Sorption isotherm, glass transitions and state diagram for freeze-dried plum skin and pulp

Differential scanning calorimetry (DSC) was used to determine phase transitions of freeze-dried plums. Samples at low and intermediate moisture contents, were conditioned by adsorption at various water activities (0.11≤a w≤0.90) at 25°C, whereas in the high moisture content region (a w>0.90) samples were obtained by direct water addition, with the resulting sorption isotherm being well described by the Guggenheim-Anderson-deBoer (GAB) model. Freeze-dried samples of separated plum skin and pulp were also analysed. At a w≤0.75, two glass transitions were visible, with the glass transition temperature (T g) decreasing with increasing a w due to the water plasticising effect. The first T g was attributed to the matrix formed by sugars and water. The second one, less visible and less plasticised by water, was probably due to macromolecules of the fruit pulp. The Gordon-Taylor model represented satisfactorily the matrix glass transition curve for a w≤0.90. In the higher moisture content range T g remained practically constant around T g′ (-57.5°C). Analysis of the glass transition curve and the sorption isotherm indicated that stability at a temperature of 25°C, would be attained by freeze dried plum at a water activity of 0.04, corresponding to a moisture content of 12.9% (dry basis). © 2006 SAGE Publications.

Role of enthalpy and entropy in moisture sorption behavior of pineapple pulp powder produced by different drying methods

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Study of the enthalpy-entropy mechanism from water sorption of orange seeds (C. sinensis cv. Brazilian) for the use of agro-industrial residues as a possible source of vegetable oil production

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

MOISTURE SORPTION CHARACTERISTICS OF PINEAPPLE PROCESSING WASTE: SHELL AND CENTRAL CYLINDER

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Removal of toxic metals in a multi metal system using sorbents for potential application to urban stormwater treatment

In the context of increasing demand for potable water and the depletion of water resources, stormwater is a logical alternative. However, stormwater contains pollutants, among which metals are of particular interest due to their toxicity and persistence in the environment. Hence, it is imperative to remove toxic metals in stormwater to the levels prescribed by drinking water guidelines for potable use. Consequently, various techniques have been proposed, among which sorption using low cost sorbents is economically viable and environmentally benign in comparison to other techniques. However, sorbents show affinity towards certain toxic metals, which results in poor removal of other toxic metals. It was hypothesised in this study that a mixture of sorbents that have different metal affinity patterns can be used for the efficient removal of a range of toxic metals commonly found in stormwater. The performance of six sorbents in the sorption of Al, Cr, Cu, Pb, Ni, Zn and Cd, which are the toxic metals commonly found in urban stormwater, was investigated to select suitable sorbents for creating the mixtures. For this purpose, a multi criteria analytical protocol was developed using the decision making methods: PROMETHEE (Preference Ranking Organisation METHod for Enrichment Evaluations) and GAIA (Graphical Analysis for Interactive Assistance). Zeolite and seaweed were selected for the creation of trial mixtures based on their metal affinity pattern and the performance on predetermined selection criteria. The metal sorption mechanisms employed by seaweed and zeolite were defined using kinetics, isotherm and thermodynamics parameters, which were determined using the batch sorption experiments. Additionally, the kinetics rate-limiting steps were identified using an innovative approach using GAIA and Spearman correlation techniques developed as part of the study, to overcome the limitation in conventional graphical methods in predicting the degree of contribution of each kinetics step in limiting the overall metal removal rate. The sorption kinetics of zeolite was found to be primarily limited by intraparticle diffusion followed by the sorption reaction steps, which were governed mainly by the hydrated ionic diameter of metals. The isotherm study indicated that the metal sorption mechanism of zeolite was primarily of a physical nature. The thermodynamics study confirmed that the energetically favourable nature of sorption increased in the order of Zn < Cu < Cd < Ni < Pb < Cr < Al, which is in agreement with metal sorption affinity of zeolite. Hence, sorption thermodynamics has an influence on the metal sorption affinity of zeolite. On the other hand, the primary kinetics rate-limiting step of seaweed was the sorption reaction process followed by intraparticle diffusion. The boundary layer diffusion was also found to limit the metal sorption kinetics at low concentration. According to the sorption isotherm study, Cd, Pb, Cr and Al were sorbed by seaweed via ion exchange, whilst sorption of Ni occurred via physisorption. Furthermore, ionic bonding is responsible for the sorption of Zn. The thermodynamics study confirmed that sorption by seaweed was energetically favourable in the order of Zn < Cu < Cd < Cr . Al < Pb < Ni. However, this did not agree with the affinity series derived for seaweed suggesting a limited influence of sorption thermodynamics on metal affinity for seaweed. The investigation of zeolite-seaweed mixtures indicated that mixing sorbents have an effect on the kinetics rates and the sorption affinity. Additionally, the theoretical relationships were derived to predict the boundary layer diffusion rate, intraparticle diffusion rate, the sorption reaction rate and the enthalpy of mixtures based on that of individual sorbents. In general, low coefficient of determination (R2) for the relationships between theoretical and experimental data indicated that the relationships were not statistically significant. This was attributed to the heterogeneity of the properties of sorbents. Nevertheless, in relative terms, the intraparticle diffusion rate, sorption reaction rate and enthalpy of sorption had higher R2 values than the boundary layer diffusion rate suggesting that there was some relationship between the former set of parameters of mixtures and that of sorbents. The mixture, which contained 80% of zeolite and 20% of seaweed, showed similar affinity for the sorption of Cu, Ni, Cd, Cr and Al, which was attributed to approximately similar sorption enthalpy of the metal ions. Therefore, it was concluded that the seaweed-zeolite mixture can be used to obtain the same affinity for various metals present in a multi metal system provided the metal ions have similar enthalpy during sorption by the mixture.

Metal Retention Experiments for the Design of Soil-Mix Technology Permeable Reactive Barriers

Soil-mix technology is effective for the construction of permeable reactive barriers (PRBs) for in situ groundwater treatment. The objective of this study was to perform initial experiments for the design of soil-mix technology PRBs according to (i) sorption isotherm, (ii) reaction kinetics and (iii) mass balance of the contaminants. The four tested reactive systems were: (i) a granular zeolite (clinoptilolite-GZ), (ii) a granular organoclay (GO), (iii) a 1:1-mixture GZ and model sandy clayey soil and (iv) a 1:1:1-mixture of GZ, GO and model soil. The laboratory experiments consisted of batch tests (volume 900mL and sorbent mass 18g) with a multimetal solution of Pb, Cu, Zn, Cd and Ni. For the adsorption experiment, the initial concentrations ranged from 0.01 to 0.5mM (2.5 to 30mg/L). The maximum metal retention was measured in a batch test (300mg/L for each metal, volume 900mL, sorbent mass 90-4.5g). The reactive material efficiency order was found to be GZ>GZ-soil mix>GZ-soil-GO mix>GO. Langmuir isotherms modelled the adsorption, even in presence of a mixed cations solution. Adsorption was energetically favourable and spontaneous in all cases. Metals were removed according to the second order reaction kinetics; GZ and the 1:1-mix were very similar. The maximum retention capacity was 0.1-0.2mmol/g for Pb in the presence of clinoptilolite; for Cu, Zn, Cd and Ni, it was below 0.05mmol/g for the four reactive systems. Mixing granular zeolite, organoclay and model soil increased the chemisorption. Providing that GZ is reactive enough for the specific conditions, GZ can be mixed to obtain the required sorption. Granular clinoptilolite addition to soil is recommended for PRBs for metal contaminated groundwater. The laboratory experiments consisted of batch tests with a multimetal solution of Pb, Cu, Zn, Cd and Ni. The four reactive materials chosen were granular zeolite, clinoptilolite and model sandy clayey soil, granular organoclay and a mix of clinoptilolite, model soil and organoclay. The reactive material efficiency order was found to be granular clinoptilolite>clinoptilolite-soil mix>clinoptilolite-soil-organoclay mix>granular organoclay. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optimization of Processing Technology for Commercial Drying of Bananas (Matooke)

Summary - Cooking banana is one of the most important crops in Uganda; it is a staple food and source of household income in rural areas. The most common cooking banana is locally called matooke, a Musa sp triploid acuminate genome group (AAA-EAHB). It is perishable and traded in fresh form leading to very high postharvest losses (22-45%). This is attributed to: non-uniform level of harvest maturity, poor handling, bulk transportation and lack of value addition/processing technologies, which are currently the main challenges for trade and export, and diversified utilization of matooke. Drying is one of the oldest technologies employed in processing of agricultural produce. A lot of research has been carried out on drying of fruits and vegetables, but little information is available on matooke. Drying of matooke and milling it to flour extends its shelf-life is an important means to overcome the above challenges. Raw matooke flour is a generic flour developed to improve shelf stability of the fruit and to find alternative uses. It is rich in starch (80 - 85%db) and subsequently has a high potential as a calorie resource base. It possesses good properties for both food and non-food industrial use. Some effort has been done to commercialize the processing of matooke but there is still limited information on its processing into flour. It was imperative to carry out an in-depth study to bridge the following gaps: lack of accurate information on the maturity window within which matooke for processing into flour can be harvested leading to non-uniform quality of matooke flour; there is no information on moisture sorption isotherm for matooke from which the minimum equilibrium moisture content in relation to temperature and relative humidity is obtainable, below which the dry matooke would be microbiologically shelf-stable; and lack of information on drying behavior of matooke and standardized processing parameters for matooke in relation to physicochemical properties of the flour. The main objective of the study was to establish the optimum harvest maturity window and optimize the processing parameters for obtaining standardized microbiologically shelf-stable matooke flour with good starch quality attributes. This research was designed to: i) establish the optimum maturity harvest window within which matooke can be harvested to produce a consistent quality of matooke flour, ii) establish the sorption isotherms for matooke, iii) establish the effect of process parameters on drying characteristics of matooke, iv) optimize the drying process parameters for matooke, v) validate the models of maturity and optimum process parameters and vi) standardize process parameters for commercial processing of matooke. Samples were obtained from a banana plantation at Presidential Initiative on Banana Industrial Development (PIBID), Technology Business Incubation Center (TBI) at Nyaruzunga – Bushenyi in Western Uganda. A completely randomized design (CRD) was employed in selecting the banana stools from which samples for the experiments were picked. The cultivar Mbwazirume which is soft cooking and commonly grown in Bushenyi was selected for the study. The static gravitation method recommended by COST 90 Project (Wolf et al., 1985), was used for determination of moisture sorption isotherms. A research dryer developed for this research. All experiments were carried out in laboratories at TBI. The physiological maturity of matooke cv. mbwazirume at Bushenyi is 21 weeks. The optimum harvest maturity window for commercial processing of matooke flour (Raw Tooke Flour - RTF) at Bushenyi is between 15-21 weeks. The finger weight model is recommended for farmers to estimate harvest maturity for matooke and the combined model of finger weight and pulp peel ratio is recommended for commercial processors. Matooke isotherms exhibited type II curve behavior which is characteristic of foodstuffs. The GAB model best described all the adsorption and desorption moisture isotherms. For commercial processing of matooke, in order to obtain a microbiologically shelf-stable dry product. It is recommended to dry it to moisture content below or equal to 10% (wb). The hysteresis phenomenon was exhibited by the moisture sorption isotherms for matooke. The isoteric heat of sorption for both adsorptions and desorption isotherms increased with decreased moisture content. The total isosteric heat of sorption for matooke: adsorption isotherm ranged from 4,586 – 2,386 kJ/kg and desorption isotherm from 18,194– 2,391 kJ/kg for equilibrium moisture content from 0.3 – 0.01 (db) respectively. The minimum energy required for drying matooke from 80 – 10% (wb) is 8,124 kJ/kg of water removed. Implying that the minimum energy required for drying of 1 kg of fresh matooke from 80 - 10% (wb) is 5,793 kJ. The drying of matooke takes place in three steps: the warm-up and the two falling rate periods. The drying rate constant for all processing parameters ranged from 5,793 kJ and effective diffusivity ranged from 1.5E-10 - 8.27E-10 m2/s. The activation energy (Ea) for matooke was 16.3kJ/mol (1,605 kJ/kg). Comparing the activation energy (Ea) with the net isosteric heat of sorption for desorption isotherm (qst) (1,297.62) at 0.1 (kg water/kg dry matter), indicated that Ea was higher than qst suggesting that moisture molecules travel in liquid form in matooke slices. The total color difference (ΔE*) between the fresh and dry samples, was lowest for effect of thickness of 7 mm, followed by air velocity of 6 m/s, and then drying air temperature at 70˚C. The drying system controlled by set surface product temperature, reduced the drying time by 50% compared to that of a drying system controlled by set air drying temperature. The processing parameters did not have a significant effect on physicochemical and quality attributes, suggesting that any drying air temperature can be used in the initial stages of drying as long as the product temperature does not exceed gelatinization temperature of matooke (72˚C). The optimum processing parameters for single-layer drying of matooke are: thickness = 3 mm, air temperatures 70˚C, dew point temperature 18˚C and air velocity 6 m/s overflow mode. From practical point of view it is recommended that for commercial processing of matooke, to employ multi-layer drying of loading capacity equal or less than 7 kg/m², thickness 3 mm, air temperatures 70˚C, dew point temperature 18˚C and air velocity 6 m/s overflow mode.

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

Physicochemical characterization of collagen fibers and collagen powder for self-composite film production

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Study of adsorption isotherms of green coconut pulp

O Brasil é considerado um dos maiores produtores e consumidores de frutas tropicais. O coco verde (Cocos nucifera L.) se destaca tanto em termos de produção e consumo quanto em quantidade de resíduos gerada por indústrias de água de coco e pelo consumo in natura. Portanto, existe uma necessidade de aproveitamento deste subproduto. Este trabalho teve por objetivo estudar as isotermas de adsorção da polpa de coco verde e determinação do calor isostérico de sorção. As isotermas de adsorção para as temperaturas de 30, 40, 50, 60 e 70 °C foram analisadas e evidenciaram curvas do tipo III, típicas de alimentos ricos em açúcares. Os dados experimentais de umidade de equilíbrio foram correlacionados por modelos da literatura. O modelo de GAB apresentou melhor concordância com os dados experimentais, entre os modelos avaliados. O calor isostérico de sorção é considerado um indicativo de forças atrativas intermoleculares entre os sítios de sorção de vapor de água, consequentemente, um importante fator para predizer a vida de prateleira de produtos desidratados.

Phase diagram for freeze-dried persimmon

Phase transitions of freeze-dried persimmon in a large range of moisture content were determined by differential scanning calorimetry (DSC). In order to study this transitions at low and intermediate moisture content domains, samples were conditioned by adsorption at various water activities (a(w) = 0.11-0.90) at 25 degreesC. For the high moisture content region, samples were obtained by water addition. At a(w) less than or equal to 0.75 two glass transitions were visible, with T(g) decreasing with increasing water activity due to water plasticizing effect. The first T(g) is due to the matrix formed by sugars and water, the second one, less visible and less plasticized by water, is probably due to macromolecules of the fruit pulp. At a(w) between 0.80 and 0.90 a devitrification peak appeared after T(g) and before T(m). At this moisture content range, the Gordon-Taylor model represented satisfactorily the matrix glass transition curve. At the higher moisture content range (a(w) > 0.90), the more visible phenomenon was the ice melting. T(g) appeared less visible because the enthalpy change involved in glass transition is practically negligible in comparison with the latent heat of melting. In the high moisture content domain T(g) remained practically constant around T(g)' (-56.6 degreesC). (C) 2001 Elsevier B.V. B.V. All rights reserved.

Thermodynamic and quality properties of lemon juice powder as affected by maltodextrin and Arabic gum

Sorption isotherms of lemon juice (LE) powders with and without additives-18% maltodextrin (MA) or 18% gum Arabic (GA) were determined at 20-50 degrees C. Addition of additives was shown to affect the isotherms in such a way that, at the same water activity, samples LE + GA and LE + MA presented lower equilibrium moisture content and were not so affected by varying temperature. The net isosteric heats of sorption of juice powders with additives were higher (less negative) than those of lemon juice powders, suggesting that there are more active polar sites in the product without addition of GA or MA. In general, the quality properties decreased with the addition of maltodextrin and gum arabic and it was obtained similar values for LE + GA and LE + MA.

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

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)