The ability of dealginated seaweed, a waste material derived from the commercial processing of seaweed for alginate production, to remove cadmium, lead, nickel, copper, chromium, silver, aluminium and gold from solution was determined. Metal sorption was found to be rapid (90% removal within 5 minutes), achieving a residual concentration of 0.9 mg L[-1] after 1 h contact time from an initial solution concentration of 10 mg L[-1]. The binding of metal by dealginate was found to be pH dependent, optimal sorption occurring at around pH 6-8 for cadmium, lead, nickel, copper and chromium and pH 3-4 for aluminium and gold respectively, suggesting an ion exchange mechanism. Determination of a molar ratio in the displacement of calcium by cadmium on dealginate supported the presence of an ion-exchange relationship, since the displacement of approximately 1 mol of calcium by 1 mol of cadmium was observed. The sorption data was best fitted in the ion exchange approximation as opposed to the Langmuir model. The binding capacities were found to be 1.2, 0.5, 1.6, 0.8, 1.2, 0.4, 0.9 and 0.4 mmol g-1 for cadmium, lead, nickel, copper, chromium, silver, aluminium and gold respectively. The ion exchange constants were calculated to be 3.3 x 10[-6], 4.1 x 10[-6], 6.2 x 10[-6], 1.8 x 10[-6], 2.3 x 10[-6], 2.4 x 10[-7],8 x 10[-10] for cadmium, lead, nickel, copper, chromium, silver and aluminium. The values of the capacities and ion exchange constants showed affinity of the biosorbent to specific metals. The identification of the binding sites on the surface of dealginated seaweed was investigated by a number of techniques. Potentiometric titration revealed three distinct pKa values, the first having a similar value to carboxyl groups, the second being comparable with that of saturated thiols and amines and the third similar to sulphonate groups. Esterification of the dealginate resulted in the subsequent reduction in metal sorption, indicating that carboxyl groups are largely responsible for sorption except in the case of aluminium and gold, where 40-60% of the metal remained in solution after modification of the surface. Evidence of the FT-IR spectra confirmed the presence of carboxyl groups in untreated dealginate, while the number of carboxyl groups was markedly reduced in the esterified sample. The occurrence of other mechanisms apart from ion exchange was suggested by the FT-IR spectrum for aluminium and gold. ESEM images of the surface of dealginated seaweed showed the algae cell structure still present in large areas. X-ray maps revealed the presence of silver, aluminium and gold associated with sulphur atoms on the dealginate surface. EXAFS results showed that cadmium, lead, copper and silver were bound to the dealginate through oxygen atoms, possibly from carboxylate groups. Evidence of gold reduction from Au (III) to Au(l) and Au(O) was also confirmed by the bond distance calculated for this metal. Methods for the on-line preconcentration of cadmium, chromium, copper and lead and chemical speciation of Cr[3+] and CrO[4][2-] using a microcolumn packed with dealginated seaweed were developed. Effective column capacities were 4.0, 8.7, 9.4 and 8.5 mumol L[-1] for cadmium, chromium, copper and lead, respectively. The application of the method was extended to the determination of zinc, cobalt, mercury, scandium, strontium, vanadium, arsenic, selenium, manganese and antimony. The analytical procedures developed for metal preconcentration and chromium speciation were validated by analyses of two Lake Ontario reference materials, TMDA 51.2 and TMDA 54.2 and a synthetic seawater sample. The findings of this study demonstrated that the sorption of metal by dealginate is mainly due to an ion-exchange mechanism. The binding capacities of the biosorbent for the elements studied were adequate for trace analysis and the use of dealginate was shown to be a cheaper alternative to synthetic resins.

Orientador: Claudio Airoldi / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-14T17:53:43Z (GMT). No. of bitstreams: 1 Macedo_ThaisRegi_D.pdf: 2848180 bytes, checksum: 54c8b1c12b90c47c6be6008afc371018 (MD5) Previous issue date: 2009 / Resumo: Este trabalho descreve a preparação, caracterização e aplicação de novos materiais híbridos inorgânico-orgânicos nanoestruturados, obtidos a partir do processo de funcionalização da superfície lamelar de derivados do RUB-18, a forma ácida do material, H-RUB-18, e a forma intercalada com moléculas orgânicas polares, CTA-RUB-18. Para esse processo, foram usados agentes sililantes contendo nitrogênio, enxofre e oxigênio como grupos ativos nas moléculas e dois métodos diferentes. Os difratogramas de raios X mostraram a cristalinidade dos materiais e as microscopias eletrônicas de varredura, a morfologia e o tamanho das partículas formadas. Os espectros de ressonância magnética nuclear de Si e C no estado sólido mostraram que as sínteses foram bem sucedidas. Os resultados obtidos através da análise elementar e da termogravimetria determinaram as quantidades de grupos orgânicos imobilizadas na superfície, o valor máximo obtido foi de 3,79 mmol de grupos por grama de material, um valor próximo da capacidade máxima de funcionalização do material, que é de 3,85 mmol g. Os híbridos nanoestruturados apresentaram estabilidade térmica até aproximadamente 540 K. Os materiais funcionalizados com grupos nitrogenados foram aplicados para a sorção de íons cobre, níquel e cobalto, enquanto os materiais sulfurados foram usados para a sorção de cádmio e chumbo de solução aquosa. As isotermas de sorção foram obtidas pelo processo de batelada, e os dados experimentais foram ajustados aos modelos de Freundlich e Langmuir-Freundlich, considerando superfícies heterogêneas. Esses dados forneceram subsídios para o conhecimento interativo do sistema, considerando a energética da interação. O efeito interativo cátion/centros básicos na interface sólido/líquido foi avaliado através da microcalorimetria e as grandezas termodinâmicas, obtidas nesses sistemas heterogêneos, propiciaram condições para estabelecer ordem energética favorável das interações. Os resultados obtidos mostraram a viabilidade da aplicação dos materiais como eficientes sorventes, para extrair cátions de um ecossistema. / Abstract: The present study describes the preparation, characterization and application of the new inorganic-organic nanostructured hybrid materials, prepared by the functionalization process of the layered surface of derivative RUB-18 material, its acidic, H-RUB-18 and intercalated, CTA-RUB-18 forms. For this process were used silylating agents containing nitrogen, sulfur and oxygen as active atoms on the molecules and two different methods. The X ray diffractograms showed the crystallinity of the materials and the electron scanning microscopy (SEM) the morphology and size of the particles formed. The nuclear magnetic resonance (NMR) spectra for Si and C nuclei in the solid state show that the syntheses were successfully performed. From the obtained elemental analysis and thermogravimetry (TG) results the amount of organic groups immobilized on the surface was determined. The maximum number was 3.79 mmol groups per gram of material, a value near to the maximum of its capacity, 3.85 mmol g. The nanostructured hybrids present thermal stability up to 540 K. The nitrogen functionalized materials were applied for sorption of copper, nickel and cobalt from aqueous solution, while the sulfur materials were used for cadmium and lead sorption from aqueous solution. The sorption isotherms were obtained by the batchwise process and the data were adjusted to the Freundlich and Langmuir- Freundlich models, considering heterogeneous surfaces. These data supply information for the interactive knowledge of the systems, considering the energy of interaction. The interactive effect of cation/basic centers at the solid/liquid interface was evaluated through microcalorimetry and the thermodynamic values, obtained in these heterogeneous systems, give conditions for establishment of a favorable energetic order in the interaction. The obtained results showed the viability of application of the materials as efficient sorbents to extract cations from an ecosystem. / Doutorado / Quimica Inorganica / Doutor em Ciências

No description available.

Ce travail décrit la synthèse d'une série de matériaux à base de biomasse d'alginate et d'algues; ces matériaux ont été conçus sous différentes formes: billes et mousses. Des procédés spécifiques ont été mis au point pour l’utilisation directe de la biomasse algale (AB, sans ajout d’autres polymères) avec le souci de développer un processus de synthèse simple et respectueux de l’environnement (production réduite de sous-produits et sans additif supplémentaire). Ces matériaux ont été testés pour la décontamination d’effluents contenant des métaux lourds (Pb(II) et Cu(II)), mais également pour la valorisation des métaux (métaux du groupe platine, PGM: Pd(II) et Pt(IV)). Différents paramètres opératoires ont été testés afin d'évaluer les capacités de sorption et les étapes limitantes, mais également d'identifier des stratégies d’amélioration des performances d’adsorption. L’incorporation de poly(éthylèneimine) (PEI) est une méthode prometteuse pour augmenter la densité de groupes réactifs (fonctions amines). Différents procédés ont été testés: (a) l'incorporation de particules de PEI réticulées avec du glutaraldéhyde (billes hétérogènes: ABA/PEI), et (b) le greffage homogène de PEI sur de l'alginate (suivi de la réticulation par le glutaraldéhyde) (billes homogènes HABA/PEI). La spectroscopie FTIR et l'analyse MEB& MEB-EDX ont été utilisées pour interpréter les mécanismes de fixation ainsi que pour caractériser la structure des matériaux. Dans une deuxième étape, les matériaux sélectionnés ont été testés pour la catalyse supportée en utilisant la réaction d'hydrogénation du 3–nitrophénol (3-NP). Les résultats sont structurés en 3 parties développées successivement: (a) synthèse des billes d’alginate, AB et AB/PEI et étude de l’adsorption de métaux lourds et de PGMs, (b) comparaison des propriétés d’adsorption du Pd(II) par les billes composites AB/PEI préparées par les voies homogène et hétérogène (et leur application aux tests en catalyse supportée), et (c) la synthèse de mousses poreuses (préparées par réaction entre l’alginate et la PEI) appliquées à l’adsorption du Pd(II) et à la catalyse supportée en réacteur à lit fixe.Si la PEI a un effet limité sur la fixation des métaux lourds (interaction avec les groupes carboxyliques de la biomasse d'alginate ou d'algues), sa présence améliore l’adsorption des métaux dans le cas des PGMs (les groupes amine protonés ont une forte affinité pour les espèces chloro-anioniques du Pd(II)) en particulier pour les billes d'alginate et AB. Tous les adsorbants ont une préférence pour le Pb(II) par rapport au Cu(II) et pour le Pd(II) par rapport au Pt(IV); la présence de PEI limite la sélectivité du matériau pour le Pb(II) et le Pd(II). La capacité de fixation et la stabilité des billes composites d'alginate/PEI ont été améliorées en utilisant le mode de synthèse homogène (la PEI étant dispersée de manière homogène dans la bille avant la réticulation par le glutaraldéhyde). Les deux supports (billes hétérogènes ou homogènes) chargés en Pd(II) (ensuite réduit) ont permis des performances catalytiques comparables bien qu’inférieures à celles des catalyseurs classiques, mais le mode homogène améliore la stabilité à long terme du matériau. Le conditionnement du support catalytique sous forme de mousse a permis de tester la réaction catalytique dans un système à lit fixe : le conditionnement sous forme de mousse améliore les propriétés de transfert de masse par rapport aux billes et la constante de vitesse apparente n'est que légèrement réduite après 30 cycles de fonctionnement. / This work describes the synthesis of a series of materials based on alginate and algal biomass (AB); these materials have been designed under different shapes: beads and foams. Special processes have been developed for directly using the algal biomass (without adding other polymers) with the double objective of simple processing and environmentally-friendly manufacturing (reduced production of sub-products and without additional resources). These materials have been tested first for metal recovery for heavy metal decontamination (Pb(II) and Cu(II)) but also for the valorization of metals (platinum groups metals, PGMs: Pd(II) and Pt(IV)). These studies were performed investigating various operating conditions in order to evaluate sorption capacities and limiting steps but also to identify the processes to be used for improving sorption performance. The incorporation of poly(ethyleneimine), PEI, is a promising method for increasing the density of highly reactive groups (amine functions). Different processes have been tested: (a) the incorporation of particles of PEI crosslinked with glutaraldehyde (heterogeneous beads: ABA/PEI), and (b) the homogeneous grafting of PEI on alginate (followed by glutaraldehyde crosslinking) (HABA/PEI beads). Several techniques have been used for characterizing the sorption process and the structure of developed sorbents, including FTIR spectroscopy, SEM & SEM-EDX analysis. In a second step selected materials have been tested for supported catalysis using the simple reaction of hydrogenation of 3–nitrophenol (3-NP) as a test reaction. The results are structured in 3 parts successively developed: (a) synthesis of alginate, AB and AB/PEI beads and testing for sorption heavy metals and PGMs, (b) comparison of Pd(II) sorption properties of AB/PEI composite beads prepared by the homogeneous and the heterogeneous routes (and their application to supported catalytic tests), and (c) synthesis of highly porous foams (prepared by reaction of alginate with PEI) and the testing of Pd(II) sorption and Pd-supported catalysis (in fixed-bed reactor). While PEI hardly affects the sorption of heavy metals (due to direct interaction with carboxylic groups of alginate or algal biomass), the presence of PEI strongly improves metal binding in the case of PGMs (the protonated amine groups strongly bind chloro-anionic PGM species). All the sorbents have a preference for Pb(II) over Cu(II) and for Pd(II) over Pt(IV), especially for alginate and AB beads because the presence of PEI limits the selectivity of the material for Pb(II) and Pd(II). Both the sorption capacity and the stability of composite alginate/PEI beads were improved while using the homogeneous synthesis mode (the PEI polymer being homogeneously dispersed in the bead before glutaraldehyde crosslinking). The two supports (heterogeneous vs. homogeneous beads) loaded with Pd(II) and subsequently reduced gave comparable catalytic performance (lower than conventional catalysts) but the homogeneous mode improves the long-term stability. The conditioning of the catalytic support as a foam allows testing the catalytic reaction in fixed-bed system: the conditioning improves mass transfer properties compared to beads and the apparent rate constant is only slightly reduced after operating 30 cycles.

<p>The filters used today to purify water are often expensive and the need to find new filter materials is substantial. Studies of pine bark have shown that this is a material that may be used as an alternative to conventional filter materials, such as activated carbon. However, the study of pine bark has shown that a leakage of phenolic compounds may occur when using the material for water purification. Therefore, the purpose of this report is to investigate the release of phenols from pine bark, in order to evaluate the use of pine bark as a filter material. Another assignment is to investigate the amount of metals adsorbed by the filter material. The studies were carried out through three leaching experiments. As leachates, double deionised water and storm water were used. The phenol concentration in the leachate was determined for both double deionised water and storm water. The degree of metal sorption was measured only for the storm water. The measured phenol concentration in the double deionised water was 4.40 mg/L and in the storm water 4.81 mg/L. These concentrations exceed the Canadian guideline value, of 4.0 μg/L, more than a 1000 times. No metal sorption occurred as the metal content of the storm water was too low. Instead a release of metals from the pine bark into the eluate of the storm water occurred. The leaching attempts also resulted in a decline of the pH-values of the two different waters. The pH-values for the double deionised water and the storm water decreased from 7.0 to 4.3 and from 6.0 to 4.2 respectively. A release of phenols was ascertained with a significant difference in concentrations between double deionised water and storm water. Therefore it is not advisable to use pine bark filters for purification of water with low concentrations of metals, as the filter material may release metals into the water under such conditions.</p><p>Keywords: pine bark, phenol, filter materials, leaching, metal sorption, toxicity</p><p>Nyckelord: furubarksflis, fenol, filtermaterial, lakning, metallsorption, toxicitet</p>

The filters used today to purify water are often expensive and the need to find new filter materials is substantial. Studies of pine bark have shown that this is a material that may be used as an alternative to conventional filter materials, such as activated carbon. However, the study of pine bark has shown that a leakage of phenolic compounds may occur when using the material for water purification. Therefore, the purpose of this report is to investigate the release of phenols from pine bark, in order to evaluate the use of pine bark as a filter material. Another assignment is to investigate the amount of metals adsorbed by the filter material. The studies were carried out through three leaching experiments. As leachates, double deionised water and storm water were used. The phenol concentration in the leachate was determined for both double deionised water and storm water. The degree of metal sorption was measured only for the storm water. The measured phenol concentration in the double deionised water was 4.40 mg/L and in the storm water 4.81 mg/L. These concentrations exceed the Canadian guideline value, of 4.0 μg/L, more than a 1000 times. No metal sorption occurred as the metal content of the storm water was too low. Instead a release of metals from the pine bark into the eluate of the storm water occurred. The leaching attempts also resulted in a decline of the pH-values of the two different waters. The pH-values for the double deionised water and the storm water decreased from 7.0 to 4.3 and from 6.0 to 4.2 respectively. A release of phenols was ascertained with a significant difference in concentrations between double deionised water and storm water. Therefore it is not advisable to use pine bark filters for purification of water with low concentrations of metals, as the filter material may release metals into the water under such conditions. Keywords: pine bark, phenol, filter materials, leaching, metal sorption, toxicity Nyckelord: furubarksflis, fenol, filtermaterial, lakning, metallsorption, toxicitet

Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2016-09-14T16:34:31Z No. of bitstreams: 1 Tese Mariangela V Lopes.pdf: 3032469 bytes, checksum: 36404d46d79768ab384fb49c544f496e (MD5) / Approved for entry into archive by NUBIA OLIVEIRA (nubia.marilia@ufba.br) on 2016-09-14T20:43:57Z (GMT) No. of bitstreams: 1 Tese Mariangela V Lopes.pdf: 3032469 bytes, checksum: 36404d46d79768ab384fb49c544f496e (MD5) / Made available in DSpace on 2016-09-14T20:43:57Z (GMT). No. of bitstreams: 1 Tese Mariangela V Lopes.pdf: 3032469 bytes, checksum: 36404d46d79768ab384fb49c544f496e (MD5) / Neste trabalho, foram desenvolvidos procedimentos e sistemas automatizados para o controle de qualidade de carnes e produtos cárneos quanto à presença de aditivos (NO2- e NO3-), degradação (evolução de H2S), presença de adulterante (SO3-) e riscos de contaminação pela capacidade sortiva de metais. O desenvolvimento destes procedimentos vem contrapor as metodologias clássicas recomendadas pelos órgãos oficiais brasileiros. Os métodos e procedimentos aqui desenvolvidos obedecem às recomendações da Química Analítica moderna, as quais priorizam precisão, exatidão, sensibilidade, custos operacionais, versatilidade, robustez, rastreabilidade, minimização de resíduos e produtividade analítica. O sistema de analise por injeção em fluxo (FIA), para análise seletora e discriminatória de H2S evoluído pela carne, foi desenvolvido baseado no método do azul de metileno. O emprego da multicomutação, associado à câmara de pervaporação, conferiu versatilidade ao sistema com produtividade analítica de 30 determinações h-1. Paralelo a isto, foi realizada uma avaliação da degradação de carnes empregando a espectroscopia no infravermelho próximo (NIR) para averiguação das condições de conservação de carnes. Os resultados foram concordantes para as duas metodologias (NIR e FIA), sendo possível detectar indícios de deterioração após 30 min de exposição da carne à atmosfera em temperatura ambiente. O desenvolvimento de sistema em fluxo para análise seqüencial de NO2- e NO3-, em produtos cárneos, utilizando câmara de tubos concêntricos (CTC) foi baseado no método de Greiss. A CTC proporcionou a divisão da zona da amostra, facilitando as determinações seqüenciais de NO2- e NO3-. A subzona da amostra que passava pelo tubo central da CTC resultava apenas na determinação do NO2-. A amostra que passava pelo tubo externo (coroa) da CTC, percolava grãos de cádmio coperizado, resultando na redução do NO3- existente à NO2-. Este sistema ofereceu boa sensibilidade para a quantificação dos analitos, apresentando limites de detecção de 0,018 e 0,036 mg L-1 para NO2- e NO3-, respectivamente. O procedimento proposto atingiu produtividade analítica de 120 determinações h-1. O desenvolvimento de sistema automatizado em fluxo para análise discriminatória de sulfito em carnes foi baseado no método da p-rosanilina. Foi empregado câmara de permeação gasosa, onde o SO3- presente na amostra, permeava através de membrana de PTFE para a reação com o reagente cromogênico. O sistema foi satisfatório para screening analysis, com produtividade analítica de 12 determinações h-1. A capacidade sortiva de metais pela carne bovina foi também avaliada. Foi avaliado o contato estático da carne com soluções de referência de Cd e Pb, preparadas com água de torneira, a pH 6. Foi empregada válvula multiportas, com oito canais para execução dos experimentos, enquanto que metais foram determinados por ICP OES. Os resultados indicaram um elevado poder sortivo, cerca de 80% para ambos os metais, evidenciando risco potencial de contaminação para as carnes submetidas a práticas inadequadas de abate e comercialização / In the present work automated systems and procedures to control the quality of meats and meat products had been developed, in concern to the additive presence (NO2- and NO3-), degradation (H2S evolution) and presence of adulterating species (SO32-). Also the metal sorption capacity on meat was evaluated. The development of these methods comes to oppose classical methods recommended by brazilian official agencies. The developed procedures follow the recommendations of the modern Analytical Chemical, which prioritizes the precision, exactness, sensitivity, traceability, robustness, reduced operational costs, lesser production of residue and raised analytical productivity. The flow analysis (FIA) procedure to discriminate H2S in meat sample was developed based on methylene blue method. Multicommutation, associated to gas permeation conferred versatility to the system with analytical throughput of 30 determinations h-1. Parallel to this, the spectroscopy in the near infrared region (NIR) was carried out to evaluate meat degradation. A flow system for sequential NO2- and NO3- analysis in meat products, using concentric tubes chamber (CTC) was based on the Greiss method. The CTC provides the division of sample zone, permitting the sequential analysis. The sample sub zone that passed for the central pipe of the CTC resulted in the determination of the NO2-. The sample that passed through external CCP pipe, percolated the cadmium column, allowing the reduction of the NO3- to NO2-. This system offers sensitivity in the quantification of anilities with detection limits of 0.036 for NO3- and 0.018 mg L-1 for NO2-, reaching 120 determinations h-1. The flow system for the screening analysis of SO32- in meat sample was based on p-rosanilne method. Chamber for gas permeation was employed. The system revealed efficient for screening analysis with analytical throughput of 12 determination h-1. The metal sorption capacity on meat was evaluated. The investigated species comprised Cd and Pb from solutions prepared with tap water at pH 6. In the experimental set, it was employed an eight channels multiport valve in order to prepare part of the samples, while the metal determinations was carried out by using ICP OES technique. The results obtained demonstrated an expressive retention capacity of meat for Cd2+ and Pb2+ ions with percentages ca. 80% (m/m) for both metals, indicating the potential risks related to the consumption of meat submitted to inappropriate conditions of abattoir, handling, storage and commercialization.

Areas were sampled in the White Rock Creek Watershed to examine sediment bound trace metal distributions and sorption relationships. A Kruskal-Wallis AOV found significant among area differences for most metals, and SNK-like multiple comparisons were used to group these areas. Kruskal-Wallis AOVs similarly found among area differences for sediment components that bind trace metals (Fe and Mn oxides and organic carbon) and physicochemical conditions that influence metal sorption (particle size and pH). Multiple correlation found numerous relationships among trace metals, sediment components, and physicochemical conditions. Statistical relationships indicate that metal partitioning to various sorption factors is metal specific. White Rock Creek Watershed trace metal concentrations are comparable to those in many urban watersheds.