Rodrigo Silveira Vieira

Sargassum seaweed as biosorbent for heavy metals

Abstract Six different species of non-living Sargassum biomass were compared on the basis of their equilibrium Cd and Cu uptake in order to evaluate potential variability in the sorption performance of different Sargassum species. Biosorption uptakes for Cd at the optimal pH of 4.5 ranged from q max =0.90xa0mmol/g for Sargassum sp. 1 to 0.66xa0mmol/g for S. filipendula I representing a 36% difference. Three species were evaluated for their Cu uptake where q max =0.93xa0mmol/g for S. vulgare ; 0.89xa0mmol/g for S. filipendula I, and 0.80 for S. fluitans , representing a 16% difference between the lowest and highest values. Potentiometric titrations were carried out on S. vulgare, S. fluitans and S. filipendula I and yielded the similar results of 1.5xa0mmol/g weakly acidic sites for S. vulgare and S. fluitans , and 1.6xa0mmol/g for S. filipendula I. Estimates of 0.3xa0mmol/g of strongly acidic sites for S. fluitans and S . filipendula I and 0.5xa0mmol/g for S. vulgare were obtained. The total number of active sites averaged 1.9±0.1xa0mmol/g. The elution efficiency for Cu-desorption from S. filipendula was determined for CaCl 2 , Ca(NO 3 ) 2 , and HCl at various concentrations and solid:liquid ratios (S/L). The highest elution efficiency was >95% for Cu for all elutants at S/L=1xa0g/l and decreased for both calcium salts with increasing S/L to less than 50% at S/L=10xa0g/l as a new batch sorption equilibrium was reached quickly. CaCl 2 was chosen to be the most suitable metal-cation desorbing agent.

Characterization of calcium oxide catalysts from natural sources and their application in the transesterification of sunflower oil

The catalytic activities of calcium oxide obtained from natural sources (crab shell and eggshell) were characterized and evaluated in the transesterification of vegetable oil. These catalysts are mainly composed of calcium carbonate, which is partially converted into CaO after calcination (900°C for 2h). The catalysts have some advantages, such as abundant occurrence, low cost, porous structure, and nontoxic. The materials were characterized by XRD, FTIR, TG/DTG, CO2-TPD, XPS, SEM, and BET methods. The thermal treatment produces small particles of CaCO3 and CaO that are responsible for the catalytic activity. The conversion from triglycerides to methyl ester was not observed in transesterification carried out using natural crab shell and eggshell. Under optimized reaction conditions, the conversions to YFAME using the calcined catalysts were: crab shell (83.10±0.27 wt.%) and eggshell (97.75±0.02 wt.%). These results, showed that these materials have promising viability in transesterification for biodiesel production.

Characterization and evaluation of copper and nickel biosorption on acidic algae Sargassum Filipendula

The marine algae Sargassum filipendula was collected from Sao Paulo seashore (Brazil) and submitted to treatment with acid. The biosorption mechanisms of Cu2+ and Ni2+ ions onto acidic algae Sargassum filipendula were examined using various analytical techniques: Fourier-transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and potentiometric titration (pHZPC). The effect of acidic treatment on algae by hydrochloric acid (pH 2.0, 3.0, 4.0 and 5.0) was evaluated for Cu2+ and Ni2+ adsorption. Alginate was extracted from raw algae and the two types of acids present in the biomass (β-D-mannuronic (M) and α-L-guluronic (G) acid) were characterized by 13C NMR. The M/G ratio was found to be 0.50. According to the pHZPC analysis, at a pH higher than 5.5 the acidified algae surface presents a negative charge. The FT-IR analyses showed that the main chemical groups involved in the biosorption were carboxylic, alcoholic, sulfonate and amino groups.

Blood protein adsorption on sulfonated chitosan and κ-carrageenan films.

Many strategies have been reported to improve compatibility of biopolymers using chemical and physical modifications. One possibility is the introduction of sulfonate groups (R-SO3(-)) in the chitosan chain. Another biopolymer with similar characteristics to those of heparin is κ-carrageenan. This study proposed to investigate the application of these two polymers, based on their potential for globular protein adsorption (BSA and fibrinogen). Polymeric films of chitosan and κ-carrageenan were prepared; all films were characterized by elemental analyses, FTIR, XPS and SEM. Characterization techniques showed that the chitosan chain was modified and confirmed the existence of sulfonate groups, as well as in the κ-carrageenan chain, indicating surfaces with similar chemical properties to those of heparin. The effect of charge density was observed for each adsorption condition (BSA at pH 5.0 and 7.4). A more pronounced adsorption rate was observed at pH 5.0 than at pH 7.4 and equilibrium adsorption was achieved, in both cases, after approximately 20 min. The equilibrium data indicate a lower adsorption rate for the sulfonated chitosan film, in comparison to the other films. These results confirm the potential of modified chitosan for use in applications in which globular protein adsorption should be avoided.

Kinetic and Thermodynamic Study on the Liquid Phase Adsorption by Starchy Materials in the Alcohol-Water System

Improving adsorptive processes demands a constant search for new adsorbents. In the case of alcohol-water separation, zeolites are widely used. The use of new adsorbents as a substitute for zeolites, mainly starch, has been proposed recently. This work is a thermodynamic and kinetic study of liquid phase adsorption of water from methanol, ethanol, propanol and butanol-water mixtures using starch as the adsorbent. The thermodynamic data were obtained by means of the static method at three different temperatures (25, 40 and 50°C), and were correlated by the Langmuir isotherm. The kinetic data were obtained in a finite liquid bath cell. The influence of temperature and molecular chain length of the alcohol on the capacity and adsorption rate were determined.

Adsorption of Copper(II) and Mercury(II) Ions onto Chemically-modified Chitosan Membranes: Equilibrium and Kinetic Properties

Cross-linked chitosan was synthesized with glutaraldehyde (chitosan–GLA) and epichlorohydrin (chitosan–ECH). The structures of these matrices were characterized by elemental analysis, Fourier-transform infrared spectrometry (FT-IR), the degree of de-acetylation and the surface topography as determined via scanning electron microscopy (SEM). After promoting interaction with the metal ion, the adsorbent was also studied using FT-IR and energy dispersive X-ray spectroscopy (EDXS). Adsorption studies for Cu(II) and Hg(II) ions were carried out in a batch process. The adsorption kinetics were tested using three models, viz. pseudo-first-order, pseudo-second-order and intra-particle diffusion. The experimental kinetic data were best fitted by the pseudo-second-order model for Cu(II) ions (R2 ≥ 0.98) and for Hg(II) ions (R2 = 0.99). Higher rate constants (k2) were obtained for the adsorption of Cu(II) ions onto chitosan–GLA [1.40 g/(mmol h)] and for Hg(II) ions onto raw chitosan [5.65 g/(mmol h)]. The adsorption rate depended on the concentration of Cu(II) and Hg(II) ions on the adsorbent surface and on the quantity of ions adsorbed at equilibrium. At 293 K, the Langmuir–Freundlich model provided a better fit to the adsorption isotherms on both raw and cross-linked chitosan membranes. The maximum adsorption capacity for Cu(II) ions was obtained with the chitosan–GLA matrix (2.7 mmol/g). A maximum adsorption capacity of 3.1 mmol/g was attained for Hg(II) ions onto the chitosan–ECH matrix.

Produção e caracterização de microesferas de quitosana modificadas quimicamente

Chitosan microspheres can be used as biomaterial, in biotechnology processes and as adsorbents. This work is concerned with the production of chitosan microspheres using spraying and coagulation processes, which allows us to control the operating parameters and to produce chitosan microspheres of several ranges and sizes. The microspheres were modified chemically in order to study their thermal, mechanical and chemical resistance. The methods used were: 1) crosslinking with glutaraldehyde; 2) crosslinking with epichlorohydrin; 3) acetylation. The microspheres obtained presented mean particle size of 140 µm and standard deviation of 11.9 µm. The modified microspheres showed thermal degradation around 300 °C, an increase of chemical stability using HCl solution and a decrease of mechanical resistance.

Dynamic adsorption of chromium ions onto natural and crosslinked chitosan membranes for wastewater treatment

Water pollution with heavy metals is a matter of major concern for public health and also for natural resource management. The present study investigated the effect of chemical modifications on biopolymeric adsorbents (based on chitosan membranes) for chromium removal using fixed-bed dynamic adsorption technique. Parameters such as flow rate, initial concentration and crosslinking agents were evaluated, from a practical point-of-view, in order to optimize the adsorption capacity of natural, glutaraldehyde and epichlorohydrin crosslinked chitosan membranes. The adsorption capacity of natural and epiclorohydrin-crosslinked chitosan membranes were very close to each other; however, glutaraldehyde-crosslinked chitosan membranes presented nearly twice the adsorption capacity compared to the other membranes, being the most promising adsorbent in such mass-transfer systems.

In vitro evaluation of anti-calcification and anti-coagulation on sulfonated chitosan and carrageenan surfaces

In recent years, great effort has been devoted to the development of biomaterials that come into contact with blood. The surfaces of these materials need to be of suitable mechanical strength, and present anti-thrombogenic and anti-calcification properties. Chitosan is a natural polymer that has attracted attention due to its potential to act as a biomaterial. However, chitosan contains amino groups in its structure that may promote thrombogenesis and calcification. A strategy to reduce these properties constitutes the introduction of sulfonate groups (R-SO3-) in the chitosan chain. Another interesting biopolymer with similar characteristics to those of heparin is carrageenan, which has sulfate groups in its structure. As such, we evaluated “in vitro” calcification and thrombogenic processes on surfaces of pristine and sulfonated chitosan and on polyelectrolyte complexes (PEC) of chitosan and carrageenan. Results indicate that PEC demonstrate significant reductions in calcification and thrombogenic potential, probably due to the presence of sulfonate groups in both the carrageenan and treated chitosan.

BSA and fibrinogen adsorption on chitosan/κ-carrageenan polyelectrolyte complexes.

PECs of chitosan/κ-carrageenan are prepared in three different volumetric rations. The complex formation is characterized in order to evaluate the blending formation. Blood compatibility is evaluated by protein adsorption (BSA and fibrinogen) and PEC toxicities are determined with fibroblast cell viability and proliferation. The swelling degree of PECs decreases when the amount of chitosan increases. Due to the linked film formation, PECs decrease BSA adsorption and increase fibrinogen adsorption when compared to the pristine chitosan and κ-carrageenan films. Although pristine chitosan and κ-carrageenan films produced similar cell expansion and viability, the PEC 50:50 vol% chitosan/κ-carrageenan PEC may be acceptable as a new scaffold for cell therapies, due to their effect on cell survival.