r(2) = 0.48, 0.44, respectively). The 9-11 th rib section was accurate and precise to estimate carcass fat percentage. We concluded the chemical composition of the body of 3/4Boer x 1/4Saanen crossbred male kids was highly correlated with the composition of body parts, specifically organs plus blood and 9-11 th rib section. Further studies should focus on evaluating these body parts for different breeds and genders under different production scenarios. (C) 2007 Elsevier B.V. All rights reserved.

Chemical attributes of a savannah Typic Hapludox soil under management systems

O trabalho teve por objetivo estudar as modificações de atributos químicos de um Latossolo Vermelho após dois anos de manejo com adubação orgânica e/ou mineral com diferentes sistemas de cultivo. O experimento foi realizado na área experimental da Universidade Estadual Paulista - UNESP, localizada no município de Selvíria, Estado do Mato Grosso do Sul, no ano agrícola 2004/2005 e 2005/2006. Os tratamentos foram: cultivo convencional; cultivo mínimo e semeadura direta. As adubações foram: testemunha (sem adubação); adubação mineral (300 kg ha-1 da fórmula 20-00-20); adubação orgânica (esterco bovino - 20 Mg ha-1); adubação orgânica (esterco bovino) + ½ adubação mineral recomendada para a cultura utilizada; 20 e 30 Mg ha-1 de lodo de esgoto. em um ano foi utilizada a soja como cultura e no seguinte o sorgo. Avaliaram-se os atributos químicos do solo em quatro camadas. Os atributos químicos do Latossolo Vermelho foram modificados no primeiro ano após as adubações; a adubação com esterco, lodo de esgoto e a combinação do esterco+adubação mineral foram eficazes em modificar os atributos químicos do solo estudado; o lodo de esgoto foi mais eficaz na recuperação do P do solo e, a semeadura direta contribuiu para o aumento de K no solo

Effect of Chemical Disinfection and Accelerated Aging on Color Stability of Maxillofacial Silicone with Opacifiers

Purpose: The purpose of this study was to evaluate the color stability of MDX4-4210 maxillofacial elastomer with opacifier addition submitted to chemical disinfection and accelerated aging.Materials and Methods: Ninety specimens were obtained from Silastic MDX4-4210 silicone. The specimens were divided into three groups (n = 30): Group I: colorless, Group II: barium sulfate opacifier, Group III: titanium dioxide opacifier. Specimens of each group (n = 10) were disinfected with effervescent tablets, neutral soap, or 4% chlorhexidine gluconate. Disinfection was conducted three times a week for 2 months. Afterward, the specimens were submitted to different periods of accelerated aging. Color evaluation was carried out after 60 days (disinfection period) and after 252, 504, and 1008 hours of accelerated aging, using a reflection spectrophotometer. Color alterations were calculated by the CIE L*a*b* system. Data were analyzed by three-way ANOVA and Tukey test (alpha = 0.05).Results: Group II exhibited the lowest color change, whereas Group III the highest (p < 0.05), regardless of the chemical disinfection and accelerated aging periods.Conclusion: Opacifier addition, chemical disinfection, and accelerated aging procedures affected the color stability of the maxillofacial silicone.

In Vitro Assessment of Chemical Activation Efficiency During In-office Dental Bleaching

Purpose: This study compared five types of chemical catalyzing agents added to 35% hydrogen peroxide gel, with regard to their capacity of intensifying in-office dental bleaching results.Methods: One-hundred and twenty bovine incisors were used, of which the crowns and roots were cut in the incisor-apical direction, to acquire the dimensions of a human central incisor. The specimens were sectioned in the mesiodistal direction by means of two longitudinal cuts, the lingual halves being discarded. The vestibular halves received prophylaxis with a bicarbonate jet, ultrasound cleaning and acid etching on the dentinal portion. Next, the specimens were stored in receptacles containing a 25% instant coffee solution for two weeks. After the darkening period, initial measurement of the shade obtained was taken with the Easy Shade appliance, which allowed it to be quantified by the CIELab* method. The samples were divided into six groups, corresponding to the chemical activator used: a) none (CON); b) ferric chloride (CF); c) ferrous sulphate (SF); d) manganese gluconate (GM); e) manganese chloride (CM); f) mulberry root extract (RA). Each group received three 10-minute applications of the gels containing the respective activating agents. Next, a new shade measurement was made.Results: The Analysis of Variance and Tukey tests (alpha=5%) showed statistically significant differences for the shade perception values (p=0.002). Groups GM, CM and RA showed significantly higher means than the control group.Conclusion: The presence of some chemical activators is capable of resulting in a significant increase in tooth shade variation.

Synthesis of SnO2 by chemical routes and its use in varistors production

Tin oxide, SnO2. is a very used compound in industry and one of its uses is as varistor. For the current requirements of the technology is necessary a strict control of the chemical purity and the particle size of the raw material; for that reason the great interest that exists at the moment to develop synthesis methods that allow to get these requirements. In this work, ceramic powders of the Sn-Co-Nb-Ti-Al system using the controlled precipitation and polymeric precursor (Pechini) methods were synthesized. The raw material obtained was characterized using X-ray diffraction (XRD), thermal analysis (DTA/FG) and scanning electron microscopy (SEM). The sintering samples shown a good varistor behavior with non-linear coefficient (alpha) values similar to 22, and Er 2083 V/cm(2). (c) 2007 Elsevier Ltd. All rights reserved.

Comparative study of cogeneration systems in a chemical industry

With the large penetration of the natural gas into the Brazilian energy structure, industries such as paper mills and chemical plants are analyzing the feasibility of implementing cogeneration schemes appropriate to this fuel. The analysis of the energy demand patterns of a chemical company from the photographic sector revealed the possibility of using combined cycles or diesel engine cogeneration schemes keeping the existing compression refrigeration units and steam or gas cycle cogeneration systems with absorption refrigeration units. In terms of economic attractiveness, an analysis based on the method of the internal rate of return was performed. The results indicated that the schemes composed by reciprocating engines and combined cycle with compression chillers, as well as the gas cycle scheme with absorption chiller, present return periods of up to 3 years, showing that the investment in cogeneration could be of interest for this plant. (C) 2000 Elsevier B.V. Ltd. All rights reserved.

Apocynin: Chemical and biophysical properties of a NADPH oxidase inhibitor

Apocynin is the most employed inhibitor of NADPH oxidase (NOX), a multienzymatic complex capable of catalyzing the one-electron reduction of molecular oxygen to the superoxide anion. Despite controversies about its selectivity, apocynin has been used as one of the most promising drugs in experimental models of inflammatory and neurodegenerative diseases. Here, we aimed to study the chemical and biophysical properties of apocynin. The oxidation potential was determined by cyclic voltammetry (Epa = 0.76V), the hydrophobicity index was calculated (logP = 0.83) and the molar absorption coefficient was determined (ε275nm = 1.1 × 104 M-1 cm-1). Apocynin was a weak free radical scavenger (as measured using the DPPH, peroxyl radical and nitric oxide assays) when compared to protocatechuic acid, used here as a reference antioxidant. On the other hand, apocynin was more effective than protocatechuic acid as scavenger of the non-radical species hypochlorous acid. Apocynin reacted promptly with the non-radical reactive species H2O2 only in the presence of peroxidase. This finding is relevant, since it represents a new pathway for depleting H2O2 in cellular experimental models, besides the direct inhibition of NADPH oxidase. This could be relevant for its application as an inhibitor of NOX4, since this isoform produces H 2O2 and not superoxide anion. The binding parameters calculated by fluorescence quenching showed that apocynin binds to human serum albumin (HSA) with a binding affinity of 2.19 × 104 M -1. The association did not alter the secondary and tertiary structure of HSA, as verified by synchronous fluorescence and circular dichroism. The displacement of fluorescent probes suggested that apocynin binds to site I and site II of HSA. Considering the current biomedical applications of this phytochemical, the dissemination of these chemical and biophysical properties can be very helpful for scientists and physicians interested in the use of apocynin.

Optimization of the immobilization of sweet potato amylase using glutaraldehyde-agarose support. Characterization of the immobilized enzyme

A simplified procedure for the preparation of immobilized beta-amylase using non-purified extract from fresh sweet potato tubers is established in this paper, using differently activated agarose supports. Beta-amylase glutaraldehyde derivative was the preparation with best features, presenting improved temperature and pH stability and activity. The possibility of reusing the amylase was also shown, when this immobilized enzyme was fully active for five cycles of use. However, immobilization decreased enzyme activity to around 15%. This seems to be mainly due to diffusion limitations of the starch inside the pores of the biocatalyst particles. A fifteen-fold increase in the Km was noticed, while the decrease of Vmax was only 30% (10.1 U mg-1 protein and 7.03 U mg-1 protein for free and immobilized preparations, respectively). © 2013 Elsevier Ltd.

Relations between the yield of bean (Phaseolus vulgaris L.) and chemical attributes of an Acrustox under no-tillage

In crop year 2006/07, in Selviria, MS, Brazil, were analyzed the productivity of beans because of the chemical attributes of an Acrustox cultivated under conditions of high technological level of management by no-tillage irrigated with pivot central. The objective was to select, among the attributes studied soil, the one with the best representation to explain the variability of agricultural productivity. Geostatistical grid was installed to collect data from soil and plant, with 117 sampling points in an area of 2,025 m(2) and homogeneous slope of 0.055 m m(-1). From the standpoint of linear and spatial bean yield was respectively explained in terms of P and soil pH. So much for the values of phosphorus (P) in the intermediate layer and subsurface between 24-26 mg dm(-3), as well as for Hydrogen (pH) in the surface layer between 5.0 to 5.4, resulted in sites with the most high yield (2,160-2,665 kg ha(-1)).

Chemical characteristics and fractionation of proteins from Moringa oleifera Lam. leaves

Moringa oleifera Lam, is a leguminous plant, originally from Asia, which is cultivated in Brazil because of its low production cost. Although some people have used this plant as food, there is little information about its chemical and nutritional characteristics. The objective of this study was to characterise the leaves of M. oleifera in terms of their chemical composition, protein fractions obtained by solubility in different systems and also to assess their nutritional quality and presence of bioactive substances. The whole leaf flour contained 28.7% crude protein, 7.1% fat, 10.9% ashes, 44.4% carbohydrate and 3.0 mg 100 g(-1) calcium and 103.1 mg 100 g(-1) iron. The protein profile revealed levels of 3.1% albumin, 0.3% globulins, 2.2% prolamin, 3.5% glutelin and 70.1% insoluble proteins. The hydrolysis of the protein from leaf flour employing sodium dodecyl sulfate (SDS) and 2-mercaptoethanol (ME) resulted in 39.5% and 29.5%, respectively. The total protein showed low in vitro digestibility (31.8%). The antinutritional substances tested were tannins (20.7 mg g(-1)), trypsin inhibitor (1.45 TIU mg g(-1)), nitrate (17 mg g(-1)) and oxalic acid (10.5 mg g(-1)), besides the absence of cyanogenic compounds. beta-Carotene and lutein stood out as major carotenoids, with concentrations of 161.0 and 47.0 mu g g(-1) leaf, respectively. Although M. oleifera leaves contain considerable amount of crude protein, this is mostly insoluble and has low in vitro digestibility, even after heat treatment and chemical attack. In vivo studies are needed to better assess the use of this leaf as a protein source in human feed. (C) 2013 Elsevier Ltd. All rights reserved.