Metals sorption in soils is influenced by several factors, including pH, ionic strength, the presence of ionic composition or organic ligands, total amount of metals, and adsorbent loading. These conditions should be considered when evaluating metal sorption capacity of soil material or when applying laboratory results to field conditions. Metal sorption experiments were conducted on Bertie sandy and Starr-Dyke clay loam soils from long-term field studies in which soils received annual applications of copper-rich pig manure for 16 years. Adsorption of Cd, Cu, Pb, and Zn as affected by different background electrolytes at various concentrations was investigated. Electrolytes were Na+, Ca2+, or Al3+ in perchlorate solution, and their concentrations ranged from 0.001 to 0.5 molc L-1. Increasing ionic strength decreased metal adsorption capacity. Electrolyte cation composition had a greater effect on adsorption than did electrolyte concentration. The order of sensitivity to cation composition of the electrolyte was Zn > Cd > Cu > Pb, and this effect was greater in Bertie sandy loam than Starr-Dyke clay loam soils. Little difference in Cu and Pb adsorption was observed between Na+ and Ca2+ in background solution. Most added Cu was adsorbed at low concentrations regardless of pH, but at high concentrations Cu sorption was strongly related to solution pH. Increases in pH resulted in greater Cu sorption due to pH-dependent negative charges and precipitation. The USEPA recommends that soil systems receiving high metal loading rates be maintained at pH 6.5 or above because of the increased metal adsorption. However, pig manure applications to the Bertie soil resulted in greater Cu in soil solution than in control (no manure) soil at pH > 6.5 due to soluble organic matter. Using the Langmuir equation to determine adsorption maxima for soil systems does not always give adequate estimates of adsorption and values from the equations are highly dependent upon soil environmental parameters. Given the limitations in prediction of adsorption maxima, and given that the amount of nonsorbed metal is as important as the adsorbed amount, the isolines of metal remaining in soil solution were provided with a given set of soil environmental factors. / Ph. D.

Poly-γ-glutamic acid (γ-PGA) is a biopolymer made up of repeating units of L-glutamic acid, D-glutamic acid or both. γ-PGA is water soluble, non-toxic and biodegradable, and can be used safely in a variety of applications that are increasing rapidly. This study investigated the production of HMW γ-PGA by five Bacillus species (B. licheniformis 1525, B. licheniformis NCTC 6816, B. licheniformis ATCC 9945a, B. licheniformis ATCC 9945a and B. subtilis (natto) ATCC 15245) in GS, C and E media for the removal of heavy metals in wastewaters. The highest γ-PGA yields of 11.69 g/l and 11.59 g/l were produced by Bacillus subtilis (natto) ATCC 15245 in GS medium and medium C respectively. Upon characterization, γ- PGAs with different properties (crystallinity, acid/salt form and molecular weights ranging from 2.56 × 105 Da to 1.65 × 106 Da) were produced. The water soluble, non-toxic, HMW (Mw 1.65 × 106 Da) γ-PGA produced by B. subtilis (natto) ATCC 15245 in medium C was investigated as a sorbent for the removal of heavy metal ions including Cu2+, Zn2+, Ni2+, Cd2+ and Ag+. The results showed that the removal of metals by γ-PGA was more dependent on the concentration of γ-PGA than the solution pH. The highest metal ions removal of 93.50%, 88.13%, 90.21%, 90.56% and 86.34% by HMW γ-PGA were obtained for Cu2+, Zn2+, Ni2+, Cd2+ and Ag+ respectively. The presence of interfering metal ions could hinder the adsorption of individual metal ions by γ-PGA. The affinities of heavy metal ions for γ-PGA followed the order: Cu2+ > Zn2+ > Ni2+ > Cd2+. The effect of molecular weight of γ-PGA on metal removal was also investigated, and it was found that metal ion adsorption capacity of γ-PGA strongly depended on its molecular weight. The maximum amount (93.50%) of Cu2+ sorbed by HMW γ-PGA was higher compared to that (59.48%) sorbed by LMW γ-PGA. Isotherm models showed that the Redlich-Peterson best described the metal adsorption capacity of γ-PGA. It was also found that a multisite adsorption mechanism occurred via the complexation of metal ions with the free α-carboxyl and possibly the amide functional groups in γ-PGA.

Made available in DSpace on 2016-08-19T12:56:32Z (GMT). No. of bitstreams: 1 Rosiane Silva Penha.pdf: 1185030 bytes, checksum: 1245e0f7f26361b970082d5de61de02b (MD5) Previous issue date: 2009-01-09 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Adsorption of some metal ions (Co2+, Ni2+, Cu2+ e Zn2+) from aqueous solutions (pH 5.0) onto in nature rice husk (0.088 <  < 0.177 mm) was investigated. All experiments were conducted by the batch adsorption techniques at room temperature (28  1°C) and under constant stirring. The adsorption amounts were determined using atomic absorption spectroscopy. The Adsorption data were studied using two well-known adsorption models: Langmuir and Freundlich. The results showed that the metal ions uptake processes mediated by rice husks were fitted Freundlich isotherm model, suggesting that all adsorptions are governed by weak electrostatic interactions. According to the equilibrium studies, the selectivity sequence can be given as: Ni2+ (0.08 mmol g-1) < Co2+ (0.16 mmol g-1) < Zn2+ (0.40 mmol g-1) < Cu2+ (0.89 mmol g-1). This result showed that natural rice rusk holds good potential to remove such metal ions from wastewater. The effect of chemical pretreatment of rice husk on adsorption was also investigated. In nature rice husk (IN) was pretreated with phosphoric acid (AF); phosphoric acid and urea (AFU) and sodium metaperiodate (MP). AFU was the best adsorbent for all metal ions investigated [Ni2+ (0,96 mmol g-1) < Cu2+ (1,20 mmol g-1) < Co2+ (1,59 mmol g-1) < Zn2+(1,80 mmol g-1)]. In addition, in nature rice husk was characterized by chemical-bromatological analyses (humidity, ash, protein, carbohydrate, starch, lipid and fibers), scanning electron microscopy, solid-state 13C NMR and specific BET surface area. Some properties of in nature and pretreated samples were studied by infrared spectroscopy, thermogravimetric analysis, X-ray diffractometry, and elemental analyses. The results showed only marginal changes among them. / Investigou-se a adsorção de alguns íons de metais (Co2+, Ni2+, Cu2+ e Zn2+) a partir de soluções aquosas (pH 5,0), em casca de arroz in natura (IN) (0,088 <  < 0,177 mm). Todos os experimentos foram conduzidos em batelada, a temperatura ambiente (28  1°C) e sob agitação constante. Dois modelos de isotermas foram aplicados aos resultados experimentais: o de Langmuir e o de Freundlich. Os resultados mostraram que as adsorções seguem o modelo da isoterma de Freundlich. De acordo com os estudos de equilíbrio, a seletividade observada para a matriz in natura foi: Ni2+ (0,08 mmol g-1) < Co2+ (0,16 mmol g-1) < Zn2+ (0,40 mmol g-1) < Cu2+ (0,89 mmol g-1). Este resultado mostrou que a matriz tem bom potencial para remover os íons citados de efluentes aquosos. O efeito do pré-tratamento químico na casca de arroz foi também investigado a fim de melhorar a capacidade de adsorção da casca de arroz. A matriz in natura foi tratada com ácido fosfórico (AF), ácido fosfórico e uréia (AFU) e metaperiodato de sódio (MP). Dentre os adsorventes examinados, AFU foi o que melhor adsorveu todas as espécies de íons de metais investigadas [Ni2+ (0,96 mmol g-1) < Cu2+ (1,20 mmol g-1) < Co2+ (1,59 mmol g-1) < Zn2+(1,80 mmol g-1)]. A matriz IN foi caracterizada por análise bromatológica (umidade, cinzas, proteínas, carboidratos, amido, lipídios e fibras), microscopia eletrônica de varredura, ressonância magnética nuclear (13C) e área superficial específica. Todas as matrizes foram caracterizadas por infravermelho, análise termogravimétrica, difratometria de raios-X e análise elementar (CHN). Os resultados mostraram apenas pequenas variações entre as matrizes investigadas.

M. Tech. (Department of Chemical Engineering, Faculty of Engineering and Technology), Vaal University of Technology / Water pollution caused by organic and inorganic contaminants represents an important ecological and health hazard. Simultaneous treatment of organic and inorganic contaminants had gradually gained great scientific interest. Advanced oxidation processes such as photocatalysis, using TiO2 as a photocatalyst, have been shown to be very robust in the removal of biorecalcitrant pollutants. These methods offer the advantage of removing the pollutants, in contrast to conventional techniques. At present, the main technical challenge that hinder its commercialization remained on the post-recovery of the photocatalyst particles after water treatment. Supporting of the photocatalyst on the adsorbent surface is important as it assists during the filtration step, reducing losses of the materials and yielding better results in degrading pollutants. To overcome this challenge, in this study composite photocatalysts of TiO2/zeolite and TiO2/silica were prepared and investigated to explore the possible application in the simultaneous removal of organic and inorganic compounds from contaminated water. The main objective of this study was to investigate the heterogeneous photocatalytic degradation of organic compounds in the presence of metal ions using composite photocatalysts. The Brunauer–Emmett–Teller (BET), Scanning Electron Microscopy and Energy Dispersive X-ray (SEM-EDX), Raman spectroscopy (RS) and zeta potential (ZP) analyses were used to characterize the prepared composite photocatalysts. The successive composite photocatalysts were used in a semi-batch reactor under an irradiation intensity of 5.5 mW/m2 (protected by a quartz sleeve) at 25 ± 3°C for the photocatalytic degradation of synthetic textile (methyl orange) and agricultural (atrazine) wastewater in the presence of ions. The effect of operating parameters such as TiO2 composition on supporting material, particle size, composite photocatalyst loading, initial pollutant concentration and pH were optimized. The effects of inorganic salts and humic acid on dye and pesticides degradation were also studied, respectively. The performance of the photocatalyst reactor was evaluated on the basis of color removal, metal ion reduction, total organic carbon (TOC) reduction, intermediates product analysis and modeling of kinetics and isotherms. Different kinetic and isotherm models were introduced and applied in this work. Important aspects such as error functions with the optimal magnitude were used for the selection of the best suitable model. / European Union. City of Mikkeli, Finland. Water Research Commission (RSA)