Submitted by (edna.saturno@ufrpe.br) on 2016-07-26T11:34:06Z No. of bitstreams: 1 Aldenise Chagas Curvello G Moreira.pdf: 1832678 bytes, checksum: 08dcbab15cec31bc62f7c570ddae3ae1 (MD5) / Made available in DSpace on 2016-07-26T11:34:06Z (GMT). No. of bitstreams: 1 Aldenise Chagas Curvello G Moreira.pdf: 1832678 bytes, checksum: 08dcbab15cec31bc62f7c570ddae3ae1 (MD5) Previous issue date: 2011-02-24 / The aim this work was to characterize "cajá-umbu" fruits coming from the germplasm's collection IPA (Instituto Agronômico de Pernambuco). Fruits of the 4 genotypes (G 2.2, G 2.3, G 3.1, G 3.2) were used to quantify the phytochemicals bioactive and evaluate the antioxidant potential. The polyphenols were quantified by spectrophotometric method, the ascorbic acid by titulometric method and carotenoids by chromatographic and spectrophotometric techniques. Hydroacetone, hydromethanolic and aqueous extracts were obtained using 3 extraction systems: a) sequential extraction: acetone 80%, methanol 80% and water, b) sequential extraction: water, methanol 80% and acetone 80% c) non¬sequential extraction. The isolated and combined extracts were submitted to the determination of total phenolic content, screened for their free DPPH- (1,1¬diphenyl-2-picrilhidrazil) and ABTS-+) (2,2'-azino-bis-(3-etilbenzotiazoline 6¬sulfonic acid) scavenging activity, and their effect on the linoleic acid peroxidation by the system of co-oxidation r3-carotene/acid linoleic and ferric thiocyanate method. The fruits showed significant content of polyphenols, low levels of ascorbic acid and carotenoids. The I3-carotene 5-6, 5'6'-diepoxide was the major component of genotypes G 2.2, G 2.3, G 3.1, and 5-6 epoxide lutein for G 3.2. The extraction procedure which employed acetone 80% as first solvent could extract a larger amount of total phenolic. Ali genotypes exhibited good DPPH- scavenging activity (ECSD value of 0.30 to 0.43, TEcSD value of 8.98 to 15.24 minutes, and EA value of 0.18 to 0.40), significant ABTS-+ scavenging capacity (55.56 a 120.08 IJMol TEAC.g-1) and high percentage of inhibition of peroxidation of linoleic acid (88.45 to 92.89%). In co-oxidation of linoleic acid/r3-carotene system exhibited moderate activity (56.91 to 69.41 % inhibition), showing that they are effective in blocking the onset of oxidation reaction (F1 <1), but the propagation phase, G 3.2 genotype showed higher efficiency (F2 <1). Therefore, fruits of "cajá-umbuzeiro" have bioactive compounds and good antioxidant potential that can contribute te the dietary intake of antioxidant. / Com o objetivo de caracterizar frutos de genótipos de cajá-umbuzeiras cultivados no Banco de Germoplasma do IPA (Instituto Agronômico de Pernambuco), frutos de 4 genótipos (G 2.2; G 2.3; G 3.1; G 3.2) foram utilizados para quantificar principais fitoquímicos bioativos e avaliar o potencial antioxidante. Os polifenóis foram quantificados por método espectrofotométrico; o ácido ascórbico por método titulométrico e os carotenóides por técnicas• cromatográfica espectrofotométrica. Os extratos hidroacetônico, hidrometanólico e aquoso forar obtidos empregando-se 03 sistemas de extração: a) extração sequencial: acetom a 80%, metanol a 80% e água; b) extração sequencial: água, metanol a 80% e acetona a 80%; c) extração não sequencial. Os extratos isolados e combinados foram avaliados quanto ao teor de fenólicos totais, a capacidade de sequestrar o radical 1, 1-difenil-2-picrilhidrazil (DPPHe) e o radical 2,2' -azino-bis-(3-etilbenzotiazolina-6-ácido sulfônico (ABTSe+), a inibição da oxidação em sistema da co-oxidação l3-caroteno/ácido linoléico e pelo método tiocianato férrico. Os frutos apresentaram teor relevante de polifenó!s, baixos teores de ácido ascórbico e de carotenóides. O l3-caroteno-5,6-5'6'-diepóxido foi o componente majoritário dos genótipos G 2.2; G 2.3; G 3.1, e a luteína-5,6 epóxido do G 3.2. O procedimento de extração que empregou a acetona 80% como primeiro solvente conseguiu extrair maior quantidade de fenólicos totais. Todos os genótipos exibiram relevante capacidade de sequestro do radical DPPH (ECsD de 0,30 a 0,43, T ECSD de 8,98 a 15,24 minutos, e EA de 0,18 a 0,40), expressiva capacidade de sequestro do radical ABTSe+ (55,56 a 120,08 IlMol TEAC.g-1) e forte inibição da peroxidação do ácido linoléico (88,45 a 92,89%). Em sistema da co-oxidação do ~-caroteno/ácido linoléico exibiram ação moderada (56,91 a 69,41 % de inibição), demonstrando serem eficientes em bloquear o início da reação) de oxidação (F1 <1), porém na fase de propagação, o genótipo G 3.2 demonstrou maior eficiência (F2<1). Os frutos do cajá-umbuzeiro apresentam em sua constituição compostos bioativos e bom potencial antioxidante, podendo contribuir com o aporte dietético de antioxidante.

A deficiência de Zn no solo causa efeitos indesejáveis na produção agrícola, pois a baixa disponibilidade deste micronutriente para as plantas promove a diminuição da atividade enzimática, além da deficiência deste elemento na alimentação, que pode levar ao estado de subnutrição. Tendo em vista a problemática do Zn no sistema solo-planta e suas variações nos compartimentos do solo, é importante a avaliação de sua fitodisponibilidade e as frações do solo que este elemento está associado. O objetivo deste trabalho foi avaliar a fitodisponibilidade e a compartimentalização de Zn no solo, para as culturas de arroz (Oryza sativa L.) e soja (Glycine max L. Merrill) e avaliar o efeito das doses de Zn sobre a nutrição e exportação deste nutriente pela cultura. Utilizou-se como plantas teste as culturas de arroz e soja para avaliar o efeito das doses de Zn sobre a nutrição e translocação deste nutriente até os grãos. Para tanto, uma amostra de um Latossolo Vermelho, textura argilosa da região de Piracicaba (SP) foi utilizada e ZnCl2 (marcado com 65Zn) como fonte. O experimento foi conduzido em casa de vegetação em DIC, com cinco doses de Zn (0, 1, 2, 4 e 8 mg kg-1 de solo), com quatro repetições. O experimento foi conduzido até a formação de grãos e foi realizada determinação de Zn por Espectrômetria de Absorção Atômica após digestão nitroperclórica e contagem do 65Zn nas partes da planta: parte aérea (PA) e panícula (P), para arroz e PA, vagem (V) e grão (G), para soja. Calculou-se a quantidade de Zn proveniente da fonte (Znpf) nas partes das plantas e o aproveitamento do Zn da fonte pelas culturas (Ap). Nas amostras de solo foram realizadas extrações por DTPA (ZnDTPA) e Mehlich-1 (ZnM1) em duas subamostragens (t1 e t2), antes da semeadura e florescimento, respectivamente. O fracionamento de Zn foi realizado em amostras de t2 nas frações: trocável (ZnTroc); ligado a carbonatos (ZnCarb); a matéria orgânica (ZnMO); a óxidos (ZnOxi) e residual (Znres). Adicionalmente, foi realizada análise do teor pseudo-total de Zn (ZnPST). Os dados obtidos foram submetidos à análise de variância pelo teste-F a 95 % de probabilidade, ajuste das variáveis em função das doses por regressões e teste de média e análises de correlações entre as principais variáveis respostas. O Zn acumulado total na planta se ajustou à regressão linear em função do aumento das doses, entretanto ao analisar as partes separadamente, só houve diferença entre as doses para a variável PA em ambas as culturas. O Znpf total nas plantas apresentou incremento com a adição das doses crescentes de Zn ao solo, entretanto, eu aproveitamento foi baixo, 12 e 8,75 % para arroz e soja, respectivamente. As doses de ZnCl2 adicionadas ao solo, aumentaram a concentração de Zn presente nas frações ZnTroc > ZnMO > ZnCarb, em ordem decrescente. O Zn total acumulado nas plantas de arroz e soja apresentam correlações crescentes para os extratores DTPA e M1 nas duas subamostragens (t1 e t2), em função das doses avaliadas. O Zn extraído pelo DTPA ou M1, apresentaram correlação significativa com o Zn extraído nas frações, na ordem decrescente, ZnTroc > ZnCarb > ZnMO / Zn deficiency in soil causes undesirable effects on agricultural production because the low availability of this micronutrient for plants promotes the decrease in enzymatic activity besides the deficiency of this element in food, which can lead to a state of malnutrition. Considering the problem of Zn in soil-plant system and its variations in soil compartments, it is important to evaluate its bioavailability and forms in soil which this element is associated. The objective of this study was to evaluate Zn bioavailability and compartmentalization in the soil, to the rice (Oryza sativa L.) and soybean (Glycine max L. Merrill) crops and evaluate the effect of Zn levels on nutrition and exportation of this nutrient by the crops. As test plant rice and soybeans were used to evaluate the effect of Zn rates on nutrition and the nutrient translocation to the grains. For this purpose, a sample of an Oxisol (FAO), an clay texture from Piracicaba (SP) region, was used and ZnCl2 (labelled with 65Zn) as a source. The experiment was conducted in a greenhouse in CRD, with five rates of Zn (0, 1, 2, 4 and 8 mg kg-1 soil), with four repetition. The experiment was conducted until the formation of grains and Zn analyzis were performed by Atomic Absorption Spectrophotometery after nitricperchloric digestion and 65Zn counting of parts: shoot (PA) and panicle (P) for rice and PA, beans pods (Pd) and grains (G) for soybeans. The amount of Zn derived from the source (Znpf) was calculated in the plant parts and the recovery of the Zn by the crops (Ap). In the soil samples, extractions were performed by DTPA (ZnDTPA) and Mehlich-1 (ZnM1) methods in two sub samples (t1 and t2) prior to seeding and flowering, respectively. The Zn fractionation was performed on samples of t2 in the fractions: exchangeable (ZnTroc); linked to carbonates (ZnCarb); to organic matter (ZnMO); to oxides (ZnOxi) and residual (Znres). Additionally, analysis of the pseudo-total content of Zn (ZnPST) was performed. Data obtained was subjected to analysis of variance by the F-test at 95% probability, adjusting the variables depending on the rates for regression and average test and analysis of correlations between the main variables. The total cumulative Zn in the plant set to the linear regression in terms of increasing rates, however when analyzing the parts separately, just the PA showed differences between doses, for both crops. The total Znpf increased with the increasing rates, however its recoveries were low, approximately 12% for rice and 8.75 % for soybean. The ZnCl2 rates in soil increased the Zn concentration in the fractions: ZnTroc > ZnMO > ZnCarb, in descending order. The total cumulative Zn in the rice and soybean plants are growing correlations for extractors DTPA and M1 for two sub samples (t1 and t2), depending on the rates evaluated. The Zn extracted by DTPA or M1 were significantly correlated with Zn extracted in fractions in descending order: ZnTroc > ZnCarb > ZnMO

Made available in DSpace on 2016-08-19T12:56:44Z (GMT). No. of bitstreams: 1 Dissertacao Maria de Lourdes.pdf: 1957911 bytes, checksum: 71ed8d1c2f93361fcb544ae3efad37e2 (MD5) Previous issue date: 2013-01-25 / In the present study it was determined the total stock of phosphorus (PT) in sediments from Anil and Bacanga rivers located on Maranhão island. Additionally, with the aim of assessing the lability of phosphorus in the sediment, it was used sequential chemical extraction according to the protocol of the European Commission (Standards, Measurements and Testing Program). The results indicate PT concentrations ranging from 877.91 to 1466.44 mg. Kgˉ¹, which allows classifying these sediments moderate to highly polluted. The geochemistry of inorganic phosphorus fraction non apatite (PINA) was in mean 32% and the sum of organic fractions (PO) and PINA, considered the greatest lability, showed mean values of 65%, indicating that most of the phosphorus has potential to migrate to interstitial water. Principal component analysis indicates that the PO is proportional to organic matter (OM) and that the silt and clay did not showed good relationship with the fractions PIA and PINA in different sediments. Infrared absorption spectra reveal the intensification of bands in the region between 1200 and 1800 cmˉ¹, which features a large amount of minerals. Aiming to study the capacity of sediment P sorption was conducted adsorption experiments. Data were adjusted by Langmuir and Freundlich equation. For each batch experiment was calculated rate constant (k), the linear coefficient of determination (R²) and the maximum amount of P adsorbed (Qmax). The Langmuir model was suitable to describe the adsorption of P in sediments, because this model showed better linear coefficient of determination (R²). The sediments have yet expressive capacity of phosphate adsorption within the parameters of adsorption isotherms, which can act as a mitigating factor against the significant contribution of phosphorus via raw sewage. / No presente estudo, foi determinado o estoque total de fósforo (TP) em sedimentos de rios Anil e Bacanga localizados na ilha do Maranhão. Além disso, com a finalidade de avaliar a labilidade de fósforo no sedimento, foi realizada a extração química sequencial de acordo com o protocolo da Comissão Europeia (normas, medidas e programa de testes). Os resultados do Rio Bacanga indicou concentrações de PT que variam de 877,91 mg kgˉ¹ e 1466,44 mg Kgˉ¹, o que permite classificar estes sedimentos em moderado a altamente poluído. A geoquímica da fração de fósforo inorgânico não apatítico (PINA) foi em média, 32% e a soma do fósforo orgânico (PO) e PINA, considerado fração lábil, apresentaram valores médios de 65%, indicando que a maior parte do fósforo tem um potencial de migrar para a água intersticial. Análise de componentes principais indicou que o PO é proporcional ao teor de matéria orgânica (MO) e que o silte e argila não apresentou bom relacionamento com frações de fósforo inorgânico apatítico (PIA) e fósforo inorgânico não apatítico (PINA) nos sedimentos. Os espectros de absorção no infravermelho revelaram a intensificação das bandas na região entre 1200 e 1800 cmˉ¹, que apresenta uma grande quantidade de minerais. Com o objetivo de estudar a capacidade de sorção de P pelos sedimentos, foi realizado experimentos de adsorção. Os dados foram ajustados pela equação de Langmuir e Freundlich. Para cada experiência foi calculada a constante de velocidade (k), o coeficiente linear de determinação (R²) e a quantidade máxima de P adsorvido (Qmáx). O modelo de Langmuir foi o mais adequado para descrever a adsorção de P nos sedimentos. Os sedimentos têm capacidade mais expressiva de adsorção de fosfato dentro dos parâmetros de isotermas, que podem atuar como um fator de mitigação contra a contribuição significativa de fósforo através de esgoto.

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2016-04-11T16:45:54Z No. of bitstreams: 1 Dissertação Christiane Monte.pdf: 2209030 bytes, checksum: eeebb11c7f77055af279832c47fc6546 (MD5) / Made available in DSpace on 2016-04-11T16:45:54Z (GMT). No. of bitstreams: 1 Dissertação Christiane Monte.pdf: 2209030 bytes, checksum: eeebb11c7f77055af279832c47fc6546 (MD5) / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências-Geoquímica. Niterói, RJ / A ressuspensão de sedimentos por processos naturais ou atividades antrópicas (como as dragagens) pode afetar a biodisponibilidade de metais-traço. Esta hipótese foi testada numa área da Baía de Sepetiba (RJ) afetada por elevada contaminação por Cd e Zn, que recebe aporte fluvial de efluentes industriais e urbanos. Desta forma, o objetivo geral do presente estudo foi avaliar os efeitos da ressuspensão de sedimentos da região afetada pelo Saco do Engenho (Baía de Sepetiba) sobre a biodisponibilidade de metais-traço potencialmente tóxicos (Cd, Cu, Ni, Pb e Zn), por meio de ensaio laboratoriais, como estratégia de abordagem visando subsidiar a avaliação de risco ambiental associado à dragagem. Amostras de 12 pontos de amostragem foram coletadas próximas ao Canal do Saco do Engenho e do Porto de Itaguaí e submetidas a dois intervalos de tempo de ressuspensão (1 hora e 24 horas). Com a exceção do Ni, os metais-traço superaram os valores de background locais. Em particular, concentrações muito elevadas de Cd e Zn foram observadas, acima dos valores de background locais 5-71 vezes e 2-56 vezes, respectivamente, e até 16 e 27 vezes acima dos valores orientadores de qualidade de sedimentos de Nível 1 adotados pela Resolução CONAMA 454/2012, respectivamente. Houve predominância da fração fracamente ligada (extraída em HCl 1 mol/L), exceto para o Ni, ocorrendo tendência de redução da biodisponibilidade potencial com a distância do Canal do Saco do Engenho em relação a Cd, Cu, Pb e Zn. As mudanças nas concentrações fracamente ligadas de Cd e Zn após a ressuspensão foram acima dos valores orientadores de Nível 1 em apenas duas amostras. Foi evidenciado que compostos de Fe e Mn são importantes fatores de influencia sobre a fração fracamente ligada aos sedimentos, enquanto o carbono orgânico total (COT) mostrou correlação com Cd, Zn e Cu na fração fortemente ligada aos sedimentos (extraída em HNO3 concentrado), demonstrando a importância da matéria orgânica para a preservação destes metais nesta fração menos susceptível a incorporação biológica. Embora tenham sido encontradas concentrações de sulfetos voláteis em meio ácido (AVS) suficientes para reter os metais simultaneamente extraídos (SEM) na fase sólida na maior parte das amostras, as concentrações de AVS não apresentaram nenhuma correlação com os metais. Os resultados evidenciam que a ressuspensão afeta a biodisponibilidade de diferentes metais, principalmente no primeiro intervalo de tempo (1 hora), refletindo mudanças abruptas em função da exposição a condições oxidantes / The re-suspension of sediments due to natural processes or anthropogenic activities (such as dredging) can influence the trace metal bioavailability. This hypothesis was tested in an area of Sepetiba Bay (RJ) affected by elevated contamination by Cd and Zn, which receive industrial and urban effluents by fluvial input. Therefore, the main objective of this study was to evaluate the effects of re-suspension of sediments from the region affected by Saco do Engenho (Baía de Sepetiba) on the bioavailability of potentially-toxic trace metals (Cd, Cu, Ni, Pb and Zn), by performing laboratory assays, as a strategy to subside the environmental risks associated to dredging. Samples from 12 sampling points were collected near the Saco do Engenho creek and the Itaguaí Harbor, being submitted to two re-suspension time intervals (1 hour and 24 hours). With the exception of Ni, trace metals exceeded local background values. In particular, very high concentrations were found for Cd (5‒71 times local background) and Zn (2‒56 times local background), corresponding to values above sediment quality guideline of Level 1 adopted by the CONAMA resolution 454/2012 (up to 16-times higher for Cd and 27-times higher for Zn). There was predominance of weakly-bound fraction (extracted in 1 mol/L HCl), except for Ni, occurring a tendency of decrease in the potential bioavailability with the distance from the Saco do Engenho creek in relation to Cd, Cu, Pb and Zn. Changes in the weakly-bound concentrations of Cd and Zn after re-suspension were above the Level 1 for two samples only. It was evidenced that Fe and Mn compounds are important factors affecting the weakly-bound fraction, while total organic carbon (TOC) showed correlations with Cd, Zn and Cu strongly-bound fraction (extracted in concentrated HNO3), demonstrating the importance of organic matter for the preservation of these metals in such fraction less susceptible to biological incorporation. Although there were acid-volatile sulfide (AVS) concentrations sufficient to retain simultaneously-extracted metals (SEM) in the solid phase in most samples, the AVS concentrations were not correlated with metals. Results evidence that re-suspension affects the bioavailability of different metals, principally in the first time interval (1 hour), reflecting abrupt changes due to exposure to oxidizing conditions

Philosophiae Doctor - PhD / The primary aim of these coal fired industries for co-disposing fly ash and brine was to use the fly ash as a sustainable salt sink. It is therefore important to study the interaction chemistry of the fly ash-brine systems to fully understand the leaching and mobility of the contaminant species, and to determine the possibility of capturing the salts from the brine solution when fly ash and brine are co-disposed. In order to achieve the aims and objectives of this study, several leaching procedures such as batch reaction tests, long-term fly ash-brine interaction tests, acid neutralization capacity (ANC) tests, up-flow percolation tests and sequential extraction tests were employed. The geochemical modeling software was applied to predict the formation of secondary mineral phases controlling the release of species in the fly ash-brine systems. Several analytical techniques such as x-ray diffraction (XRD), x-ray fluorescence (XRF), scanning electron microscopy-energy dispersion spectroscopy (SEM-EDS), inductively coupled plasma-mass spectroscopy (ICP-MS) and ion chromatography (IC) were applied to characterize the fresh fly ashes, solid residues recovered from the fly ash-brine interaction tests, the brine sample used in this study and the leachate samples in order to determine the chemical and mineralogical compositions and speciation of the waste materials. / South Africa

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23495号 / 工博第4907号 / 新制||工||1767(附属図書館) / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 米田 稔, 教授 清水 芳久, 教授 高岡 昌輝 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

<p>Predmet izučavanja ove disertacije je ispitivanje mogućnosti imobilizacije&nbsp;toksičnih metala u sedimentu primenom imobilizacione tehnike&nbsp;solidifikacije/stabilizacije portland cementom, kalcijum-oksidom, prirodnim zeolitom,&nbsp;letećim pepelom, kaolinitom, montmorilonitom, i različitim sme&scaron;ama ovih agenasa&nbsp;kao i određivanje njihove efikasnosti u zavisnosti od brojnih faktora. Efikasnost&nbsp;imobilizacionih postupaka praćena je kori&scaron;ćenjem tzv. testova izluživanja, odnosno&nbsp;određivanjem koncentracije metala koji su u toku određenog vremena iz imobilisane&nbsp;faze pre&scaron;li u mobilnu fazu gde se smatraju potencijalno opasnim i biodostupnim.&nbsp;Krajnji cilj svakog testa izluživanja je mogućnost procene adekvatnosti primene&nbsp;određene imobilizacione, odnosno remedijacione tehnike. Efikasnost imobilizacionih&nbsp;postupaka zavisi i od određenih osobina: pH rastvora, dodatka imobilizacionog agensa&nbsp;&scaron;to je istraživanjem ispitano. Na osnovu ovog testa, odnosno &nbsp; odnosa kumulativne&nbsp;frakcije metala koja je oslobođena iz imobilizacione sme&scaron;e u mobilnu fazu i vremena&nbsp;određen je tip mehanizma koji omogućava transport metala &nbsp;(spiranje, difuzija,&nbsp;rastvaranje). Takođe su određeni i i parametri (koeficijenti difuzije, indeksi&nbsp;izlužljivosti) koji&nbsp; će poslužiti za ocenu efikasnosti prethodno primenjenih&nbsp;imobilizacionih tehnika. Primenjeni su i modifikovani testovi izluživanja sa ciljem &scaron;to&nbsp;bolje simulacije realnih uslova. U modifikovanim testovima izluživanja kori&scaron;ćen je&nbsp;rastvor sa pH 3,25 da bi se simulirali uslovi koji opona&scaron;aju kisele ki&scaron;e, odnosno uslovi&nbsp;u realnom sistemu. Takođe je kor&scaron;ćen i rastvor huminskih materija sa ciljem&nbsp;simulacije uslova velikog organskog opterećenja do kojeg bi moglo doći u slučaju&nbsp;akcidentnih situacija (na primer poplava) i generalno uslova koji se stvaraju u &nbsp;prirodi&nbsp;pri raspadanju organskog materijala (li&scaron;će, trava, itd.). Rezultati dobijeni simulacijom&nbsp;ovih uslova će dalje omogućiti modelovanje pona&scaron;anja metala u smislu dugoročnog&nbsp;&quot;izluživanja&quot; iz tretiranog sedimenta kao i procenu najefikasnijih agenasa &nbsp; za&nbsp;imobilizaciju različitih metala u sedimentu. Na osnovu dobijenih rezultata, zaključeno&nbsp;je da su optimalni agensi za imobilizaciju metala u sedimentu sme&scaron;a cementa i kreča&nbsp;(5% cementa i 10% kreča), sme&scaron;a montmorilonita i kreča (30% montmorilonita i 10%&nbsp;kreča), leteći pepeo (30%) i zeolit (30%). U ovim sme&scaron;ama dominantan mehanizam&nbsp;izluživanja je difuzija, a ove sme&scaron;e se mogu smatrati inertnim otpadom po svim&nbsp;ispitivanim kriterijumima. Ovi rezultati se mogu upotrebiti za projektovanje i&nbsp;izgradnju pilot postrojenja na kome bi se ispitala efikasnost ovih agenasa za&nbsp;remedijaciju sedimenta u realnim uslovima. Dobijeni podaci su neprocenjivi sa&nbsp;aspekta ekonomski i ekolo&scaron;ki prihvatljivog upravljanja sedimentom.</p> / <p>This work is concerned with exploring the possibilities of immobilization of toxic&nbsp;metals in sediments using solidification/stabilization as imobilization technique and&nbsp;using Portland cement, calcium oxide, natural zeolite, flying ash, kaolinite, montmorilonite, and various mixtures of these agents and determine their&nbsp;effectiveness depending on many factors. Performance of imobilization procedures&nbsp;was followed by the use of so-called leaching tests and determination of the metals&nbsp;concentration that are within a specified interval of time leached from the immobile phase and as such can be considered potentially hazardous and bioavailable. The ultimate goal of every leaching test is to assess the adequacy of the possibility of applying certain imobilization or remediation technique. Performance of imobilizaction procedures depends on certain characteristics: pH of solution, additon of imobilization agent, etc. Based on this test, ie relation between the cumulative fraction of metal leached from imobilization mixture and time, the type of leaching mechanism that allows the transport of metals (wash-off, diffusion, dissolution) was determined. Other parameters which will serve for evaluating the efficiency of the previously applied imobilization techniques (diffusion coefficients, leaching indices) were also determined. Modified leaching tests were applied with the aim of better simulation of real conditions on the field. In the modified leaching tests the solution with pH 3.25 was used to simulate conditions that mimic acid rain and conditions in the real system. The humic acid solution was also used with the aim to simulate high organic loads which could occur in the case accident situation (eg floods) and the general conditions that are created in naturewhen decaying organic material (leaves, grass, etc.). The results obtained by simulating these conditions will enable the modeling of behavior of metals in terms of long-term leaching period from the treated sediment and assess the most effective agents for the immobilization of various metals in the sediments. Based on these results, it was concluded that the optimal agents for immobilization of metals in the sediment mixture of cement and lime (5% cement and 10% lime), a mixture montmorilonite and&nbsp; lime (30% montmorilonite and 10% lime), fly ash (30%) and zeolite (30%). In these mixtures dominant leaching mechanism is diffusion, and these mixtures can be considered as inert waste by all tested criteria. These results can be used to design and builda pilot plant in which order to evaluate the effectiveness of these agents for remediation of sediment in real &nbsp;terms. The obtained data are invaluable from the aspect of economic and ecologically acceptable management of sediment.</p>

The demand for metals is great for the purpose of developing green technologies, and EU has listed 30 metals and minerals that are of critical importance for the maintenance and evolving of today’s society, so called critical materials. However, mining of raw materials generates mine waste which can have adverse effect on human health, ecosystems, and surrounding areas. To be able to prevent the release of toxic levels of elements from mine waste, an understanding of how different elements behave in the secondary environments is necessary in order to use the most successful methods for mining remediation. It is common that secondary minerals, such as gypsum and/or HFOs (hydrous ferric oxides), forms in mine waste or in downstream environments, depending on the geochemical conditions. From prior studies, it is well established that trace elements are sorbed by HFO. But studies are scares regarding co-precipitation of elements with secondary gypsum formation, and few studies investigates the possibility of critical elements to be captured by secondary minerals. In this study, a prior unknown white precipitation along with tailings material from the Smaltjärnen tailings beach in Yxsjöberg, Sweden, has been investigated by combining mineralogical studies (SEM-EDS and DXRD analysis) with sequential extraction. The aim with the study was to identify the precipitation and to examine if critical elements had co-precipitated with the precipitation and HFOs within the sample. From the results it was possible to prove that the white precipitation was gypsum (CaSO4*2H2O), and it was indicated that some of the critical elements (beryllium for instance) showed affinity for gypsum, and that bismuth, tungsten, and chromium were sorped by HFOs. The combining of chemical analysis with mineralogical studies was of great importance for determining in which mineral phases the leached elements were situated, and the study has shown that secondary gypsum formation can be an important sink for some critical elements. More studies should be performed within this field of research to further investigate the importance of secondary minerals for scavenging of elements, not only to prevent toxic levels to be leached, but also to capture these elements in the purpose of re-mining. / Idag är behovet av metaller stort inom användningsområden för att utveckla gröna teknologier. EU har därför listat 30 metaller och mineral (kritiska material) som anses vara kritiska för att underhålla och utveckla dagens samhälle. Men brytning av råmaterial resulterar i generering av gruvavfall där avfallet potentiellt kan utgöra en risk för att skada bland annat människors hälsa och ekosystem. För att kunna förhindra att giftiga halter av grundämnen släpps ut från gruvavfall så krävs en förståelse om hur olika ämnen beter sig i sekundära miljöer, för att på så sätt kunna tillämpa de mest framgångsrika metoderna för sanering och återställning av gruvområden. Det är vanligt förekommande att sekundära mineraler (såsom gips och järnhydroxider) fälls ut i gruvavfallet och/eller nedströms om gruvområdet beroende på de geokemiska förhållandena. Tidigare studier har visat att spårämnen kan binda till järnhydroxider, men endast ett fåtal studier undersöker samutfällning av olika spårämnen tillsammans med sekundärt gips. Hur specifikt kritiska metaller kan fångas upp av sekundära mineral är ännu inte välstuderat. I denna studie har en vit, tidigare okänd, utfällning provtagits från en av deponierna med anrikningssand i den historiska volframgruvan i Yxsjöberg. Utfällningen identifierades genom att kombinera mineralogiska studier (SEM-EDS och DXRD analys) med kemiska lakvattenanalyser från en sekventiell lakning. Målet med studien var att mineralogiskt karaktärisera den okända utfällningen och att undersöka om kritiska ämnen möjligen samutfällts tillsammans med de sekundära mineralen. Studien visade att utfällningen var sekundärt gips (CaSO4*2H2O) och det kunde påvisas att vissa kritiska metaller visade affinitet för gipset (exempelvis beryllium) och att andra kritiska metaller samutfällts/adsorberats av järnhydroxider. Att kombinera dom olika metoderna visade sig att vara till stor nytta för att kunna påvisa vilka mineral dom olika grundämnena var bundna till, och studien har även visat att sekundärt gips kan vara en sänka för vissa kritiska metaller. Mer studier bör utföras inom detta forskningsområde i framtiden för att vidare undersöka hur sekundära mineral kan binda kritiska metaller, inte endast för att förhindra att giftiga halter av metaller släpps ut, utan också för att undersöka möjligheten att återvinna gruvavfallet för utvinning av kritiska metaller.

ii SUMMARY This master thesis deals with selectivity assessment of an arsenic sequential extraction procedure for evaluating mobility in mine wastes. A modified sequential extraction procedure was designed on the basis of preliminary tests of extraction efficiency and selectivity for the synthetic As mineral phases (scorodite, amorphous iron arsenate, schwertmannite, goethite, jarosite) and five natural samples (Kaňk, Dlouhá Ves, Giftkies, Roudný) that were previously characterized for As concentration and speciation. The modified sequential extraction has five steps. The first leaching step was performed in nitrogen-purged deionized H2O for 10 hours; next step involved 0.01M NH4H2PO4 leaching for 16 hours. Phases in the third step were dissolved with 0.2M Tamm`s reagent in darkness for 2 hours. The fourth step was represented by 0.2M of Tamm`s reagent heated in water bath at 80řC for 4 hours. Strong acid solutions HCl/KClO3/HNO3 were used to leach sulphide phases in the last step. The testing of the sequential extraction procedure using model mixtures showed a good discrimination of several fractions: adsorbed arsenic, arsenic associated with poorly crystalline oxyhydroxide, hydroxosulfate and arsenate phases (amorphous iron arsenate, schwertmannite, ferrihydrite), arsenic associated with crystalline...

Foram conduzidos dois experimentos em casa-de-vegetação com solo contaminado acidentalmente com metais pesados. No primeiro deles objetivou-se avaliar o potencial das espécies vegetais Brassica juncea, Raphunus sativus L., Hybiscus cannabinus e Amaranthus crentus em absorver, translocar e acumular zinco, cobre, manganês, chumbo e boro na parte aérea e assim atuarem na recuperação do solo estudado. No segundo experimento avaliou-se a aplicação dos materiais orgânicos: Solomax, turfa e concentrado húmico mineral como amenizantes de toxidez dos elementos citados para Brassica juncea. Em um terceiro experimento em laboratório, avaliou-se a capacidade de retenção de zinco pelos materiais orgânicos estudados. As variáveis avaliadas foram: produção de material vegetal; quantidades absorvida e acumulada de Zn, Cu, Mn, Pb e B; índices de translocação e remoção desses elementos pelas plantas. No solo foram determinados os teores total e disponível (DTPA e CaCl2 0,01 mol L-1) de Zn, Cu, Mn e Pb. No extrato de saturação foram determinados os teores solúvel (ICP-OES) e livre (eletroforese capilar) dos elementos citados, que também foram determinados na parte aérea da Brassica juncea. Resultados das determinações analíticas também foram introduzidos no programa de especiação iônica MINTEQ. Foram avaliados ainda os efeitos dos materiais orgânicos na distribuição dos metais pesados nas frações do solo. No ajuste dos dados do experimento de retenção de zinco foi a empregado o modelo de Freundlich e calculado o coeficiente de distribuição Kd. Embora as espécies tenham sido capazes de acumular quantidades elevadas dos elementos na parte aérea, elas não puderam ser consideradas hiperacumuladoras. O Amaranthus crentus e a Brassica juncea apresentaram os maiores índices de remoção para Zn, Mn e B. Os materiais orgânicos apresentaram valores elevados de Kd refletindo a alta afinidade do zinco pela fase sólida e elevada capacidade dos materiais orgânicos em imobilizar o elemento. Os elevados coeficientes de correlação obtidos para as isotermas de adsorção indicam que o modelo Freundlich pode ser utilizado para descrever a adsorção do Zn pelos materiais. A quantidade de Zn removida pelos materiais, em termos percentuais variou com o material e com o pH, sendo favorecida nos valores mais elevados. A turfa e o concentrado húmico reduziram os teores de metais extraídos por DTPA e CaCl2 sendo esta redução refletida nos teores acumulados pela Brassica juncea, contudo esta redução não foi suficiente para impedir os efeitos fitotóxicos dos elementos. A especiação dos metais mostrou que o Zn e o Mn encontraram-se principalmente na forma livre, enquanto que o Cu e o Pb apresentaram-se complexados à matéria orgânica dissolvida. Não foram observadas correlações significativas entre os teores dos metais determinados diretamente por eletroforese capilar e indiretamente pelo programa de especiação. O fracionamento seqüencial dos metais indicou que grande parte dos metais está ligada a frações pouco disponíveis do solo. Conclui-se que a aplicação da turfa e do concentrado húmico mineral juntamente com o cultivo do Amaranthus crentus e da Brassica juncea podem auxiliar na recuperação a longo prazo de solos contaminados com Zn, Mn Pb e B. / Two pot trials were carried out using a heavy metal accidentally contaminated soil. In the first one it was evaluated the plant absorbing, translocating and accumulating power for zinc, copper, manganese, lead and boron by the following vegetal species: Brassica juncea, Raphunus sativus L., Hybiscus cannabinus and Amaranthus crentus, so they could help in the rehabilitation of the studied soil. In the second pot trial it was evaluated the application of the following organic materials: Solomax, peat, and humic mineral concentrate for heavy metal toxicity amelioration for Brassica juncea. In a laboratory experiment it was evaluated the zinc retention capacity for the above mentioned organic materials. The measured variables were plant dry matter yield, absorbed and accumulated amounts of Zn, Cu, Mn, Pb and B; the translocation index and the removal index of metal by the mentioned plant species. The total and available (DTPA and CaCl2 001 mol L-1) content of Zn, Cu, Mn and Pb, were determined in soil samples. Concerning the soil saturation extract, the soluble and free forms of the mentioned elements were determined by ICPOES and capillary electrophoresis respectively. The same metals were also determined in the plant tissue of Brassica juncea. Analytical results were introduced in the chemical equilibrium program MINTEQ in order to calculate the concentration of the free forms of Zn, Cu, Mn, and Pb. A fractioning scheme for metals in soil was carried out in order to evaluate the effect of adding sources of organic carbon. The Freundlich model was used to account for zinc adsorption by the studied organic materials and the distribution coefficient Kd was also calculated. Although the plant species were able to accumulate high amounts of metal in the aerial part, that could not be considered as a hipper-accumulation process. The highest metal removal indexes were observed for Brassica juncea and Amaranthus crentus. Organic materials showed high values of Kd, reflecting its high affinity for zinc and a great capacity of zinc immobilization as well. Freundlich model was very effective in describing the adsorption isotherms as indicated by the high determination coefficients. Zinc retention was affected by the organic material type and pH, being favored by the highest studied pH values. Peat and humic mineral concentrate reduced the amounts of metals extracted by DTPA and CaCl2 in soil but the reduction was not great enough to avoid toxic effects in plants. Zn and Mn were present mostly as free cations in soil saturation extract while Pb and Cu were complexed by dissolved organic matter. It was not detected any significant correlation between free metal contents directly determined by capillary electrophoresis and those estimated by MINTEQ. Metal sequential extraction showed that most of them occurred in the least available fractions of soil. Peat and humic mineral concentrate application to soil associated with Amaranthus crentus and Brassica juncea cultivation may be used in long term amelioration of soils contaminated with Zn, Mn, Pb and B.