Kinetic,isotherm and thermodynamic investigations on adsorption of trace elements and pigments from soybean oil using high voltage electric field-assisted bleaching: A comparative study

In this study, the amounts of trace elements (Fe (II) and Cu (II)) and pigments (chlorophyll and carotenoid) in soybean oil were evaluated under high voltage electric field (HVEF) bleaching method at different voltage (10 and 20 kV), temperature (35–65 °C), time (0−30 min) and clay percentage (0.5–2 %) and then were compared to the industrial bleaching method (IBM). The kinetic data of ions and pigments adsorbed on activated bentonite clay under IBM and HVEF at two voltages of 10 and 20 kV followed the mechanism of the pseudo-first-order model (PFOM). The carotenoid and chlorophyll equilibrium data followed a Freundlich isotherm type model, which demonstrated multilayer adsorption under HVEF. The thermodynamic parameters (ΔG°, ΔH°, and ΔS°) displayed that the adsorption of trace metal ions and pigments on bentonite clay under IBM and HVEF were feasible, endothermic and spontaneous between 35 and 65 °C. The results indicated that the HVEF, especially at higher voltage, has a high remarkable capability to remove metal ions and pigments from soybean oil than the IBM. The highest removal capacity for metal and pigments of soybean oil bleaching were obtained in the order of HVEF-20 kV > HVEF-10 kV > IBM.     

The surface structure of a complex substrate revealed by enzyme kinetics and Freundlich constants for α-amylase interaction with the surface of starch

Background

Starch is a main source of carbohydrate in human diets, but differences are observed in postprandial glycaemia following ingestion of different foods containing identical starch contents. Such differences reflect variations in rates at which different starches are digested in the intestine. In seeking explanations for these differences, we have studied the interaction of α-amylase with starch granules. Understanding this key step in digestion should help with a molecular understanding for observed differences in starch digestion rates.

Methods

For enzymes acting upon solid substrates, a Freundlich equation relates reaction rate to enzyme adsorption at the surface. The Freundlich exponent (n) equals 2/3 for a liquid-smooth surface interface, 1/3 for adsorption to exposed edges of ordered structures and 1.0 for solution–solution interfaces. The topography of a number of different starch granules, revealed by Freundlich exponents, was compared with structural data obtained by differential scanning calorimetry and Fourier transform infrared spectroscopy with attenuated total internal reflectance (FTIR-ATR).

Results

Enzyme binding rate and FTIR-ATR peak ratio were directly proportional to n and Δ_gelH was inversely related to n. Amylase binds fastest to solubilised starch and to granules possessing smooth surfaces at the solid–liquid interface and slowest to granules possessing ordered crystalline surfaces.

Conclusions

Freundlich exponents provide information about surface blocklet structures of starch that supplements knowledge obtained from physical methods.

General Significance

Nanoscale structures at the surface of starch granules influence hydrolysis by α-amylase. This can be important in understanding how dietary starch is digested with relevance to diabetes, cardiovascular health and cancer.     

Sorption of Co, Cu, Ni and Zn from industrial effluents by the submerged aquatic macrophyte Myriophyllum spicatum L.

The submerged aquatic plant Myriophyllum spicatum L. (Eurasian water milfoil) has been suggested as an efficient plant species for the treatment of metal-contaminated industrial wastewater. The process of metal removal by plants involves a combination of rapid sorption on the surface and slow accumulation and translocation in the biomass. This study focussed on the sorption/desorption characteristics of the surface of M. spicatum for Co, Cu, Ni and Zn. Batch sorption tests with mixed metal solutions covering a range of 0, 1, 5, 10, 50 and 100 mg l⁻¹ of each metal, were performed. For Co, Ni and Zn, the sorption process was well described by the Langmuir model, whereas sorption of Cu was better described by the Freundlich model. The biomass showed the highest affinity for Cu and Zn. Langmuir sorption maxima of Co, Ni and Zn were 2.3, 3.0 and 6.8 mg g⁻¹ DM, respectively. At the highest initial concentration of 100 mg l⁻¹, a maximum of 29 mg g⁻¹ DM of Cu was sorbed onto the surface of the biomass. Desorption by 0.1 M HCl did not fully recover the metals sorbed onto the surface and there was evidence of leaching from within the biomass. Recovery of heavy metals and regeneration of the biomass by washing with 0.1 M HCl was therefore not suggested as a viable strategy.     

Filter materials for phosphorus removal from wastewater in treatment wetlands—A review

This paper aims to collect and analyse existing information on different filter media used for phosphorus (P) removal from wastewater in constructed wetlands. The most commonly used materials are categorized as natural materials (considered in 39 papers), industrial byproducts (25 papers) and man-made products (10 papers). A majority of studies on sorbents have been carried out in lab-scale systems as batch experiments, and only very few studies have highlighted results on full-scale systems. Among the great variety of filter media studied, most of materials had a pH level >7 and high Ca (CaO) content. The highest P-removal capacities were reported for various industrial byproducts (up to 420 g P kg⁻¹ for some furnace slags), followed by natural materials (maximum 40 g P kg⁻¹ for heated opoka) and man-made filter media (maximum 12 g P kg⁻¹ for Filtralite). We found a significant positive Spearman Rank Order Correlation between the P retention and CaO and Ca content of filter materials (R² = 0.51 and 0.43, respectively), whereas the relation of P retention to pH level was weak (R² = 0.22) but significant. There is probably an optimal level of hydraulic loading rate at which the P removal is the highest. Additional important factors determining the applicability of filter materials in treatment wetlands such as saturation time, availability at a local level, content of heavy metals, and the recyclability of saturated filter media as fertilizer should be taken into consideration.     

Copper adsorption kinetics of cultured algal cells and freshwater phytoplankton with emphasis on cell surface characteristics

Comparative studies were carried out on the adsorption of copper by a range of laboratory-cultured algae and freshwater phytoplankton samples. The level of surface mucilage associated with the cultured algae ranged from high (Anabaena spiroides, Eudorina elegans) to moderate (Anabaena cylindrica, Microcystis aeruginosa) to complete absence (Chlorella vulgaris, Asterionella formosa, Aulacoseira varians, Ceratium hirundinella). With laboratory cultures, the rapid uptake, EDTA release and quantitative similarity between living and dead (glutaraldehyde-fixed) algae were consistent with physical binding of Cu at the cell surface. The higher Cu adsorption per unit surface area and longer adsorption time of mucilaginous algae in the time-course study, and the relatively high level of Cu bound to mucilage found by X-ray microanalysis suggest that mucilage played an important role in metal binding. For all species examined, Cu adsorption kinetics (external Cu concentrations 1 to 1000 mg L⁻¹) showed a clear fit to the Freundlich, but not the Langmuir isotherm, indicating a monolayer adsorption model with heterogenous binding sites. The Freundlich adsorption capacity constant (K_f) was higher in mucilaginous (3.96–12.62) compared to nonmucilaginous (0.36–3.63) species, but binding intensity (Freundlich constant 1/n) did not differ between the two cell types. The results suggest that mucilaginous algal species may have potential as biosorbents for treatment of industrial effluents containing heavy metals. Investigation of the Cu adsorption behavior of four mixed phytoplankton samples also revealed a good fit to the Freundlich, but not the Langmuir, isotherm. Freundlich constants were in the range 2.3–3.2 for samples dominated by Chlorophyta, Bacillariophyta and Cyanophyta, but recorded a value of 7.4 in the sample dominated by Dinophyta. Comparison with data from laboratory monocultures suggested that the adsorption kinetics of mixed environmental phytoplankton samples cannot be predicted simply in terms of the major algal species.     

Sorption of chromium(VI) from aqueous solution by cassava (Manihot sculenta Cranz.) waste biomass

The sorption of highly toxic Cr(VI) ions by cassava waste biomass was quantitatively investigated. The sorption was found to be influenced by several physico-chemical factors such as agitation speed, temperature, contact time, pH, and sorbent/sorbate ratio. The adsorption data at equilibrium were fitted to Freundlich and Langmuir isotherms. The monolayer sorption capacity was found to be 61.79 mg of Cr(VI) per gram of biomass. The kinetics of Cr(VI) adsorption to pure cassava-tuber-bark wastes were determined based on a pseudo-second-order-rate model using the batch-sorption technique at a temperature of 30 degrees. The kinetics data suggest that the adsorption process is exothermic, and that the rate-limiting step is physisorption. Negative DeltaG(ads) values indicate that the adsorption is spontaneous and exothermic in nature. Also, under optimal conditions (in agitated 1M H(2)SO(4) at 30 degrees), the cassava waste biomass appears to be recyclable.     

Sorption behavior of Cd, Cu, Pb, and Zn and their interactions in phytoremediated soil

The aim of our study was to compare the sorption properties of a contaminated soil before and after two types of phytoremediation (natural phytoextraction vs. phytostabilization with dolomite limestone (DL) application). Soil from a pot experiment in controlled greenhouse conditions performed for two vegetation periods was used for the study. Lead, as the main contaminant in the studied soil, was easily desorbed by Cu, especially due to the increased affinity of Cu for soil organic matter; hence input of Cu to the studied soil can present another environmental risk in soils contaminated with other metals (such as Pb). In addition, the sorption behavior of chosen metals from single-element solutions differed from multielement solutions. The obtained results proved the different sorption behavior of metals in the single-element solution compared to the multi-element ones. Soil sorption behavior of Cd, Cu, and Zn decreased with the presence of the competitive metals; nevertheless, Pb sorption potential was not influenced by other competitive metals. Natural phytoextraction showed no significant effect on the sorption of Cd, Cu, Pb, and Zn onto the soil On the other hand, phytostabilization associated with DL application improved the soil sorption efficiency of all chosen metals, especially of Cu.     

Methods for Estimating the Parameters of Nonlinear Adsorption Isotherms of Langmuir and Freundlich Types from a Response Curve of Pulse Input of an Adsorbate

Methods for estimating the parameters of nonlinear adsorption isotherms of Langmuir and Freundlich types from a pulse response curve are proposed here based on the migration rate of an adsorbate at a constant concentration and the mean residence time of the adsorbate in a bed. The methods were used to estimate the parameters in isotherms for various combinations of adsorbent and adsorbate. The isotherms estimated by the proposed methods were compared with those estimated by conventional methods. It was demonstrated that the proposed methods could evaluate the parameters with fairly good precision when the type of isotherm was known. The criteria for discriminating the type of isotherm from the pulse response curve are also described.     

Metabolism-independent binding of toxic metals by Ulva lactuca: cadmium binds to oxygen-containing groups, as determined by NMR

The metabolism-independent metal binding characteristics of Ulva lactuca were investigated using both freeze-dried thalli and cell walls stripped of intracellular material by incubation in Triton-X followed by methanol. Biosorption of Cd, Zn, Cu and Co by freeze-dried thallus was concentration-dependent and followed Freundlich and Langmuir isotherms. The Freundlich plot suggested that freeze-dried U. lactuca had the greatest binding affinity for Cu compared with Cd, Zn and Co. The BET (Brunauer–Emmett–Teller) plot, which indicates a more complex form of adsorption, and the Scatchard plot were not adequate models for Cu adsorption. The Scatchard plot of Cd suggested that two Cd binding sites were available on the freeze-dried thallus, with the second, lower affinity site only becoming available at Cd loading capacities greater than 4.9mmol g dry wt. Cd nuclear magnetic resonance (NMR) studies confirmed that two binding sites were available for Cd on the freeze-dried algal powder, though only one was available on the cell wall, and that the affinity of the binding sites was greater for Cu than for Cd. The results of the NMR experiments suggested that Cd binds to oxygen-containing functional groups in the algal powder and on the cell wall. It is proposed that sulphate or hydroxyl groups attached to polysaccharide subunits are possible sites.