RESUMO
Driven by climate change and human activity, Sargassum blooming rates have intensified, producing copious amount of the invasive, pelagic seaweed across the Caribbean and Latin America. Battery recycling and lead-smelter wastes have heavily polluted the environment and resulted in acute lead poisoning in children through widespread heavy metal contamination particular in East Trinidad. Our study details a comprehensive investigation into the use of Sargassum (S. natans), as a potential resource-circular feedstock for the synthesis of calcium alginate beads utilized in heavy metal adsorption, both in batch and column experiments. Here, ionic cross-linking of extracted sodium alginate with calcium chloride was utilized to create functional ion-exchange beads. Given the low quality of alginates extracted from Sargassum which produce poor morphological beads, composite beads in conjunction with graphene oxide and acrylamide were used to improve fabrication. Stand-alone calcium alginate beads exhibited superior Pb2+ adsorption, with a capacity of 213 mg g-1 at 20 °C and pH 3.5, surpassing composite and commercial resins. Additives like acrylamide and graphene oxide in composite alginate resins led to a 21-40% decrease in Pb2+ adsorption due to reduced active sites. Column operations confirmed Alginate systems' practicality, with 20-24% longer operating times, 15 times lower adsorbent mass on scale-up and 206% smaller column diameters compared to commercial counterparts. Ultimately, this study advocates for Sargassum-based Alginate ion-exchange beads as a bio-based alternative in Trinidad and developing nations for dealing with heavy metal ion waste, offering superior heavy metal adsorption performance and supporting resource circularity.
Assuntos
Alginatos , Resinas de Troca Iônica , Chumbo , Sargassum , Sargassum/química , Alginatos/química , Adsorção , Chumbo/química , Resinas de Troca Iônica/químicaRESUMO
Polystyrene divinylbenzene-based ion exchange resins are employed extensively within nuclear power plants (NPPs) and research reactors for purification and chemical control of the cooling water system. To maintain the highest possible water quality, the resins are regularly replaced as they become contaminated with a range of isotopes derived from compromised fuel elements as well as corrosion and activation products including 14C, 60Co, 90Sr, 129I, and 137Cs. Such spent resins constitute a major proportion (in volume terms) of the solid radioactive waste generated by the nuclear industry. Several treatment and conditioning techniques have been developed with a view toward reducing the spent resin volume and generating a stable waste product suitable for long-term storage and disposal. Between them, pyrolysis emerges as an attractive option. Previous work of our group suggests that the pyrolysis treatment of the resins at low temperatures between 300 and 350 °C resulted in a stable waste product with a significant volume reduction (>50%) and characteristics suitable for long-term storage and/or disposal. However, another important issue to take into account is the complexity of the off-gas generated during the process and the different technical alternatives for its conditioning. Ongoing work addresses the characterization of the ion exchange resin treatment's off-gas. Additionally, the application of plasma technology for the treatment of the off-gas current was studied as an alternative to more conventional processes utilizing oil- or gas-fired post-combustion chambers operating at temperatures in excess of 1000 °C. A laboratory-scale flow reactor, using inductively coupled plasma, operating under sub-atmospheric conditions was developed. Fundamental experiments using model compounds have been performed, demonstrating a high destruction and removal ratio (>99.99%) for different reaction media, at low reactor temperatures and moderate power consumption. The role of H2O as an important participant of the oxidation mechanisms in plasma conditions was established. The combination of both processes could represent a simple, safe, and effective alternative for treating spent ion exchange resins with a large reduction of generated gaseous byproducts in fuel cycle facilities where processes that utilize open flames are undesirable.
Assuntos
Gases/análise , Resinas de Troca Iônica/química , Pirólise , Resíduos Radioativos , Gerenciamento de Resíduos/métodos , Radioisótopos de Césio , Radioisótopos de Cobalto , Radioisótopos do Iodo , Troca Iônica , Centrais Nucleares , Oxirredução , Gases em Plasma , Radioisótopos de Estrôncio , Resíduos/análiseRESUMO
Hot pressurized liquid extraction has been used to obtain polyphenols; however, its operating conditions can generate hydroxymethylfurfural, a potential human carcinogen. The addition of ethanol can reduce process temperatures and retain extraction efficiencies, but the ethanol may reduce the recovery of polyphenols in the subsequent purification stage, affecting the antioxidant properties of the extracts. This study evaluates a combined hot pressurized liquid extraction-resin purification process to obtain polyphenol extracts from spent ground coffee reduced in hydroxymethylfurfural. A multifactorial design was developed to determine the combined effect of the extraction (ethanol content: 0-16% and temperature: 60-90 °C) and purification (ethanol: 60-80%) conditions on some chemical properties of the extracts. The highest recovery of polyphenols (~8 mg GAE/g dry coffee solids) and reduction of hydroxymethylfurfural (95%) were obtained at 90 °C and 16% of ethanol during extraction and 80% of ethanol during purification. These operating conditions retained the antioxidant capacity of the crude extract between 60% and 88% depending on the determination method and recovered 90, 98, and 100% of 4-feruloylquinic acid, epicatechin, and 5-feruloylquinic acid, respectively after purification. The combined process allows differential polyphenols' recovery and enhances the safety of the extracts. Our computational chemistry results ruled out that the overall selectivity of the integrated process was correlated with the size of the polyphenols.
Assuntos
Antioxidantes/isolamento & purificação , Catequina/isolamento & purificação , Coffea/química , Ácidos Cumáricos/isolamento & purificação , Extração Líquido-Líquido/métodos , Sementes/química , Etanol/química , Análise Fatorial , Furaldeído/análogos & derivados , Furaldeído/química , Humanos , Resinas de Troca Iônica/química , Extratos Vegetais/química , PressãoRESUMO
In this work, the combined use of ultrasound energy and molecular sieves was investigated for the synthesis of ethyl butyrate, ester with mango and banana notes, catalyzed by the immobilized lipase from Thermomyces lanuginosus (Lipozyme TL-IM). Initially, the best concentrations of biocatalysts (35%) and butyric acid (0.7M) were tested using ultrasound as an alternative to mechanical agitation. The amount of acid in the reaction could be increased by 2-fold when compared to previous works where mechanical agitation was used. In the next step, substrate molar ratio and reaction temperature were optimized and the best conditions were at their lowest levels: 1:1 (acid:alcohol), and 30°C, reaching 61% of conversion in 6h. Molecular sieves (3Å) were added to optimized reaction medium in order to remove the formed water and improve the maximum yield. The reaction yield increased 1.5 times, reaching 90% of conversion in 6h, when 60mg of molecular sieves per mmol of butyric acid was used. Finally, the reuse of Lipozyme TL-IM for the ultrasound-assisted synthesis of ethyl butyrate was verified for 10 batches, without any appreciable loss of activity, whereas in systems using mechanical agitation, the biocatalyst was completely inactivated after 5 batches. These results suggest that the combined use of ultrasound and molecular sieves greatly improve esterification reactions by stabilizing the enzyme and increasing yields.
Assuntos
Ascomicetos/enzimologia , Biocatálise , Butiratos/síntese química , Técnicas de Química Sintética/métodos , Enzimas Imobilizadas/metabolismo , Lipase/metabolismo , Ultrassom , Butiratos/química , Enzimas Imobilizadas/química , Esterificação , Resinas de Troca Iônica/química , Lipase/química , TemperaturaRESUMO
A simple and green technique named polymer-supported ionic liquid solid phase extraction (PSIL-SPE) was developed for mercury (Hg) species determination. Inorganic Hg (InHg) species was complexed with chloride ions followed by its introduction into a flow injection on-line system to quantitatively retain the anionic chlorocomplex (HgCl4(2-)) in a column packed with CYPHOS(®) IL 101-impregnated resin. The trapped InHg was then reduced with stannous chloride (SnCl2) and eluted with the same flow of reducing agent followed by cold vapor atomic absorption spectrometry (CV-AAS) detection. Organic mercury species (OrgHg) did not interact with the impregnated resin and were not retained into the column. Total concentration of OrgHg was evaluated by difference between total Hg and InHg concentration. A 95% extraction efficiency was achieved for InHg when the procedure was developed under optimal experimental conditions. The limit of detection obtained for preconcentration of 40 mL of sample was 2.4 ng L(-1) InHg. The relative standard deviation (RSD) was 2.7% (at 1 µg L(-1) InHg and n=10) calculated from the peak height of absorbance signals (Gaussian-shape and reproducible peaks). This work reports the first polymer-supported IL solid phase extraction approach implemented in a flow injection on-line system for determination of Hg species in mineral, tap and river water samples.
Assuntos
Água Doce/química , Compostos de Metilmercúrio/isolamento & purificação , Compostos de Fenilmercúrio/isolamento & purificação , Extração em Fase Sólida/métodos , Poluentes Químicos da Água/isolamento & purificação , Concentração de Íons de Hidrogênio , Resinas de Troca Iônica/química , Limite de Detecção , Compostos Organofosforados/química , Oxirredução , Reprodutibilidade dos Testes , Espectrofotometria Atômica , Compostos de Estanho/químicaRESUMO
A radiochemical method has been adapted to determine (59)Ni and (63)Ni in samples of radioactive wastes from the water cleanup system of the IEA-R1 nuclear research reactor. The process includes extraction chromatographic resin with dimethylglyoxime (DMG) as a functional group. Activity concentrations of (59)Ni and (63)Ni were measured, respectively, by X-ray spectrometry and liquid scintillation counting, whereas the chemical yield was determined by ICP-OES. The average ratio of measured activity concentrations of (63)Ni and (59)Ni agree well with theory.
Assuntos
Carvão Vegetal/química , Resinas de Troca Iônica/química , Níquel/análise , Resíduos Radioativos/análise , Radioisótopos/análise , Radiometria/métodos , Brasil , Carvão Vegetal/análise , Resinas de Troca Iônica/análise , Teste de Materiais/métodos , Níquel/química , Doses de Radiação , Radioisótopos/químicaRESUMO
The performance of a system composed of an organic cation exchanger (Dowex 50Wx8) and a chelating agent (EDTA) previously described for the successful production of (90)Y via a (90)Sr/(90)Y generator is assessed under dynamic conditions. In an attempt to overcome the established limitation of ion-exchange resins for the separation of subcurie quantities of activity, (90)Y is repeatedly isolated from an 11.8-GBq (320 mCi) (90)Sr cow using a three-column tandem arrangement. The high recovery and radionuclidic purity obtained for (90)Y and the parameters of the separation (time, eluant concentration, pH and flow rate range) strongly suggest that Ci quantities of (90)Y can be handled satisfactorily by the ion-exchange method. No replacement or treatment of the cow, low waste generation and (90)Sr losses less than 0.1% after each run were observed during the present study which, in combination with the low cost of this resin, may result in an attractive alternate method for the production of large quantities of (90)Y.
Assuntos
Quelantes/química , Cromatografia por Troca Iônica/métodos , Resinas de Troca Iônica/química , Ácido Edético/química , Radioisótopos de Estrôncio/química , Radioisótopos de Estrôncio/isolamento & purificação , Fatores de Tempo , Radioisótopos de Ítrio/química , Radioisótopos de Ítrio/isolamento & purificaçãoRESUMO
An extracellular lipase was isolated from Pseudomona cepacia by expanded bed adsorption on an Amberlite 410 ion-exchange resin. Enzyme characterization and hydrodynamic study of a chromatography column were done. Enzyme purification was done at three condition of expanded bed height (H): at one and half (6cm), at two (8cm) and at three (12cm) times the fixed bed height (H(0)=4cm). The results showed that the experimental data was fitted to the Richardson and Zaki equation, and the comparison between the experimental and calculated terminal velocities showed low relative error. In enzyme purification for better condition, a purification factor of about 80 times was found at 6cm of expanded bed height, or 1.5 times of expansion degree. Purified lipase had an optimal pH and a temperature of 8 and 37 degrees C, respectively.
Assuntos
Álcalis/química , Burkholderia cepacia/enzimologia , Lipase/isolamento & purificação , Adsorção , Proteínas de Bactérias/análise , Soluções Tampão , Concentração de Íons de Hidrogênio , Hidrólise , Resinas de Troca Iônica/química , Azeite de Oliva , Óleos de Plantas , TemperaturaRESUMO
Protein adsorption of large proteins on ion-exchange membrane columns was theoretically and experimentally investigated using batch and fixed-bed systems. Thyroglobulin was used as the model protein. The study strongly suggests that part of the protein is physically retained inside the column during frontal mode operation. These experimental results were used to obtain a filtration function of the chromatographic system. In the theoretical analysis of the frontal protein adsorption, a model was integrated by the serial coupling of the membrane-transport model, the filtration model and the system-dispersion model. Two different techniques were employed in the estimation of the maximum adsorption capacity, the equilibrium desorption constant and the forward interaction rate constant, which are the parameters of the membrane-transport model. The fit of the model to the experimental data was not possible using the equilibrium parameters obtained in the batch experiments. The parameter estimation using a simplex optimization routine coupled to the solution of the partial differential model equations yields full prediction of the adsorption phenomena.
Assuntos
Cromatografia por Troca Iônica/métodos , Resinas de Troca Iônica/química , Membranas Artificiais , Modelos Químicos , Proteínas/química , Proteínas/isolamento & purificação , Simulação por Computador , Desenho Assistido por Computador , Desenho de Equipamento , Análise de Falha de Equipamento , Peso Molecular , Reprodutibilidade dos Testes , Sensibilidade e EspecificidadeRESUMO
In this work, flame atomic absorption spectrometry (FAAS) was used as a detector for the determination of zinc in natural water samples with a flow-injection system coupled to solid-phase extraction (SPE). In order to promote the on-line preconcentration of zinc from samples a minicolumn packed with 35 mg of a styrene-divinylbenzene resin functionalized with (S)-2-[hydroxy-bis(4-vinylphenyl)methyl]pyrrolidine-1-carboxylic acid ethyl esther was utilized. The system operation was based on Zn(II) ion retention at pH 9.5 +/- 0.5 in such a minicolumn with analyte elution, at the back flush mode, with 1 mol L(-1) HCl directly to the FAAS nebulizer. The influence of the chemical (sample pH, buffer concentration, HCl eluent concentration and effect of the ionic strength) and flow (sample and eluent flow rates and preconcentration time) parameters that could affect the performance of the system were investigated as well as the possible interferents. At the optimum conditions, for 2 min of preconcentration time (9.9 ml of sample volume), the developed methodology presented a detection limit of 1.1 microg L(-1), a RSD of 3.5% at 10 microg L(-1) and an analytical throughput of 24 h(-1). Whereas, for 4 min of the preconcentration time (19.8 ml of sample volume) a detection limit of 0.98 microg L(-1), a RSD of 6.5% at 5 microg L(-1) and a sampling frequency of 13 h(-1) are reported.