Hygroscopic properties of solid agro-industrial by-products used in solid-state fermentation

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Estimation of water retention curve from mercury intrusion porosimetry and van Genuchten model

The water retention curve (WRC) is a hydraulic characteristic of concrete required for advanced modeling of water (and thus solute) transport in variably saturated, heterogeneous concrete. Unfortunately, determination by a direct experimental method (for example, measuring equilibrium moisture levels of large samples stored in constant humidity cells) is a lengthy process, taking over 2 years for large samples. A surrogate approach is presented in which the WRC is conveniently estimated from mercury intrusion porosimetry (MIP) and validated by water sorption isotherms: The well-known Barrett, Joyner and Halenda (BJH) method of estimating the pore size distribution (PSD) from the water sorption isotherm is shown to complement the PSD derived from conventional MIP. This provides a basis for predicting the complete WRC from MIP data alone. The van Genuchten equation is used to model the combined water sorption and MIP results. It is a convenient tool for describing water retention characteristics over the full moisture content range. The van Genuchten parameter estimation based solely on MIP is shown to give a satisfactory approximation to the WRC, with a simple restriction on one. of the parameters.

Secagem convectiva da microalga spirulina platensis: avaliação das propriedades físicas e bioquímicas

O objetivo no presente estudo foi investigar a operação de secagem da microalga Spirulina platensis em camada delgada através da modelagem matemática e otimização da operação, avaliando as características do produto final através de análises físico-químicas. Foram analisados os dados da umidade de equilíbrio para a isoterma de adsorção a 10, 20 e 30°C e de dessorção a 40, 50 e 60°C, através dos modelos de GAB e BET. O calor isostérico foi determinado pela aplicação da equação de Clausius-Clapeyron. O modelo de GAB apresentou melhor ajuste aos dados experimentais. Os valores da área superficial calculados pelos modelos de GAB e BET foram próximos. O calor isostérico e a entropia diferencial da isoterma de dessorção apresentaram comportamento similar. A teoria da compensação entalpia-entropia foi aplicada nas isotermas, indicando que são controladas pela entalpia. A cinética de secagem foi analisada na faixa de temperatura de 50-70°C, através dos modelos de Lewis, Henderson e Pabis, Henderson, Page e Overhults. O modelo de Henderson e Pabis foi escolhido por apresentar maior significado físico para estimar o valor de difusividade efetiva (Def), sendo os valores encontrados na faixa de 5,54 - 6,60×10-11 m 2 /s, para as temperaturas de 50 e 60°C, respectivamente, e de 1,58×10-10 m2 /s para a temperatura de 70°C. A energia de ativação apresentou um valor de 47,9 kJ/mol. A secagem alterou a cor quando comparada ao material in natura. A secagem foi otimizada na faixa de espessuras e temperaturas do ar de secagem de 3-7 mm e de 50-70ºC, respectivamente, através da metodologia de superfície de resposta para ácido tiobarbitúrico (TBA) e perda de ficocianina no produto final. A melhor condição de secagem foi a 55°C e a 3,7 mm, apresentando uma perda de ficocianina de aproximadamente 37% e valor de TBA de 1,5 mgMDA/kgamostra. Nesta condição de secagem, a composição de ácidos graxos da microalga Spirulina não apresentou diferença significativa (P > 0,05) em relação a microalga in natura.

Stability Testing of Spray- and Spouted Bed-Dried Extracts of Passiflora alata

The aim of this research was to perform a stability testing of spray- and spouted bed-dried extracts of Passiflora alata Dryander (Passion flower) under stress storage conditions. Spouted bed- and spray-dried extracts were characterized by determination of the average particle diameter (dP), apparent moisture content (XP), total flavonoid content (TF), and vitexin content. Smaller and more irregular particles were generated by the spouted bed system due to a higher attrition rate (surface erosion) inside the dryer. The SB dryer resulted in an end product with higher concentration of flavonoids (approximate to 10%) and lower moisture content (1.6%, dry basis) than the spray dryer, even with both dryers working at similar inlet drying air temperature and ratio between the extract feed flow rate to drying air flow rate (Ws/Wg). Samples of the spouted bed- and spray-dried extracts were stored at two different temperatures (34 and 45 degrees C) and two different relative humidities (52 and 63% RH for 34 degrees C; 52 and 60% RH for 45 degrees C) in order to perform the stability testing. The dried extracts were stored for 28 days and were analyzed every 4 days. The flavonoid vitexin served as the marker compound, which was assayed during the storage period. Results revealed shelf lives ranging from 9 to 184 days, depending on the drying process and storage conditions.

Sorção e persistência da sorgoleona em um Latossolo Vermelho-Amarelo

The root exudates produced by sorghum contain a biologically active constituent known as sorgoleone. The behavior of sorgoleone in a Red-Yellow Latosol was studied. The sorption model of sorgoleone in soil was better adjusted to the Freundlich equation, through the coefficients Kf (capacity of sorption) and 1/n (linearity of the isotherm). The persistence of sorgoleone in soil and its possible degradation were also evaluated by monitoring their residues in the soil along the time. Recovery rate of sorgoleone from the soil reached 93% after 24h. It was verified that sorgoleone is strongly sorbed in the soil and its half-life is 10 days, under the experimental conditions. The presence of sorgoleone or its metabolites was not detected in the soil after 60 days.

Determinação do coeficiente de distribuição (Kd) de benzo(a)pireno em solo por isotermas de sorção

Leaking of diesel oil from gas stations is frequent in Brazil. The presence of polycyclic aromatic hydrocarbons (PAHs), which are highly toxic is an indication of contamination by heavy hydrocarbons from diesel oil. Here were present the determination of the distribution coefficient (Kd) of benzo(a)pyrene (the most carcinogenic of the PAHs) in tropical soils using the sorption isotherm model. The sorption curves acquired for benzo(a)pyrene were of the S-type, probably due to the water/methanol experimental conditions. The sorption curves allowed calculation of the distribution coefficient (Kd). The experimental Kd values were lower than those calculated from literature Koc values (partition coefficient normalized by organic carbon), due mainly to the cosolvency effect and the percentage of organic matter and clay in soil.

NOVO SORVENTE DE HIDROFOBICIDADE REDUZIDA PARA EXTRAÇÃO EM FASE SÓLIDA: PREPARAÇÃO E CARACTERIZAÇÃO

C18 chemically bonded sorbents have been the main materials used in solid phase extraction (SPE). However, due their high hydrophobicity some hydrophobic solutes are strongly retained leading to the consumption of larger quantities of organic solvent for efficient recoveries. This work presents a sorbent with lower hydrophobicity but similar selectivity to the C18 sorbent, prepared by thermal immobilization of poly(dimethylsiloxane-co-alkylmethylsiloxane) (PDAS) on silica. PDAS has organic chains with methyl groups alternating with octadecyl or hexadecyl groups in its monomeric unities. For the Si(PDAS) sorbent presented, the polymeric layer was physically adsorbed on the silica surface with 12% carbon load. Although the coating of silica with the polymeric layer was incomplete, the PDAS provided better protection for the silica surface groups, promoting mostly hydrophobic interactions between analytes and the sorbent. Sorption isotherm studies revealed that the retention of hydrophobic solutes on Si(PDAS) was less intense than on conventional sorbents, confirming the lower hydrophobicity of the lab-made sorbent. Additional advantages of Si(PDAS) include simplicity and low cost of preparation, making this material a potential sorbent for the analysis of highly hydrophobic solutes.

Synthesis, characterization and catalytic evaluation of cubic ordered mesoporous iron-silicon oxides

Iron was successfully incorporated in FDU-1 type cubic ordered mesoporous silica by a simple direct synthesis route. The (Fe/FDU-1) samples were characterized by Rutherford back-scattering spectrometry (RBS), small angle X-ray scattering (SAXS). N(2) sorption isotherm, X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). The resulting material presented an iron content of about 5%. Prepared at the usual acid pH of -0.3, the composite was mostly formed by amorphous silica and hematite with a quantity of Fe(2+) present in the structure. The samples prepared with adjusted pH values (2 and 3.5) were amorphous. The samples` average pore diameter was around 12.0 nm and BET specific surface area was of 680 m(2) g(-1). Although the iron-incorporated material presented larger lattice parameter, about 25 nm compared to pure FDU-1, the Fe/FDU-1 composite still maintained its cubic ordered fcc mesoporous structure before and after the template removal at 540 degrees C. The catalytic performance of Fe/FDU-1 was investigated in the catalytic oxidation of Black Remazol B dye using a catalytic ozonation process. The results indicated that Fe/FDU-1 prepared at the usual acid pH exhibited high catalytic activity in the mineralization of this pollutant when compared to the pure FDU-1. Fe(2)O(3) and Fe/FDU-1 prepared with higher pH of 2 and 3.5. (C) 2010 Elsevier B.V. All rights reserved.

Estudos de sorção de um corante aniônico modelo em partículas de quitosana reticulada

Textile activity results in effluents with a variety of dyes. Among the several processes for dye-uptaking from these wastewaters, sorption is one of the most effective methods, chitosan being a very promising alternative for this end. The sorption of Methyl Orange by chitosan crosslinked particles was approached using equilibrium and kinetic analyses at different pH s. Besides the standard pseudo-order analysis normally effectuated (i.e. pseudo-first-order and pseudo-second-order), a novel approach involving a pseudo-nth-order kinetics was used, nbeing determined via non-linear regression, using the Levenberg-Marquardt method. Zeta potential measurements indicated that electrostatic interactions were important for the sorption process. Regarding equilibrium experiments, data were well fitted to a hybrid Langmuir-Freundlich isotherm, and estimated Gibbs free energy of adsorption as a function of mass of dye per area of chitosan showed that the process of adsorption becomes more homogeneous as the pH of the continuous phase decreased. Considering the kinetics of sorption, although a pseudo-nth-order description yielded good fits, a kinetic equation involving diffusion adsorption phenomena was found to be more consistent in terms of a physicochemical description of the sorption process

Application of compression test in analysis of mechanical and color changes in grapefruit juice powder as related to glass transition and water activity

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Study of the interactions of Neptunium with humic substances and the clay mineral montmorillonite by direct and non direct speciation methods

For the safety assessment of radioactive waste, the possibility of radionuclide migration has to be considered. Since Np (and also Th due to the long-lived 232-Th) will be responsible for the greatest amount of radioactivity one million years after discharge from the reactor, its (im)-mobilization in the geosphere is of great importance. Furthermore, the chemistry of Np(V) is quite similar (but not identical) to the chemistry of Pu(V). Three species of neptunium may be found in the near field of the waste disposal, but pentavalent neptunium is the most abundant species under a wide range of natural conditions. Within this work, the interaction of Np(V) with the clay mineral montmorillonite and melanodins (as model substances for humic acids) was studied. The sorption of neptunium onto gibbsite, a model clay for montmorillonite, was also investigated. The sorption of neptunium onto γ-alumina and montmorillonite was studied in a parallel doctoral work by S. Dierking. Neptunium is only found in ultra trace amounts in the environment. Therefore, sensitive and specific methods are needed for its determination. The sorption was determined by γ spectroscopy and LSC for the whole concentration range studied. In addition the combination of these techniques with ultrafiltration allowed the study of Np(V) complexation with melanoidins. Regrettably, the available speciation methods (e.g. CE-ICP-MS and EXAFS) are not capable to detect the environmentally relevant neptunium concentrations. Therefore, a combination of batch experiments and speciation analyses was performed. Further, the preparation of hybrid clay-based materials (HCM) montmorillonitemelanoidins for sorption studies was achieved. The formation of hybrid materials begins in the interlayers of the montmorillonite, and then the organic material spreads over the surface of the mineral. The sorption of Np onto HCM was studied at the environmentally relevant concentrations and the results obtained were compared with those predicted by the linear additive model by Samadfam. The sorption of neptunium onto gibbsite was studied in batch experiments and the sorption maximum determined at pH~8.5. The sorption isotherm pointed to the presence of strong and weak sorption sites in gibbsite. The Np speciation was studied by using EXAFS, which showed that the sorbed species was Np(V). The influence of M42 type melanodins on the sorption of Np(V) onto montmorillonite was also investigated at pH 7. The sorption of the melanoidins was affected by the order in which the components were added and by ionic strength. The sorption of Np was affected by ionic strength, pointing to outer sphere sorption, whereas the presence of increasing amounts of melanoidins had little influence on Np sorption.

The plasticisation effect of glycerol and water on the gelatinisation of wheat starch

In the extrusion manufacture of starch-based thermoplastics, such as biodegradable packaging materials, glycerol is an effective additive as a plasticiser, that is, to diminish the brittle nature of the product and provide the desired extent of flexibility. However, the addition of glycerol may also affect the gelatinisation behaviour of the starch-water mixture, and hence the required processing conditions for producing a homogeneously gelatinised starch-based material. The effect of glycerol on the gelatinisation of wheat starch was studied using differential scanning calorimetry (DSC). Mixtures of starch, water and glycerol were investigated with a water content ranging from 12 - 40% and a glycerol concentration up to 75%. Dependent on composition, the enthalpy of gelatinisation ranged from 1.7 - 12.6 J/g (on a dry starch basis), while the onset and peak temperatures varied from 54 to 86 degreesC and 60 to 90 degreesC, respectively. As expected, water acted as a plasticiser in that the onset temperature for gelatinisation (TO) decreased with increasing moisture content. Glycerol, however, increased To. It is shown that the T-0 of starch-glycerol-water mixtures may be predicted on the basis of the effective moisture content of the starch fraction of these mixtures resulting from the relative speed of moisture absorption by glycerol and starch, respectively. Moisture sorption kinetics of wheat starch and glycerol in 100% relative humidity were determined and used to predict the preferential water absorption by glycerol in starch-glycerol-water mixtures and hence the resulting T-0 of the system.

Non-additivity of attractive potentials in modeling of N-2 and Ar adsorption isotherms on graphitized carbon black and porous carbon by means of density functional theory

We present a new approach accounting for the nonadditivity of attractive parts of solid-fluid and fluidfluid potentials to improve the quality of the description of nitrogen and argon adsorption isotherms on graphitized carbon black in the framework of non-local density functional theory. We show that the strong solid-fluid interaction in the first monolayer decreases the fluid-fluid interaction, which prevents the twodimensional phase transition to occur. This results in smoother isotherm, which agrees much better with experimental data. In the region of multi-layer coverage the conventional non-local density functional theory and grand canonical Monte Carlo simulations are known to over-predict the amount adsorbed against experimental isotherms. Accounting for the non-additivity factor decreases the solid-fluid interaction with the increase of intermolecular interactions in the dense adsorbed fluid, preventing the over-prediction of loading in the region of multi-layer adsorption. Such an improvement of the non-local density functional theory allows us to describe experimental nitrogen and argon isotherms on carbon black quite accurately with mean error of 2.5 to 5.8% instead of 17 to 26% in the conventional technique. With this approach, the local isotherms of model pores can be derived, and consequently a more reliab * le pore size distribution can be obtained. We illustrate this by applying our theory against nitrogen and argon isotherms on a number of activated carbons. The fitting between our model and the data is much better than the conventional NLDFT, suggesting the more reliable PSD obtained with our approach.

Application of density functional theory to equilibrium adsorption of argon and nitrogen on amorphous silica surface

We present a new version of non-local density functional theory (NL-DFT) adapted to description of vapor adsorption isotherms on amorphous materials like non-porous silica. The novel feature of this approach is that it accounts for the roughness of adsorbent surface. The solid–fluid interaction is described in the same framework as in the case of fluid–fluid interactions, using the Weeks–Chandler–Andersen (WCA) scheme and the Carnahan–Starling (CS) equation for attractive and repulsive parts of the Helmholtz free energy, respectively. Application to nitrogen and argon adsorption isotherms on non-porous silica LiChrospher Si-1000 at their boiling points, recently published by Jaroniec and co-workers, has shown an excellent correlative ability of our approach over the complete range of pressures, which suggests that the surface roughness is mostly the reason for the observed behavior of adsorption isotherms. From the analysis of these data, we found that in the case of nitrogen adsorption short-range interactions between oxygen atoms on the silica surface and quadrupole of nitrogen molecules play an important role. The approach presented in this paper may be further used in quantitative analysis of adsorption and desorption isotherms in cylindrical pores such as MCM-41 and carbon nanotubes.

Modeling of adsorption in finite cylindrical pores by means of density functional theory

Adsorption of argon at its boiling point infinite cylindrical pores is considered by means of the non-local density functional theory (NLDFT) with a reference to MCM-41 silica. The NLDFT was adjusted to amorphous solids, which allowed us to quantitatively describe argon adsorption isotherm on nonporous reference silica in the entire bulk pressure range. In contrast to the conventional NLDFT technique, application of the model to cylindrical pores does not show any layering before the phase transition in conformity with experimental data. The finite pore is modeled as a cylindrical cavity bounded from its mouth by an infinite flat surface perpendicular to the pore axis. The adsorption of argon in pores of 4 and 5 nm diameters is analyzed in canonical and grand canonical ensembles using a two-dimensional version of NLDFT, which accounts for the radial and longitudinal fluid density distributions. The simulation results did not show any unusual features associated with accounting for the outer surface and support the conclusions obtained from the classical analysis of capillary condensation and evaporation. That is, the spontaneous condensation occurs at the vapor-like spinodal point, which is the upper limit of mechanical stability of the liquid-like film wetting the pore wall, while the evaporation occurs via a mechanism of receding of the semispherical meniscus from the pore mouth and the complete evaporation of the core occurs at the equilibrium transition pressure. Visualization of the pore filling and empting in the form of contour lines is presented.