Arsenic contamination in drinking water has been a cause of serious concerns across the United States as well as throughout the world. Over 70 million people in Eastern India, Bangladesh, Vietnam, Taiwan, and Northern China have been victims of arsenic poisoning. The USEPA has classified arsenic as a Class A carcinogen and recently reduced the Maximum Contaminant Level (MCL) in drinking water from 50ppb to 10ppb. The deadline for all the water utilities to meet this level is 23rd January 2006. To meet those drinking water standards, small water utilities need low cost and effective arsenic removal techniques. Natural zeolites such as Chabazite are excellent sorbents for several metallic and radioactive cations. Modifying the zeolite structure can effectively enhance the adsorption capacities of these zeolites for removal of heavy metals. The present work investigates the adsorption capacities of Cuprous and Ferrous treated Chabazite for removal of arsenic. This investigation is a part of a broader project directed at developing an effective pretreatment process that uses modified Chabazite in conjugation with Microfiltration (MF) or Ultrafiltration (UF) for removal of organic and inorganic contaminants. The goal of this research is to determine how well Cuprous and Ferrous treated Chabazite sorbs arsenic in its trivalent and pentavalent state. The other objectives of this research are to examine which modification of the chabazite has the higher removal efficiency of arsenic. This study will also compare arsenic adsorption on the modified zeolites in response to competitive adsorption of various anions present in natural source waters such as sulfates, hydroxides, and chlorides. The potential benefit of this study is to find the most effective treatment of for removal of arsenic species from aqueous solutions. This investigation may provide small water utilities, with a cost effective way for removal of arsenic and thus meet the recommended new regulatory maximum contaminant level (MCL).

>Magister Scientiae - MSc / There are huge amount of natural clinoptilolite available in South Africa which can be utilised for wastewater treatment of ammonia and chromium if their characteristics are properly known. However, these deposits have not been well characterised but in this study, the untreated clinoptilolite materials were fully characterised using techniques such as SEM-EDS, HRTEM-SAED, XRD, XRF, FTIR and BET. After acid pretreatment with several extractions, the pretreated samples were again characterised using the above mentioned techniques. These pretreated materials were used for NH₄⁺ and Cr³⁺ adsorption of wastewater. The three natural South African clinoptilolite samples used in this study were from ECCA Holdings (ESC and EHC samples) and Pratley (PC sample) deposits obtained from Western Cape and KwaZulu-Natal Province respectively. This study revealed that the chemical composition and mineral phases of South African clinoptilolites vary considerably from site to site, even clinoptilolite mined from the same deposit sites. The XRD analyses showed that Pratley clinoptilolite (PC) was the most pure clinoptilolite sample (81.41 %) compared to the purity of EHC (67.88 %) and ESC (44.0 %) sample. The ECCA Holdings untreated clinoptilolite samples contained dense phases such as quartz which was not found in Pratley sample. Quartz was found to be the most dominant impurity in both ECCA Holding sample. The cation exchange capacity (CEC) of ESC, EHC and PC samples were found to be 1.23, 1.81 and 2.90 meq/g respectively and these results were compared to that of XRF analyses. The acid solutions of 0.02 and 1.0 M HCl were used to pretreat natural clinoptilolite to determine the optimum acid concentration and number of extractions required to fully replace the exchangeable cations. The pretreatment results showed that 0.02 M HCl was the optimum acid concentration for acid pretreatment of clinoptilolite samples. Between 7 and 22 extractions were required to remove Na⁺, K⁺, Ca²⁺ and Mg²⁺ without causing much dealumination of the framework. Sodium ion was found to be weakly bound cation in the clinoptilolite framework, since it could be completely exchanged by H⁺ after 7 extractions with 0.02 M HCl acid solution. Potassium ion was found to be strongly bound in the clinoptilolite framework since it could not be completely exchanged during the acid pretreatment process even after 22 extractions. The HRTEM-SAED and BET results showed that ESC, EHC and PC were all polycrystalline and microporous materials respectively. It was found that the adsorption capacity of the treated Pratley clinoptilolite sample was increased by 36 % for NH₄⁺ removal, compared to that of the untreated PC sample. The adsorption study results showed that the pretreatment of clinoptilolite samples using 150 mL volumes of 0.02 M HCl with 7 acid extractions at 25 °C for ESC pretreated and EHC pretreated. The pretreatment of PC sample at 22 extractions could remove high percentage of NH₄⁺ (98.11 %) within a short contact time of 10 min. The pretreated Pratley clinoptilolite sample was found to be the best NH₄⁺ adsorbent (98.11 % NH₄⁺ removal) compared to EHC treated (93.89 % NH₄⁺ removal) and ESC treated (75.00 % NH₄⁺ removal) clinoptilolite samples. However, acid-pretreated Pratley clinoptilolite did not sufficiently remove Cr³⁺ (16.10 %) from synthetic wastewater showing that it is not a good adsorbent for this particular metal ion removal. Despite several studies that have been conducted on clinoptilolite, no study has been carried out on the pretreatment and comparison of sorption capacity of different South African clinoptilolites for the removal of NH₄⁺ from wastewater. This study has been able improve on the acid-pretreatment procedure for clinoptilolite. This study demonstrated that it is not only the acid concentration that is important but also the number of extractions needed to remove all the exchangeable cations from the clinoptilolite framework. This study has also been able to prove that South African clinoptilolite can treated ammonia from wastewater.

Vanadium is a white bright metal that belongs to group 5 in the periodic table of elements. It can exist in different oxidation states from -2 to +5 although the forms can be found naturally in the environment are (III), (IV) and (V). As vanadium is toxic at high concentrations, and as vanadium is a common contaminant from e.g., steel slags, more detailed knowledge on the environmental behavior of this metal is required. One important property is its sorption to soils, as this will determine the bioavailability and the risk of leaching from soils. In surface soils vanadium(V) is commonly the predominating redox species. Therefore the purpose of this study was to determine vanadium(V) sorption in 7 different soils in order to investigate the factors determining vanadium(V) sorption and to estimate the capacity of the soils to bind vanadium. From laboratory adsorption experiments, vanadium sorption has been studied as a function of pH, vanadium(V) concentration, and phosphorus status. The adsorbed vanadium(V) of investigated soils was compared on the basis of the Freundlich parameters m and log Kf. The clay content of the soil and the content of oxalate soluble iron and aluminum were two important factors for the vanadium(V) sorption behavior. The higher the values of these soil properties, the stronger was vanadium(V) sorption. Among the soils investigated here the sorption strength was highest for the Kungängen A3 soil and then decreased in the following order Säby, Kungsängen D3, Pustnäs, Termunck, Guadalajara and Zwijnaarde. It is notable that the three soils with the strongest vanadium(V) sorption were clay soils, whereas the other four were sandy or silty soils. The pH dependence of vanadium sorption was also determined. The results show that the percentage sorbed vanadium(V) increases with decreasing pH. This is due probably to the anion properties of vanadium(V) (i.e. vanadate) in combination with increased positive surface charge on the soil colloids at lower pH. Moreover there is a competition between phosphate and vanadium(V) for sorption sites, which will cause less vanadium(V) sorption in soils. Therefore both the pH value and the phosphorus status are two additional factors that influence the vanadium sorption properties of soils.

No description available.

Orientador: Susanne Rath / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-21T08:01:07Z (GMT). No. of bitstreams: 1 Doretto_KeityMargareth_D.pdf: 2722057 bytes, checksum: d4c5a2090af2c524cc8d28125e30eaa2 (MD5) Previous issue date: 2012 / Resumo: Antimicrobianos, entre eles as sulfonamidas, têm sido amplamente utilizados em medicina veterinária para fins terapêuticos e profiláticos. Uma vez excretados os fármacos e/ou metabólitos podem levar a contaminação do meio ambiente e estudos sobre o impacto ambiental ainda são escassos. Em adição, no Brasil, ainda não existe uma fiscalização de medicamentos veterinários. A não conformidade dos medicamentos reflete diretamente na saúde animal, como também é um tópico relevante quanto à segurança alimentar. Assim sendo, métodos foram desenvolvidos e validados para a determinação de sulfadiazina (SDZ), sulfadimetoxina (SDM) e sulfaquinoxalina (SQX) em medicamentos de uso veterinário por cromatografia líquida de alta eficiência associada a um detector de arranjo de fotodiodos (HPLC-DAD). Os resultados obtidos indicam a necessidade de controle de qualidade dos fármacos de uso veterinário comercializados no Brasil. Ainda, o trabalho estudou a sorção da SDZ, SDM e SQX em quatro solos característicos do Estado de São Paulo. Os estudos foram conduzidos conforme recomendação do Guia OECD 106. As sulfonamidas foram quantificadas nas soluções de solo por um método HPLC-DAD previamente validado. Os dados de adsorção/dessorção das sulfonamidas nos quatro solos foram ajustados com isotermas de Freundlich na forma linear ou logarítmica. Um fenômeno de histerese de adsorção/dessorção foi evidente em todos os solos. Os baixos valores do coeficiente de Freundlich (KF) obtidos sugerem fraca adsorção das sulfonamidas nos solos avaliados e, portanto, estas tendem a ser lixiviados e, por sua vez apresentam potencial para contaminar águas superficiais e subterrâneas / Abstract: Antimicrobials, including sulfonamides, have been widely used in veterinary medicine for therapeutic and prophylactic purposes. Once excreted, drugs and/or metabolites can contaminate the environment. Environmental impact studies are still scarce. In addition, in Brazil, there is no surveillance of veterinary medicines. The poor quality of drugs may reflect directly on animal health and is also a topic relevant to food safety. Therefore, methods were developed and validated for the determination of sulfadiazine (SDZ), sulfadimethoxine (SDM) and sulfaquinoxaline (SQX) in veterinary drugs, using high performance liquid chromatography coupled to a photodiode array detector (HPLC-DAD). The obtained results indicate the need for a quality control program of veterinary drugs comercialized in Brazil. Moreover, the present work aim studied the sorption of sulfonamides (SDZ, SDM and SQX) in four characteristic soils of the State of São Paulo. The studies were conducted as recommended by the OECD Guidelines 106. The sulfonamides were quantified in the soil solutions by a previously validated HPLC-DAD method. Adsorption/desorption data of sulfonamides in soils were fitted to Freundlich isotherms in the linear or logarithmic forms. A hysteresis of adsorption/desorption was evident in all four soils evaluated. The low values of the Freundlich coefficient (KF) obtained suggest weak adsorption of sulfonamides in soils, and therefore they tend to be leached and present high potential to contaminate surface and groundwater / Doutorado / Quimica Analitica / Doutora em Ciências

Made available in DSpace on 2014-07-29T16:24:20Z (GMT). No. of bitstreams: 1 dissertacao Mara Lemke de castro.pdf: 1167143 bytes, checksum: 4fa69c36a360ed8098578d282470d5a8 (MD5) Previous issue date: 2009-07-31 / The intensification of the use of land for farming has caused great concern, mainly due to the impacts that these activities are causing the environment, particularly with regard to it s contamination by chemicals. The application of chemicals and waste ground and in several, or in plants in order to take agronomically solid waste, improve productivity and increase agricultural production has been growing in the practices of cultivation. The form of improper disposal of waste in the soil, without any control of dose and form of application, and without knowledge of their ability to assimilate the different soil types, possibly predisposing the occurrence of contamination and pollution along the profile these soils and may reach the water table and contaminate groundwater. This work aimed the analysis of the retention of some heavy metals in Ultisol, Oxisol Typic Acrustox, Quartzipsamment and Kandic Oxisol found in savannah soil of the Goiás. Heavy metals in tests were Cadmium (Cd+2), lead (Pb+2), copper (Cu+2), chromium (Cr+3 and Cr+6), nickel (Ni+2) and zinc (Zn+2). The sorption of the heavy metals in soil was evaluated by batch method and described by potential and linear models of the Freundlich isotherm. For the establishment of sorption isotherm were added in 5,0 cm3 of soil and 50,0 cm3 of solution containing the heavy metal being assessed with different concentrations within the limits acceptable soil. The potential and linear sorption isotherm submitted a good adjusted to describe the behavior of adsorption of heavy metals in different classes of soil studied. The detention of heavy metals in descending order was the Ultisol: Cr+3 > Cr+6 > Ni+2 > Zn+2 > Cu+2 > Pb+2 > Cd+2; Oxisol Typic Acrustox: Cr+3 > Cr+6 > Ni+2 > Cu+2 > Cd+2 > Zn+2 > Pb+2; Quartzipsamment: Cr+6 > Cr+3 > Cu+2 > Pb+2 > Ni+2 > Zn+2 > Cd+2; Kandic Oxisol: Cr+3 > Cr+6 > Pb+2 > Cu+2 > Zn+2 > Ni+2 > Cd+2. The Quartzipsamment presented a less retention metal comparison other classes of soil, and therefore more vulnerable to contamination of groundwater. / A intensificação do uso das terras para fins agropecuários tem causado grande preocupação, devido, principalmente, aos impactos que essas atividades vêm causando ao meio ambiente, sobretudo no que diz respeito à sua contaminação por substâncias químicas. A aplicação de produtos químicos e de resíduos diversos no solo e, ou, nas plantas, com o propósito de aproveitar agronomicamente resíduos sólidos, melhorar a produtividade e aumentar a produção agrícola, tem sido crescente nas práticas de cultivo. A forma inadequada de disposição de resíduos no solo, sem qualquer controle das doses e da forma de aplicação, e sem o conhecimento da capacidade de sua assimilação pelos diferentes tipos de solos, possivelmente, predispõem a ocorrência de contaminação e de poluição ao longo do perfil desses solos, podendo alcançar o lençol freático e contaminar as águas subterrâneas. Objetivou-se com este trabalho a análise da retenção de alguns metais pesados nas classes de solo Argissolo Vermelho Eutrófico, Latossolo Vermelho Acriférrico, Neossolo Quartzarênico e Nitossolo Vermelho Eutroférrico encontrados em áreas de cultivo do Estado de Goiás. Os metais tóxicos avaliados nos ensaios de sorção foram cádmio (Cd+2), chumbo (Pb+2), cobre (Cu+2), cromo (Cr+3 e Cr +6), níquel (Ni+2) e zinco (Zn+2). A sorção dos metais foi avaliada pelos modelos potencias e lineares da isoterma de Freundlich. Para o estabelecimento de isotermas de sorção foram adicionados em 5,0 cm3 de solo e 50,0 cm3 de solução contendo o metal tóxico a ser avaliado com diferentes concentrações, respeitando os limites aceitáveis. As isotermas de sorção potencial e linear apresentaram um bom ajuste para descrever o comportamento de adsorção dos metais tóxicos nas diferentes classes de solos estudadas. A sequência da retenção dos metais tóxicos em ordem decrescente foi, para o Argissolo Vermelho Eutrófico: Cr+3 > Cr+6 > Ni+2 > Zn+2 > Cu+2 > Pb+2 > Cd+2; Latossolo Vermelho Acriférrico: Cr+3 > Cr+6 > Ni+2 > Cu+2 > Cd+2 > Zn+2 > Pb+2; Neossolo Quartzarênico: Cr+6 > Cr+3 > Cu+2 > Pb+2 > Ni+2 > Zn+2 > Cd+2; Nitossolo Vermelho Eutroférrico: Cr+3 > Cr+6 > Pb+2 > Cu+2 > Zn+2 > Ni+2 > Cd+2. O Neossolo Quartzarênico apresentou uma menor retenção de metais em comparação às demais classes de solo, sendo, portanto, mais vulnerável à contaminação das águas subterrâneas.

Made available in DSpace on 2017-07-10T19:24:24Z (GMT). No. of bitstreams: 1 Mariana_ sbizzaro.pdf: 1501907 bytes, checksum: 5610159e30f98d52848320f90146f751 (MD5) Previous issue date: 2016-02-12 / The agricultural sector has great influence in Brazilian economy. Furthermore, agricultural yield has been associated with pesticides application during crop cycle, which atrazine is applied for example, since it can cause environmental contamination when it does not reach its target. Thus, there are some essential and imperative options that can minimize contamination and negative impacts during agricultural practices. So, present study aimed at evaluating the ability of three biochars in atrazine adsorption. Therefore, three biochars produced from bamboo culm were used, whose species is Phyllostachys aurea, and temperature ranged at 350 ºC, 450 ºC and 550 ºC. The three studied biochars were named as BE350, BE450 and BE550. They were characterized based on their physical and chemical properties by elemental analysis, characterization of functional groups (Infrared Spectroscopy Fourier Transform - FTIR), surfaces morphology evaluation (Scanning Electron Microscopy - SEM) as well as specific surface area (ASEBET) and porosity. A kinetic study was carried out to determine the equilibrium period of adsorption process and the kinetic mechanism that controls such process. Langmuir and Freundlich isotherms were also modeled during this trial. Atrazine determination, after the adsorption test, was carried out by High Performance Liquid Chromatography (HPLC). The obtained analyses showed that the adsorption capacity of biochars decreased in the following order: BE 450> BE 350 > BE 550, and such capacity has been associated with the physical and chemical characteristics of biochars. The three studied biochars are well represented by the kinetic model of pseudo-second order. At last, all biochars have shown high affinity to adsorb atrazine; however, the biochar that was produced at 450 ºC has shown the highest adsorption capacity. / O setor agrícola possui grande destaque na economia brasileira, a produção agrícola está associada ao uso de pesticidas durante o ciclo das culturas, como é o caso da atrazina, que pode causar a contaminação do ambiente, quando não atinge seu alvo. Sendo assim, alternativas que minimizem as contaminações e impactos negativos da prática agrícola são essenciais e urgentes. Desta forma, o presente estudo teve por objetivo avaliar a capacidade de três biocarvões, em adsorver o herbicida atrazina. Para tanto, foram utilizados três biocarvões, produzidos a partir do colmo de bambu, da espécie Phyllostachys aurea à 350ºC, 450ºC e 550ºC, nomeados BE350, BE450 e BE550. Os biocarvões foram caracterizados quanto as propriedades físicas e químicas, por meio de análise elementar, caracterização de grupos funcionais (Espectroscopia de Infravermelho com Transformada de Fourier - FTIR), avaliação da morfologia das superfícies (Microscopia Eletrônica de Varredura - MEV), bem como, área superficial específica (ASEBET) e porosidade. Estudo cinético foi realizado, visando determinar o tempo de equilíbrio do processo de adsorção, bem como, o mecanismo cinético que controla o processo. Também foram modeladas isotermas de Langmuir e Freundlich. A determinação da atrazina, após os ensaios de adsorção, foi realizada por Cromatografia Líquida de Alta Performance (CLAE). As análises realizadas apontaram que a capacidade de adsorção dos biocarvões diminuiu na ordem de BE 450 > BE 350 > BE 550, e tal capacidade está associada às características físicas e químicas dos biocarvões. Os três biocarvões são bem representados pelo modelo cinético de pseudo-segunda ordem. Todos biocarvões exibiram elevada afinidade para a adsorção do herbicida atrazina, contudo, o biocarvão produzido à 450 ºC demonstra maior capacidade de adsorção

Made available in DSpace on 2017-07-10T19:25:01Z (GMT). No. of bitstreams: 1 tatiane_texto.pdf: 2558616 bytes, checksum: c23ff4ce31df2fb07ce669109433709c (MD5) Previous issue date: 2011-08-08 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Swine wastewater application into soil to reuse water on cropping provides the addition of total and dissolved organic matter to soil, which interferes in the dynamics of pesticides in soil. This study aims at evaluating the effects of total and dissolved organic matter application from two systems of swine wastewater, biodigestor and lagoon treatments, in alachlor sorption, desorption, leaching and formation of bound residues into soil. The batch method was used to test sorption and desorption and the results were presented in Freundlich isotherms. The evaluation of miscible displacement of alachlor, in soil treated with total and dissolved organic matter, was performed by disturbed soil columns, by monitoring the concentration of alachlor in leachate, total organic carbon and pH. Extraction and quantification of desorption, extractable and bound residues were carried out. After that, it was registered the chemical fractionation of humic substances in extracts containing organic matter of low molecular weight, humic acids and fulvic acids, which were characterized by infrared spectroscopy and total organic carbon concentration. The swine wastewater addition promoted greater sorption and desorption of alachlor compared to Control. The dissolved organic matter promoted less sorption of alachlor in soil when compared to total organic matter, resulting in an increased leaching of alachlor. The dissolved organic matter did not show desorption residues, only extractable ones. The highest amount of total organic carbon was in organic matter of low molecular weight, spectroscope characterized, by the presence of carboxylate anions, which are important in sorption process. The total organic matter has contributed to the emergence of new sorption sites in soil column and the solids present in its composition blocked the movement of pesticide, resulting in lower leaching of alachlor. The dissolved organic matter interacted with alachlor and / or competed with the sorption sites of soil, promoting greater losses by leaching of this herbicide. / A aplicação de água residuária de suinocultura ao solo como reúso de água na agricultura resulta na adição de matéria orgânica total e dissolvida, que interferem na dinâmica dos pesticidas no solo. Objetivou-se avaliar o efeito da aplicação de matéria orgânica total e dissolvida proveniente de dois sistemas de tratamento de água residuária de suinocultura, biodigestor e esterqueira, na adsorção, dessorção, lixiviação e formação de resíduos ligados de alaclor no solo. O método do equilíbrio foi utilizado para o teste de adsorção e dessorção e os resultados foram apresentados em isotermas de Freundlich. A avaliação do deslocamento miscível do alaclor no solo tratado com matéria orgânica total e dissolvida foi realizada por ensaios em colunas de solo deformado, monitorando-se a concentração de alaclor no lixiviado, teor de carbono orgânico total e pH. Realizou-se a extração e quantificação dos resíduos dessorvíveis, extraíves e ligados do solo. Na sequência, fez-se o fracionamento químico das substâncias húmicas em extratos contendo matéria orgânica de baixo peso molecular, ácidos húmicos e ácidos fúlvicos, que foram caracterizados por espectroscopia infravermelha e pela concentração de carbono orgânico total. A adição de água residuária de suinocultura promoveu maior adsorção e dessorção do alaclor comparado ao Controle. A matéria orgânica dissolvida promoveu menor adsorção de alaclor ao solo comparada à total, resultando em maior lixiviação. A matéria orgânica dissolvida não apresentou resíduos dessorvíveis, apenas extraíveis. A maior quantidade de carbono orgânico total esteve presente na matéria orgânica de baixo peso molecular, caracterizada espectroscopicamente, pela presença de ânions carboxilatos, importantes no processo de adsorção. A matéria orgânica total contribuiu com o surgimento de novos sítios de sorção na coluna de solo e os sólidos presentes em sua composição bloquearam a passagem do pesticida, resultando em menores perdas de alaclor por lixiviação. A matéria orgânica dissolvida interagiu com o alaclor e/ou competiu com os sítios sortivos do solo, promovendo maiores perdas deste herbicida por lixiviação.

Made available in DSpace on 2017-05-12T14:47:13Z (GMT). No. of bitstreams: 1 Thaisa _Pegoraro.pdf: 1491826 bytes, checksum: 1b9380fd12ae09c6e6128b1816c0215e (MD5) Previous issue date: 2015-02-23 / Biochar, also known as terra preta do índio, is a highly porous material and is a result of biomass pyrolysis in oxygen-controlled conditions and low temperatures (up to 600 oC). Due to the viable manufacturing process and the wide variety of applications, it is a promising material for various uses. Among the main uses of biochar, studies indicate its potential in improving soil quality, besides being a way of contributing to carbon sequestration from the atmosphere and used in the retention of organic and inorganic contaminants in the environment. This work aimed to present a review of the concepts and current studies on biochar, for a better understanding of the subject (Paper 1). The objective was to also investigate the adsorption of pharmaceuticals carbamazepine (CBZ) and lincomycin (LMC) by six biochars under the influence of surface characteristics of biochar (produced from Brazilian pepper and sugarcane bagasse, in temperatures of 300 o, 400 o and 600o C) and environmental factors (pH and adsorption competition between CBZ and LMC) (Paper 2). The latest study aimed to understand the effects of exposure of dissolved organic matter (DOM) in the surface properties of three biochars produced from sugarcane bagasse, in the CBZ adsorption (Paper 3). Batch equilibrium tests were performed in constant temperature, varying pH, and the data were adjusted in Freundlich isotherms. For the DOM test, the biochars were previously loaded with humic acid, tannic acid, gallic acid, and catechol in concentrations equivalent to those found in soils. The values of Kd, n and KF were reported and analyzed. As a result, it was found that biochars produced from sugarcane bagasse and high pyrolysis temperature were more effective in CBZ and LMC adsorption. In the biochar produced from bagasse at 300° C, the adsorption of CBZ was not affected by the presence of functional groups on the surface of biochar. LMC, which is ionized at pH 7.6, is more easily binded to negatively charged biochars when pH is acidic (pH<pKa). Furthermore, it was found that the CBZ and LMC compete for the same adsorption sites, regardless the variation of pH solution. In general, DOM affected adsorptive properties of biochars and attenuated CBZ adsorption, especially for biochars produced in higher temperatures because of the greater complexity of its structure, when DOM enters or blocks the biochar micro and mesoporous. It was concluded that the use of biochar as a product of sustainable feature looks promising, but there are still some gaps in the current literature about the positive and negative impacts of its use. Laboratory results indicate a possible use of biochar in removing organic compounds from water, which can replace less effective existing treatment technologies. There is to be considered, however, several factors that influence this process and more studies are needed to corroborate such evidence. / O biocarvão, também conhecido como terra preta do índio, é um material de alta porosidade e é resultado da pirólise da biomassa em condições de oxigênio controlado e baixas temperaturas (até 600 oC). Devido ao viável processo de produção e à ampla variedade de aplicações, trata-se de um material promissor para diversos usos. Dentre as principais utilidades do biocarvão, estudos indicam seu potencial na melhoria da qualidade do solo, além de ser uma forma de contribuir para o sequestro de carbono da atmosfera e ser utilizado na retenção de contaminantes orgânicos e inorgânicos no ambiente. Nesse trabalho, objetivou-se realizar uma revisão sobre os conceitos e estudos atuais sobre biocarvão, para uma melhor compreensão do tema (Artigo 1). Objetivou-se também investigar o processo de adsorção dos fármacos carbamazepina (CBZ) e lincomicina (LMC) por seis biocarvões, sob a influência de características superficiais do biocarvão (produzidos a partir de pimenta brasileira e bagaço de cana-de-açúcar, a 300o, 400o e 600o C) e fatores ambientais (pH e competição sortiva entre CBZ e LMC) (Artigo 2). No último estudo, objetivou-se compreender os efeitos da exposição da matéria orgânica dissolvida (MOD) nas propriedades superficiais de três biocarvões produzidos a partir de bagaço de cana-de-açúcar, na adsorção de CBZ (Artigo 3). Ensaios de equilíbrio de adsorção foram realizados em batelada e temperatura constante, variando o pH, e os dados foram ajustados em isotermas de Freundlich. Para o ensaio com MOD, os biocarvões foram previamente carregados com ácido húmico, ácido tânico, ácido gálico e catecol em concentrações equivalentes às de matéria orgânica encontrada em solos. Os valores de Kd, KF e n foram reportados e analisados. Como resultado, verificou-se que biocarvões produzidos a partir da biomassa de bagaço de cana-de-açúcar e altas temperaturas de pirólise foram mais efetivos na adsorção de CBZ e LMC. Em biocarvão produzido a partir de bagaço de cana-de-açúcar, a 300 oC, a adsorção de CBZ não foi afetada pela presença de grupos funcionais na superfície do biocarvão. Já a LMC, que é ionizada a pH 7,6, liga-se mais facilmente a biocarvões carregados negativamente quando o pH é ácido (pH<pKa). Além disso, verificou-se que a CBZ e LMC competem entre si pelos mesmos sítios sortivos, independente da variação do pH da solução. A MOD afetou as propriedades adsortivas de biocarvões para CBZ, principalmente em biocarvões produzidos a maiores temperaturas, devido à maior complexidade de sua estrutura, entrando ou bloqueando os micro e mesoporos do biocarvão. Conclui-se que o uso do biocarvão como um produto de característica sustentável parece ser promissor, porém, lacunas ainda existem na literatura atual sobre os impactos positivos e negativos do seu uso. Os resultados laboratoriais indicam um possível uso do biocarvão na remoção de compostos orgânicos da água, o que pode substituir tecnologias de tratamento existentes menos eficazes. Há, porém, de se considerar diversos fatores de influência nesse processo e mais estudos devem ser realizados a fim de corroborar com tais evidências.

Made available in DSpace on 2017-05-12T14:47:40Z (GMT). No. of bitstreams: 1 Mariana_ sbizzaro.pdf: 1501907 bytes, checksum: 5610159e30f98d52848320f90146f751 (MD5) Previous issue date: 2016-02-12 / The agricultural sector has great influence in Brazilian economy. Furthermore, agricultural yield has been associated with pesticides application during crop cycle, which atrazine is applied for example, since it can cause environmental contamination when it does not reach its target. Thus, there are some essential and imperative options that can minimize contamination and negative impacts during agricultural practices. So, present study aimed at evaluating the ability of three biochars in atrazine adsorption. Therefore, three biochars produced from bamboo culm were used, whose species is Phyllostachys aurea, and temperature ranged at 350 ºC, 450 ºC and 550 ºC. The three studied biochars were named as BE350, BE450 and BE550. They were characterized based on their physical and chemical properties by elemental analysis, characterization of functional groups (Infrared Spectroscopy Fourier Transform - FTIR), surfaces morphology evaluation (Scanning Electron Microscopy - SEM) as well as specific surface area (ASEBET) and porosity. A kinetic study was carried out to determine the equilibrium period of adsorption process and the kinetic mechanism that controls such process. Langmuir and Freundlich isotherms were also modeled during this trial. Atrazine determination, after the adsorption test, was carried out by High Performance Liquid Chromatography (HPLC). The obtained analyses showed that the adsorption capacity of biochars decreased in the following order: BE 450> BE 350 > BE 550, and such capacity has been associated with the physical and chemical characteristics of biochars. The three studied biochars are well represented by the kinetic model of pseudo-second order. At last, all biochars have shown high affinity to adsorb atrazine; however, the biochar that was produced at 450 ºC has shown the highest adsorption capacity. / O setor agrícola possui grande destaque na economia brasileira, a produção agrícola está associada ao uso de pesticidas durante o ciclo das culturas, como é o caso da atrazina, que pode causar a contaminação do ambiente, quando não atinge seu alvo. Sendo assim, alternativas que minimizem as contaminações e impactos negativos da prática agrícola são essenciais e urgentes. Desta forma, o presente estudo teve por objetivo avaliar a capacidade de três biocarvões, em adsorver o herbicida atrazina. Para tanto, foram utilizados três biocarvões, produzidos a partir do colmo de bambu, da espécie Phyllostachys aurea à 350ºC, 450ºC e 550ºC, nomeados BE350, BE450 e BE550. Os biocarvões foram caracterizados quanto as propriedades físicas e químicas, por meio de análise elementar, caracterização de grupos funcionais (Espectroscopia de Infravermelho com Transformada de Fourier - FTIR), avaliação da morfologia das superfícies (Microscopia Eletrônica de Varredura - MEV), bem como, área superficial específica (ASEBET) e porosidade. Estudo cinético foi realizado, visando determinar o tempo de equilíbrio do processo de adsorção, bem como, o mecanismo cinético que controla o processo. Também foram modeladas isotermas de Langmuir e Freundlich. A determinação da atrazina, após os ensaios de adsorção, foi realizada por Cromatografia Líquida de Alta Performance (CLAE). As análises realizadas apontaram que a capacidade de adsorção dos biocarvões diminuiu na ordem de BE 450 > BE 350 > BE 550, e tal capacidade está associada às características físicas e químicas dos biocarvões. Os três biocarvões são bem representados pelo modelo cinético de pseudo-segunda ordem. Todos biocarvões exibiram elevada afinidade para a adsorção do herbicida atrazina, contudo, o biocarvão produzido à 450 ºC demonstra maior capacidade de adsorção