Avaliação da biodegradação do dibenzotiofeno utilizando lodos ativados

During the oil refining process a huge discard volume of water occurs, which carries the contaminants from the process. A class of contaminant compounds resulting from the petrochemical industry are the Polyaromatic Hydrocarbons (PAH's). To evaluate the biodegradation of Dibenzothiophene in refinery water a synthetic wastewater was prepared to be treated using activated sludge. For this, a 2 3 Composite Design (plus 3 central points and six axial points) was carried out. The planning had as independent variables (factors) the initial concentration of DBT, pH and time of biodegradation. Biodegradation of DBT was assayed following the parameters COD, pH, temperature, SS, VSS, FVS, SVI. Concerned to the chromatographic conditions, a methodology was validated in order to verify the presence of DBT and its metabolite, 2-HBF, in the final wastewater treated by activated sludge system using a liquid - liquid extraction coupled to HPLC / UV analysis. The parameters used for validation were DL, QL, linearity, recovery and repeatability. As for optimization, the results indicated that the studied methodology can be used in monitoring the DBT degradation and 2- HBF by activated sludge, as they showed excellent linearity values, coefficients of variation, so as satisfactory recovery percentage. COD reduction efficiency tests showed an average percentage of 64.4%. The increasing trend for the results for the TSS and VSS tests showed that the activated sludge was well tailored. The best operating conditions for the reduction of COD were observed when operated with median concentrations of DBT, a higher time to biodegradation, and pH in both the acidic range as the basic one. The biodegradability of the DBT was confirmed by determining the presence of HBF-2. The highest concentrations of HBF-2 were obtained in extreme concentrations of DBT and pH, and higher biodegradation times.

Formulação de pasta de cimento flexível utilizando planejamento experimental

Steam injection is an oil recovery method accomplished by introducing steam directly into the oil well to the reservoir. The steam causes dilation of the casing, which, after reduction in temperature, tends to return to the initial dimensions: causing the formation of cracks in the cement and loss of hydraulic isolation.. In this context, the type of the SBR latex is used to improve the flexibility of the cement matrix by reducing the amount of fatigue failure. To prevent these failures, the mechanical resistance parameters should be carefully adjusted to well conditions. This work aims to study the mechanical behavior of cement slurry systems additivated with SBR latex for cementing oil wells subject to steam injection. Through the central composite factorial design was studied the behavior of the compressive strength by varying the density of the paste between 1.75 g /cm³ (14.6 lb/ Gal) and 1.89 g/cm³ (15,8lb / Gal), curing time between 4 days and 28 days and concentration of SBR Latex between 0 L / m³ and 534.722 L / m³ (0 gpc and 4 gpc). The results showed that increasing the concentration of SBR latex, within the given ranges, there was a decreased compression resistance and elastic modulus by increasing the elastic deformability of the slurry. From the results it can determine best slurries formulation conditions in oil well cementing operations subject to steam injection.

Formulação de pasta de cimento flexível utilizando planejamento experimental

Steam injection is an oil recovery method accomplished by introducing steam directly into the oil well to the reservoir. The steam causes dilation of the casing, which, after reduction in temperature, tends to return to the initial dimensions: causing the formation of cracks in the cement and loss of hydraulic isolation.. In this context, the type of the SBR latex is used to improve the flexibility of the cement matrix by reducing the amount of fatigue failure. To prevent these failures, the mechanical resistance parameters should be carefully adjusted to well conditions. This work aims to study the mechanical behavior of cement slurry systems additivated with SBR latex for cementing oil wells subject to steam injection. Through the central composite factorial design was studied the behavior of the compressive strength by varying the density of the paste between 1.75 g /cm³ (14.6 lb/ Gal) and 1.89 g/cm³ (15,8lb / Gal), curing time between 4 days and 28 days and concentration of SBR Latex between 0 L / m³ and 534.722 L / m³ (0 gpc and 4 gpc). The results showed that increasing the concentration of SBR latex, within the given ranges, there was a decreased compression resistance and elastic modulus by increasing the elastic deformability of the slurry. From the results it can determine best slurries formulation conditions in oil well cementing operations subject to steam injection.

Obtenção de concentrado proteico do farelo de arroz e avaliação das propriedades químicas e funcionais

Esta dissertação é composta por 5 artigos.

Alternativas de uso da borra de café através de hidrólise ácida, enzimática, ou como substrato para a produção das enzimas: lacase e celulase

In the industrial production of soluble coffee, huge amounts of extracted coffee residues are generated; onaverage, for eachtonne of green coffee extracted, 480 kg of coffee ground waste is produced. This is a solid residue currently used to generate energy at the steam boilers from the soluble coffee industry. Some is also used or as fertilizer on agriculture fields. Seeking a better end use, the work reported here aimed to study the viability of hydrolyzing the coffee ground residue for the production of carbohydrates. Hydrolysis was undertaken with hydrochloric acid at different temperatures and pressures, using a water bath or autoclave.An enzymatic hydrolysis with Viscozyme Lwas developed using Whatman filter paper No1 and the optimal conditions were determined using a rotational central composite experimental design (DCCR).The best conditions to hydrolyze filter paper cellulose were 50 FBG (Fungal β-glucanase) of Viscozyme L at pH 4.0 for 1.0 h and 45 ºC. The ground coffee was hydrolyzed under the same conditions as described above for filter paper, however this enzymatic hydrolysis was not efficient. A combination of enzymatic hydrolysis as a pre-treatment for the ground coffee followed by acid hydrolysis using HCl conducted in an autoclave (120 C for 2.0 h) resulted in higher production of glucose as analyzed by HPLC. Another end use of the ground coffee evaluated was as source of substrate in the culture medium to grow Botryosphaeria rhodina MAMB-05 to produce the enzymes laccase and cellulase. Highest enzyme titres obtained were with 8% (w/v) coffee grounds to which was added a minimum salts medium(Vogel), under agitation conditions (180 rpm) at 28ºC. The phenolic compounds present in the coffee grounds appear to have induced laccase by Botryosphaeria rhodina.

Produção de lipidios funcionais por ação de lipase fúngica

A modificação estrutural de óleos e gorduras é uma das principais áreas de interesse de pesquisa em diferentes setores industriais. No caso da indústria de alimentos, a interesterificação é empregada para melhorar propriedades nutricionais e funcionais, em que se obtêm compostos diferentes dos que lhes deram origem. As lipases microbianas são os biocatalisadores mais utilizados industrialmente, por serem mais estáveis, específicas e com propriedades bem mais diversificadas que as lipases de outras fontes. Este trabalho objetivou, primeiramente, a caracterização da gordura da pele de frango (GPF) e sua comparação com óleo de soja, como referência, visando a utilização de GPF em reações de interesterificação. Para isto foram caracterizados quanto aos índices de rancidez hidrolítica e oxidativa, bem como de matéria insaponificável, índices de saponificação, refração e iodo. Foi realizado ainda o fracionamento e perfil de ácidos graxos destes lipídios e suas frações, com o cálculo de seus índices nutricionais. Foi verificado que a GPF apresentou qualidade satisfatória devido aos baixos índices de acidez (0,65 g ácido oleico.100 g -1 ), peróxido (2,14 meq.kg-1 ), p-anisidina (0,70 unidades de absorvância.g-1 ), além de fonte de ácidos graxos mono-insaturados (40%), sendo fonte promissora para estudos de interesterificação. Em um segundo momento o objetivo foi produzir lipídios modificados ricos em ácidos graxos essenciais a partir da gordura da pele de frango e ácidos graxos ramificados, utilizando lipase sn-1,3 específica e interesterificação do tipo acidólise. Foram estudados os fatores concentração de enzima, adição de água, proporção de substratos e tempo, segundo um planejamento experimental fatorial completo 2 4 . As separações analíticas foram executadas em placas de cromatografia de camada delgada, sendo as frações posteriormente extraídas, ressuspensas e injetadas no cromatógrafo a gás. Foi verificado que a adição de água ao meio reacional apresentou efeito significativo (p<0,05) para todos ácidos graxos avaliados dos triacilgliceróis, sendo que para o ácido essencial linoleico (C18:2) o efeito do tempo de reação também foi significativo, sendo verificado que quanto maior o tempo de reação, menor a quantidade de água a ser adicionada. Em um terceiro momento, o objetivo foi produzir éster fenólico a partir do DHCA, além de realizar reações de transesterificação deste éster com tricaprilina. Para a reação de transesterificação, foi utilizado um delineamento composto central rotacional (DCCR) variando a quantidade de enzima, tempo de reação e temperatura sobre a resposta (%) dos reagentes consumidos. A lipase Novozym® 435 de Candida antarctica foi utilizada como catalisador de todas reações. Foi verificado que a maior produção de éster (50%) ocorreu em oito dias. Nas reações de transesterificação, as relações molares em que houve maior consumo do éster produzido foram 1:5 e 1:10, sendo obtidos 21,1% e 29,6% de residual de dihidrocafeato de octila, respectivamente em 24 h. Foi observado que em altas temperaturas e tempo superior a 26 h, houve o menor residual de dihidrocafeato de octila (18,2%). Foram identificados três diferentes compostos fenólicos, contendo em sua estrutura dihidrocafeato de octila e ácido caprílico.

Recuperação de carotenóides microbianos por diferentes técnicas de ruptura celular

O objetivo deste trabalho foi utilizar diferentes técnicas químicas (dimetilsulfóxido, ácido clorídrico, acético e lático), técnicas mecânicas (banho ultrassônico, abrasão com pérolas de vidro, maceração com terra diatomácea, ruptor ultrassônico e imersão em nitrogênio líquido) e técnica enzimática (preparado enzimático comercial Glucanex®) para a recuperação de carotenoides a partir da ruptura da parede celular das leveduras Sporidiobolus pararoseus e Rhodotorula mucilaginosa isoladas de amostras ambientais. Para isso a obtenção de biomassa foi realizada através de cultivos submersos no meio YM, a 25 °C, 180 rpm por 168 h. Para a ruptura celular, a operação de congelamento da biomassa (-18°C por 48 h) foi estudada. Os métodos de secagem convencional por ar forçado (35°C/48h) e liofilização (-80°C/48h, em ultrafreezer, seguido de liofilizador até alcançar 2% de umidade da amostra) também foram avaliados. Nas técnicas químicas aplicadas, o dimetilsulfóxido apresentou os melhores resultados para as duas leveduras, porém o seu uso é limitado devido a sua toxicidade. Para S. pararoseus, os maiores valores encontrados foram para o ácido clorídrico, seguido do acético e do lático, sendo detectada diferença entre eles quando aplicado o congelamento. Com R. mucilaginosa, os maiores valores foram encontrados para os ácidos acético e lático, seguido do ácido clorídrico, no qual o congelamento da biomassa também não influenciou a recuperação dos carotenoides. Dentre as técnicas mecânicas estudadas, para a levedura S. pararoseus, o banho ultrassônico e a abrasão com pérolas de vidro apresentaram os resultados mais promissores comparados ao DMSO (84,79±2,34 e 76,87±2,06 μg/g respectivamente), onde o processo de congelamento da biomassa não influenciou positivamente no percentual de extratibilidade e na concentração específica dos carotenoides quando utilizada estas técnicas. Com Rhodotorula mucilaginosa, o banho ultrassônico propiciou a recuperação da maior concentração específica de carotenoides (193,5±25,8 μg/g), sendo que o processo de congelamento também não influenciou positivamente no percentual de extratibilidade e na concentração específica dos carotenoides. Através do Delineamento Central Composto Rotacional (DCCR) 23 foi possível avaliar que a levedura S. pararoseus não demonstrou nenhum efeito sob as variáveis pH, temperatura e concentração de enzima. Assim, a melhor condição de trabalho escolhida foi pH 7,4, 30 ºC e concentração de enzima de 1,0 g/gcs, onde apresentou a concentração específica de 42,6 μg/g e volumétrica de 308 μg/L de carotenoides. Para R. mucilaginosa, a condição ótima foi definida como 1,0 g/gcs, pH 5,0 e temperatura de 30 ºC, onde foi encontrado 115,1±8,1 μg/g e 470,1±38,8 μg/L para a concentração específica e volumétrica de carotenoides, respectivamente. A utilização de técnicas combinadas empregando banho ultrassônico e lise enzimática não proporcionou melhorias nos resultados para ambas as leveduras. A liofilização provocou um ganho de 20% e 13,7% na concentração específica dos carotenoides das leveduras S. pararoseus e R. mucilaginosa, respectivamente, onde o congelamento da biomassa não influenciou significativamente (p<0,05) a recuperação de carotenoides provenientes das duas leveduras, podendo ser eliminada do processo. Assim, para S. pararoseus o banho ultrassônico e as pérolas de vidro apresentaram os melhores resultados na recuperação de carotenoides, e para R. mucilaginosa o melhor resultado foi alcançado com o banho ultrassônico.

Estudo cinético do branqueamento do óleo da carpa (Cyprinus carpio L)

O óleo de pescado é caracterizado por ser uma fonte rica de ácidos graxos poliinsaturados ω-3, desde modo a sua oxidação lipídica se torna mais favorável quando comparado com outros óleos de origem vegetal. O objetivo do presente trabalho foi a otimização da etapa de branqueamento através da metodologia de superfície de resposta, sendo utilizado misturas de carvão ativado e terra ativada (Tonsil) para a remoção da cor e dos produtos de oxidação, procurando-se preservar o conteúdo total de carotenóides no óleo de carpa. O óleo bruto de carpa (Cyprinus carpio L.) para a realização do trabalho foi obtido a partir da realização de ensilagem ácida, passando posteriormente pelas etapas de refino: degomagem, neutralização, lavagem, secagem e branqueamento. A otimização da etapa de branqueamento foi realizada através de um planejamento fatorial composto central, com os fatores de estudo: a quantidade de adsorvente (Ads) e a quantidade de carvão ativado (Ca), sendo consideradas como respostas o conteúdo total de carotenóides e o valor de TBA. Na melhor condição do branqueamento do óleo de carpa foi realizado um estudo cinético, e para o cálculo das constantes cinéticas foram utilizados os modelos de Brimberg modificado e de Langmuir-Hinshelwood, A condição ótima do branqueamento foi com 2% de adsorvente e 10% de carvão ativado, onde ocorreram menores perdas de carotenóides (44,40%), com redução da cor escura presente no óleo de (85,62%) e redução do valor de TBA (73,10%), obtendo-se um óleo branqueado de carpa com qualidade oxidativa e melhor aspecto em relação à cor. Os dois modelos cinéticos representaram de forma satisfatória os dados experimentais do branqueamento do óleo de carpa, pelos altos coeficientes de determinação e baixos erros médios relativos apresentados. Foi possível observar que ocorreu uma rápida adsorção dos pigmentos carotenóides, e após 30 min a adsorção foi menos eficiente. Nos óleos bruto e branqueado de vísceras de carpa não foi identificada diferença significativa entre as concentrações de ácidos graxos, demonstrando que as etapas de refino utilizadas não alteraram o perfil de ácidos graxos do óleo bruto.

Isolamento, seleção e cultivo de leveduras com potencia biotecnológico para a produção de endo-xilaneses

Xilanases são enzimas que catalisam a hidrólise das xilanas e têm sido em grande parte, obtidas a partir de bolores e bactérias. No entanto poucos estudos têm sido relatados sobre a produção destas enzimas por leveduras. O presente trabalho teve como objetivo isolar leveduras de diferentes fontes vegetais visando à produção de xilanases, além de maximizar sua produção, estudar o uso de diferentes fontes de nitrogênio e cultivar as leveduras em meios contendo coprodutos agroindustriais. As amostras de alimentos e resíduos foram enriquecidas em caldo extrato de malte e levedura e isoladas em Ágar Nutriente Wallerstein, as leveduras isoladas foram, a seguir, avaliadas quanto à capacidade de degradar xilana presente no meio e produzir halos de hidrólise, os quais foram visualizados através do uso do corante vermelho congo. Os micro-organismos selecionados como potenciais produtores de xilanase foram crescidos em meio complexo líquido e as atividades enzimáticas de endoxilanase, β-xilosidase, carboximetilcelulase, celulase total, pH e concentração de biomassa foram avaliadas ao longo de 96 h de cultivo. Dentre as leveduras isoladas, sete foram selecionadas, e a 18Y foi a que apresentou a maior atividade de endo- xilanase (2,7 U.mL-1 ), sendo esta isolada de chicória e identificada como Cryptococcus laurentii. Esta estirpe apresentou capacidade de produzir xilanase com baixos níveis de celulase, sendo assim selecionada neste trabalho. A maximização de endo-xilanase foi avaliada fazendo uso de planejamento experimental onde primeiramente foi realizado um planejamento fracionário 2 6-2 para verificar os efeitos do pH inicial e as concentrações de xilana, peptona, (NH4)2SO4, extrato de levedura e KH2PO4 sobre a atividade enzimática. Após selecionar as variáveis xilana, peptona, pH e extrato de levedura foi realizado um delineamento composto central rotacional (24 ) onde todos os cultivos foram mantidos a 30°C, 150 rpm durante 96 h sendo retiradas alíquotas para determinação das atividades, pH e biomassa. A produção máxima foi de 6,9 U.mL-1 usando 10,0 g.L-1 de extrato de levedura, 10,0 g.L-1 de peptona, 10,0 g.L-1 de xilana, 1,0 g.L-1 de (NH4)2SO4 em pH 6,5 o que permitiu um incremento de mais de 250% sobre a atividade. Posteriormente foram realizados ensaios avaliando diferentes fontes e concentrações de nitrogênio orgânico e inorgânico. A presença de NH4NO3 e (NH₄)₂SO₄ usados na concentração de 3% proporcionaram as maiores atividades de endo-xilanase (6,2 e 6,0 U.mL-1 respectivamente). O sulfato de amônio foi selecionado e fixado em 1 g.L-1 e logo após um planejamento completo 22 foi realizado onde as variáveis xilana e extrato de levedura foram estudadas e as demais fixadas. As condições ótimas estabelecidas para a produção da enzima foram: concentração de xilana de 18,6 g.L-1 , concentração de extrato de levedura de 10 g.L-1 atingindo 14 U.mL-1 . Após a maximização enzimática estudou-se o crescimento de Pichia pastoris NRRL Y-1603 e Cryptococcus laurentti em cinco substratos agroindustriais visando a possibilidade estes substratos substituírem a xilana em cultivos para a produção de endo-xilanase. Os ensaios foram realizados utilizando os subtratos pré-tratados com NaOH 4% e não tratados. Para inserção dos mesmos aos meios de cultivo, estes foram moídos e adicionados na concentração de 2%. O pré-tratamento para todos as fontes de hemicelulose foi eficiente e promoveu aumento nas atividades produzidas. Cryptococcus laurentti apresentou maior atividade enzimática (8,7 U.mL-1 ) em farelo de arroz desengordurado e pré- tratado enquanto que a levedura Pichia pastoris NRRL Y-1603 apresentou sua melhor condição para produção de endo-xilanase quando cultivada em meio contendo casca de aveia e o farelo de arroz pré-tratados, alcançando atividades máximas de 7,6 e 7,5 U.mL-1 .

Produção de enzimas quitosanolíticas utilizando Paenibacillus ehimensis e Paenibacillus chitinolyticus para obtenção de quitoologossacarídeos

The acquisition of oligosaccharides from chitosan has been the subject of several studies in the pharmaceutical, biochemical, food and medical due to functional properties of these compounds. This study aimed to boost its production of chitooligosaccharides (COS) through the optimization of production and characterization of chitosanolytic enzymes secreted by microorganisms Paenibacillus chitinolyticus and Paenibacillus ehimensis, and evaluating the antioxidant potential of the products obtained. In the process of optimizing the production of chitosanase were employed strategies Fractional Factorial Experimental Design and Central Composite Rotatable Design. The results identified the chitosan, peptone and yeast extract as the components that influenced the production of chitosanase by these microorganisms. With the optimization of the culture media was possible to obtain an increase of approximately 8.1 times (from 0.043 to 0.35 U.mL U.mL-1) and 7.6 times (from 0.08 U.mL-1 to 0.61 U.mL-1) in the enzymatic activity of chitosanase produced by P. chitinolyticus and P. ehimensis respectively. Enzyme complexes showed high stability in temperature ranges between 30º and 55º C and pH between 5.0 and 9.0. Has seen the share of organic solvents, divalent ions and other chemical agents on the activity of these enzymes, demonstrating high stability of these crude complexes and dependence of Mn2+. The COS generated showed the ability of DPPH radical scavenging activity, reaching a maximum rate of scavenging of 61% and 39% when they were produced with enzymes of P. ehimensis and P. chitinolyticus respectively. The use of these enzymes in raw form might facilitate its use for industrial applications

Síntese do Poli (ácido láctico) por policondensação direta utilizando um planejamento fatorial

The environmental impact caused by the disposal of non-biodegradable polymer packaging on the environment, as well as the high price and scarcity of oil, caused increase of searches in the area of biodegradable polymers from renewable resources were developed. The poly (lactic acid) (PLA) is a promising polymer in the market, with a large availability of raw material for the production of its monomer, as well as good processability. The aimed of this study was synthesis PLA by direct polycondesation of lactic acid, using the tool of experimental design (DOE) (central composite rotatable design (CCRD)) to optimize the conditions of synthesis. The polymer obtained was characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), viscosimetric analysis, differential scanning calorimeter (DSC) and size exclusion chromatography (SEC). The results confirmed the formation of a poly (lactic acid) semicrystalline in the syntheses performed. Through the central composite rotatable design was possible to optimize the crystallization temperature (Tc) and crystallinity degree (Xc). The crystallization temperature maximum was found for percentage of catalyst around the central point (0,3 (%W)) and values of time ranging from the central point (6h) to the upper level (+1) (8h). The crystallization temperature maximum was found for the total synthesis time of 4h (-1) and percentage of catalyst 0,1(W%) (-1). The results of size exclusion chromatography (SEC) showed higher molecular weights to 0,3 (W%) percent of catalyst and total time synthesis of 3,2h

System-on-a-Chip (SoC) based Hardware Acceleration in Register Transfer Level (RTL) Design

Today, modern System-on-a-Chip (SoC) systems have grown rapidly due to the increased processing power, while maintaining the size of the hardware circuit. The number of transistors on a chip continues to increase, but current SoC designs may not be able to exploit the potential performance, especially with energy consumption and chip area becoming two major concerns. Traditional SoC designs usually separate software and hardware. Thus, the process of improving the system performance is a complicated task for both software and hardware designers. The aim of this research is to develop hardware acceleration workflow for software applications. Thus, system performance can be improved with constraints of energy consumption and on-chip resource costs. The characteristics of software applications can be identified by using profiling tools. Hardware acceleration can have significant performance improvement for highly mathematical calculations or repeated functions. The performance of SoC systems can then be improved, if the hardware acceleration method is used to accelerate the element that incurs performance overheads. The concepts mentioned in this study can be easily applied to a variety of sophisticated software applications. The contributions of SoC-based hardware acceleration in the hardware-software co-design platform include the following: (1) Software profiling methods are applied to H.264 Coder-Decoder (CODEC) core. The hotspot function of aimed application is identified by using critical attributes such as cycles per loop, loop rounds, etc. (2) Hardware acceleration method based on Field-Programmable Gate Array (FPGA) is used to resolve system bottlenecks and improve system performance. The identified hotspot function is then converted to a hardware accelerator and mapped onto the hardware platform. Two types of hardware acceleration methods – central bus design and co-processor design, are implemented for comparison in the proposed architecture. (3) System specifications, such as performance, energy consumption, and resource costs, are measured and analyzed. The trade-off of these three factors is compared and balanced. Different hardware accelerators are implemented and evaluated based on system requirements. 4) The system verification platform is designed based on Integrated Circuit (IC) workflow. Hardware optimization techniques are used for higher performance and less resource costs. Experimental results show that the proposed hardware acceleration workflow for software applications is an efficient technique. The system can reach 2.8X performance improvements and save 31.84% energy consumption by applying the Bus-IP design. The Co-processor design can have 7.9X performance and save 75.85% energy consumption.

Function propagation through nested systems

Concepts of function are central to design but statements about a device's functions can be interpreted in different ways. This raises problems for researchers trying to clarify the foundations of design theory and for those developing design support-tools that can represent and reason about function. By showing how functions relate systems to their sub-systems and super-systems, this article illustrates some limitations of existing function terminology and some problems with existing function statements. To address these issues, a system-relative function terminology is introduced. This is used to demonstrate that systems function not only with respect to their most local super-system, but also with respect to their more global super-systems. © 2012 Elsevier Ltd. All rights reserved.

Agar extraction from integrated multitrophic aquacultured Gracilaria vermiculophylla: Evaluation of a microwave-assisted process using response surface methodology

Microwave-assisted extraction (MAE) of agar from Gracilaria vermiculophylla, produced in an integrated multitrophic aquaculture (IMTA) system, from Ria de Aveiro (northwestern Portugal), was tested and optimized using response surface methodology. The influence of the MAE operational parameters (extraction time, temperature, solvent volume and stirring speed) on the physical and chemical properties of agar (yield, gel strength, gelling and melting temperatures, as well as, sulphate and 3,6-anhydro-Lgalactose contents) was evaluated in a 2^4 orthogonal composite design. The quality of the extracted agar compared favorably with the attained using traditional extraction (2 h at 85ºC) while reducing drastically extraction time, solvent consumption and waste disposal requirements. Agar MAE optimum results were: an yield of 14.4 ± 0.4%, a gel strength of 1331 ± 51 g/cm2, 40.7 ± 0.2 _C gelling temperature, 93.1 ± 0.5ºC melting temperature, 1.73 ± 0.13% sulfate content and 39.4 ± 0.3% 3,6-anhydro-L-galactose content. Furthermore, this study suggests the feasibility of the exploitation of G. vermiculophylla grew in IMTA systems for agar production.

Studies on Advanced Oxidation Processes for the Removal of Acetamiprid from Wastewater

Pollution of water with pesticides has become a threat to the man, material and environment. The pesticides released to the environment reach the water bodies through run off. Industrial wastewater from pesticide manufacturing industries contains pesticides at higher concentration and hence a major source of water pollution. Pesticides create a lot of health and environmental hazards which include diseases like cancer, liver and kidney disorders, reproductive disorders, fatal death, birth defects etc. Conventional wastewater treatment plants based on biological treatment are not efficient to remove these compounds to the desired level. Most of the pesticides are phyto-toxic i.e., they kill the microorganism responsible for the degradation and are recalcitrant in nature. Advanced oxidation process (AOP) is a class of oxidation techniques where hydroxyl radicals are employed for oxidation of pollutants. AOPs have the ability to totally mineralise the organic pollutants to CO2 and water. Different methods are employed for the generation of hydroxyl radicals in AOP systems. Acetamiprid is a neonicotinoid insecticide widely used to control sucking type insects on crops such as leafy vegetables, citrus fruits, pome fruits, grapes, cotton, ornamental flowers. It is now recommended as a substitute for organophosphorous pesticides. Since its use is increasing, its presence is increasingly found in the environment. It has high water solubility and is not easily biodegradable. It has the potential to pollute surface and ground waters. Here, the use of AOPs for the removal of acetamiprid from wastewater has been investigated. Five methods were selected for the study based on literature survey and preliminary experiments conducted. Fenton process, UV treatment, UV/ H2O2 process, photo-Fenton and photocatalysis using TiO2 were selected for study. Undoped TiO2 and TiO2 doped with Cu and Fe were prepared by sol-gel method. Characterisation of the prepared catalysts was done by X-ray diffraction, scanning electron microscope, differential thermal analysis and thermogravimetric analysis. Influence of major operating parameters on the removal of acetamiprid has been investigated. All the experiments were designed using central compoiste design (CCD) of response surface methodology (RSM). Model equations were developed for Fenton, UV/ H2O2, photo-Fenton and photocatalysis for predicting acetamiprid removal and total organic carbon (TOC) removal for different operating conditions. Quality of the models were analysed by statistical methods. Experimental validations were also done to confirm the quality of the models. Optimum conditions obtained by experiment were verified with that obtained using response optimiser. Fenton Process is the simplest and oldest AOP where hydrogen peroxide and iron are employed for the generation of hydroxyl radicals. Influence of H2O2 and Fe2+ on the acetamiprid removal and TOC removal by Fenton process were investigated and it was found that removal increases with increase in H2O2 and Fe2+ concentration. At an initial concentration of 50 mg/L acetamiprid, 200 mg/L H2O2 and 20 mg/L Fe2+ at pH 3 was found to be optimum for acetamiprid removal. For UV treatment effect of pH was studied and it was found that pH has not much effect on the removal rate. Addition of H2O2 to UV process increased the removal rate because of the hydroxyl radical formation due to photolyis of H2O2. An H2O2 concentration of 110 mg/L at pH 6 was found to be optimum for acetamiprid removal. With photo-Fenton drastic reduction in the treatment time was observed with 10 times reduction in the amount of reagents required. H2O2 concentration of 20 mg/L and Fe2+ concentration of 2 mg/L was found to be optimum at pH 3. With TiO2 photocatalysis improvement in the removal rate was noticed compared to UV treatment. Effect of Cu and Fe doping on the photocatalytic activity under UV light was studied and it was observed that Cu doping enhanced the removal rate slightly while Fe doping has decreased the removal rate. Maximum acetamiprid removal was observed for an optimum catalyst loading of 1000 mg/L and Cu concentration of 1 wt%. It was noticed that mineralisation efficiency of the processes is low compared to acetamiprid removal efficiency. This may be due to the presence of stable intermediate compounds formed during degradation Kinetic studies were conducted for all the treatment processes and it was found that all processes follow pseudo-first order kinetics. Kinetic constants were found out from the experimental data for all the processes and half lives were calculated. The rate of reaction was in the order, photo- Fenton>UV/ H2O2>Fenton> TiO2 photocatalysis>UV. Operating cost was calculated for the processes and it was found that photo-Fenton removes the acetamiprid at lowest operating cost in lesser time. A kinetic model was developed for photo-Fenton process using the elementary reaction data and mass balance equations for the species involved in the process. Variation of acetamiprid concentration with time for different H2O2 and Fe2+ concentration at pH 3 can be found out using this model. The model was validated by comparing the simulated concentration profiles with that obtained from experiments. This study established the viability of the selected AOPs for the removal of acetamiprid from wastewater. Of the studied AOPs photo- Fenton gives the highest removal efficiency with lowest operating cost within shortest time.