Diss. (sammanfattning) Uppsala : Sveriges lantbruksuniv. / Härtill 4 uppsatser.

Σκοπός της παρούσας μελέτης είναι η κατανόηση του μηχανισμού ρόφησης του φαινανθρενίου σε δείγματα γαιανθράκων και των αντίστοιχων χουμικών τους οξέων και η διερεύνηση της καταλληλότητας τους ως ροφητικών υλικών για την απορρύπανση ποτάμιων και λιμναίων συστημάτων, στα οποία υπάρχει πρόβλημα ρύπανσης από πολυκυκλικούς αρωματικούς υδρογονάνθρακες. Για την επίτευξη του σκοπού αυτού μελετήθηκαν τέσσερα δείγματα λιγνίτη και δύο δείγματα τύρφης και τα αντίστοιχα δείγματα των χουμικών οξέων. Η μεθοδολογία που ακολουθήθηκε για την απομόνωση των χουμικών οξέων βασίστηκε στην τροποποιημένη μεθοδολογία, που προτείνεται από την IHSS (International Humic Substances Society). Για τη μελέτη της ρόφησης φαινανθρενίου κατασκευάστηκαν οι ισόθερμες καμπύλες ρόφησης, ύστερα από την πραγματοποίηση πειραμάτων ρόφησης με συγκεντρώσεις φαινανθρενίου σε υδατικά διαλύματα 30, 50, 100, 300 και 500 μg/l. Τα αποτελέσματα δείχνουν ότι η ρόφηση στα περισσότερα δείγματα των χουμικών οξέων είναι μεγαλύτερη από ό,τι στα αντίστοιχα δείγματα των μητρικών τους γαιανθράκων. Επίσης στα δείγματα των γαιανθράκων παρατηρείται μεγαλύτερη ρόφηση στις χαμηλές συγκεντρώσεις φαινανθρενίου από ό,τι στις υψηλές, με αποτέλεσμα η ρόφηση να μην είναι γραμμική. Σχετικά με τη χρήση τους ως ροφητικά υλικά για απορρύπανση για δυο δείγματα λιγνίτη προτείνεται η χημική τους επεξεργασία, προκειμένου να χρησιμοποιηθούν ως ροφητικά υλικά, ενώ για τα υπόλοιπα δείγματα η διαφορά στη ροφητική ικανότητα μεταξύ των μητρικών γαιανθράκων και των παραγόμενων χουμικών οξέων δεν είναι τόσο σημαντική, με αποτέλεσμα να μπορεί να χρησιμοποιηθεί απευθείας το μητρικό υλικό / The scope of this study is the determination of the phenanthrene sorption mechanism for some Greek lignite and peat samples, as well as for their extracted humic acids. The scope is to assess their suitability for application in remediation of fresh water environments from polycyclic aromatic hydrocarbons (PAHs) For the extraction of the humic acids, the methodology provided by the IHHS (International Humic Substances Society) with some alterations, was applied. The sorption experiments were conducted by mixing 0,004 g of the sorbent within water solutions of phenanthrene at different concentrations of 30, 50, 100, 300 and 500 μg/l. The results show that phenanthrene sorption is higher in the humic acid samples rather than in the original lignite and peat. The original samples display higher sorption at low phenanthere concentration solutions (30 μg/l) than at the denser phenanthrene concentration solution (500 μg/l). Thus, the sorption in these samples is non-linear. In order to use these materials as sorbents, the TH4 and MT6 samples might have to be treated, because sorption is higher in the humic acid fraction than in the source material. The rest of the samples display lower variation in the sorption capacity between the humic acid samples and the original samples, thus there is no need for chemical treatment.

[pt] Dentre os contaminantes químicos liberados nos corpos de água, chumbo e cádmio são extremamente prejudiciais para os seres vivos. As sustâncias húmicas, devido à sua estrutura molecular complexa, que compreende grupos carboxílicos, fenólicos e éter, são adsorventes eficazes para poluentes orgânicos e metais. Neste contexto, o principal objetivo do presente trabalho foi avaliar o potencial do ácido húmico (AH) como adsorvente para chumbo e cádmio em meio aquoso e determinar os parâmetros cinéticos e termodinâmicos do processo. AH foi extraído de uma amostra de carvão, coletada na área de mineração do Estado de Santa Catarina, previamente oxidada com HNO3 concentrado em condições de refluxo, conforme a metodologia recomendada pela IHSS. O AH obtido foi caraterizado por técnicas de análise elementar, FTRI, análise termogravimétrica e MEV. Os resultados da caracterização foram similares aos relatados na literatura. Foram realizados ensaios de adsorção para cada cátion, em diferentes níveis de pH da solução, e a partir desta avaliação previa ficou determinado o valor de pH em 5. Os ensaios de adsorção com variação da concentração inicial dos cátions foram realizados separadamente para cada metal em batelada, empregando as seguintes condições: 50 mL de uma solução de cátion (0 a 100 mg L-1), 50 mg de AH, agitação mecânica (175 rpm) e temperatura constante (25 graus Celsius). Após 24 horas, os sistemas foram centrifugados e a concentração de cada metal no sobrenadante foi determinada por espectrometria de absorção atómica. As isotermas obtidas para Pb e Cd apresentaram uma curva em forma de L, o que indica que os sítios adsorventes disponíveis no AH tendem à saturação. Comparativamente a capacidade de adsorção máxima para o Pb foi mais elevada (77 mg g-1) do que aquela apresentada para o Cd (12 mg g-1). Tal fato indica uma maior afinidade dos sítios de adsorção do AH para o Pb. Comparativamente, foram feitos ensaios de adsorção com AH de Leonardita (padrão da IHSS) e carvão mineral oxidado. Para a determinação dos parâmetros termodinâmicos, foram realizados ensaios de adsorção em três temperaturas diferentes (15, 25, 35 graus Celsius). O processo de adsorção foi de natureza endotérmico, com um valor de entalpia de 7,86 kJ mol-1 e um valor de entropia de 23,11 J mol-1 K-1. A cinética de adsorção segue um modelo cinético de pseudo-segunda ordem com constates de taxa de 0,065 mg g-1 min-1 e 0,025 mg g-1 min-1 para Pb (Co 17,60 mg L-1) e Cd (Co 6,41 mg L-1), respetivamente. Os resultados obtidos no presente estudo mostram que o AH de carvão mineral pode eventualmente ser empregado para a remoção de metais pesados em meio aquoso, porem estudos sobre otimização de seu potencial devem ser todavia realizados. / [en] Among the released chemical contaminants into water bodies, lead and cadmium are extremely harmful to living things. The humic substances, due to their complex molecular structure that comprises both aliphatic and aromatic moieties as well as carboxylic, phenolic and ether groups are effective adsorbents for organic pollutants and metals. In this context, the main objective of this study was to evaluate the potential of humic acid (HA), extracted from previously oxidized coal, as adsorbent for lead and cadmium in aqueous solutions and determine the kinetic and thermodynamic parameters of the process. HA was extracted from a coal sample, collected in the mining area of the State of Santa Catarina, previously oxidized with HNO3 concentrated in reflux conditions, according to the methodology recommended by the IHSS. The HA obtained was characterized by elemental analysis techniques, FTRI, thermogravimetric analysis and SEM. The characterization results were similar to those reported in the literature. Adsorption experiments were carried out for each cation in different pH levels, and from this evaluation it was determined the value of pH at 5. The adsorption experiments with a variation of the initial concentration of cations were performed separately for each metal by employing the following conditions: 50 ml of a cation solution (0 to 100 mg L-1), 50 mg of HA, mechanical agitation (175 rpm) and constant temperature (25 Celsius degrees). After 24 hours, the system was centrifuged and the concentration of each metal in the supernatant was determined by atomic absorption spectrometry (AA). The isotherms obtained for Pb and Cd showed a L-shaped curve, indicating that the available sorptive sites on HA tending to a saturation point. Compared maximum adsorption capacity for Pb was higher (77mg g-1) than that shown for Cd (12mg g- 1). This fact indicates a higher affinity the adsorption sites of HA for Pb. Comparatively, adsorption experiments were performed with HA Leonardite (standard IHSS) and oxidized coal. For the determination of the thermodynamic parameters, adsorption experiments were performed at three different temperatures (15, 25, 35 Celsius Degrees). The adsorption process is endothermic nature, with a value of enthalpy of 7.86 kJ mol-1 and a value of entropy 80.54 mol-1 K-1. The adsorption kinetics follows a kinetic model of the pseudo-second-order with rate constants 0.065 g mg-1 min-1 and 0.025 mg g-1 min-1 for Pb (Co 17.60 mg L-1) and Cd ( Co 6.41 mg L-1), respectively. The results obtained in this study show that the coal HA can optionally be employed for removing heavy metals from aqueous media, but studies for their potential should however be realized.

Submitted by Izabel Franco (izabel-franco@ufscar.br) on 2016-09-12T18:27:51Z No. of bitstreams: 1 TeseAWAA.pdf: 1989758 bytes, checksum: 3b9bb42707bd9a2782fcc39bd906d77d (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-13T19:53:13Z (GMT) No. of bitstreams: 1 TeseAWAA.pdf: 1989758 bytes, checksum: 3b9bb42707bd9a2782fcc39bd906d77d (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-13T19:53:23Z (GMT) No. of bitstreams: 1 TeseAWAA.pdf: 1989758 bytes, checksum: 3b9bb42707bd9a2782fcc39bd906d77d (MD5) / Made available in DSpace on 2016-09-13T19:53:30Z (GMT). No. of bitstreams: 1 TeseAWAA.pdf: 1989758 bytes, checksum: 3b9bb42707bd9a2782fcc39bd906d77d (MD5) Previous issue date: 2015-08-13 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / The humic substances (HS) are important to aquatic ecosystems. In this study we investigated the kinetics and molecular variations of dissolved fulvic acids (FA) and humic acids (HA) formed from aquatic macrophytes decomposition under aerobic and anaerobic conditions. The results supported the proposition and validation of kinetic models that treated the formation, transformation and mineralization of dissolved SH. Although mineralization and humification are concurrent events, the aerobic condition favored these two processes contributed primarily to HA formation. The detritus showed different mineralization and HS formation potentials. Larger amounts of HS were related to higher carbon content in the detritus and lower mineralization of dissolved organic carbon (DOC). The SH mass loss rates were lower than the refractory fraction of particulate detritus, showing the recalcitrance of dissolved HS. The DOC with higher C/N proportions presented higher coefficient rates. The HS presented similar characteristics regardless of detritus source. However, aerobic conditions favored variation of polysaccharides content in HS, indicating transformation of these compounds. Aerobic conditions favored dissolved HS mineralization and its assimilation by microorganisms. The AH presented higher reactive fraction than FA, and was an important precursor of FA. The FA presented refractory characteristics and formed less HA, indicating that the liginocellulosic compounds of the detritus are the main precursors of HA. / As substâncias húmicas (SH) são de grande importância para os ecossistemas aquáticos. Nesse estudo investigaram-se a cinética e a variação molecular de ácidos fúlvicos (AF) e húmicos (AH) dissolvidos formados da degradação de macrófitas aquáticas, em condições aeróbias e anaeróbias. Os resultados subsidiaram a proposição e validação de modelos cinéticos que trataram da formação, transformação e mineralização das SH dissolvidas. Embora a mineralização e a humificação sejam eventos concorrentes, a condição aeróbia favoreceu esses dois processos e contribuiu, principalmente, com a formação dos AH. Os detritos apresentaram diferentes potencias de mineralização e formação de SH dissolvidas. As maiores quantidades de SH foram relacionadas com o maior teor de carbono no detrito e menor degradação do carbono orgânico dissolvido (COD). Os coeficientes de perda de massa das SH foram inferiores aos da fração refratária particulada dos detritos, evidenciando a recalcitrância das SH dissolvidas. O COD apresentou coeficientes de mineralização maiores nos meios com relações C/N maiores. As SH apresentaram características semelhantes independentemente da origem do detrito. Entretanto, houve variações maiores de polissacarídeos em condição aeróbia, indicando que houve maior transformação desses compostos nessa condição. Os ambientes aeróbios favoreceram a degradação das SH dissolvidas e a incorporação pelos microrganismos. O AH apresentou maior fração reativa que o AF e, por conseguinte, foi indicado como potencial precursor de AF. Os AF apresentaram características mais refratárias e formaram menos AH, indicando que os compostos lignocelulósicos dos detritos foram os principais precursores dos AH.

O lixiviado de aterro sanitário é uma água residuária com elevada concentração de DQO, DBO, amônia, traços de metais pesados e substâncias orgânicas dificilmente biodegradáveis, tais como substâncias húmicas e celulósicas (lignina). Dada essas características, torna-se necessário que ele seja recolhido e devidamente tratado para evitar danos ao meio ambiente e à saúde humana. Uma prática que tem sido adotada por alguns municípios brasileiros é o direcionamento do lixiviado para tratamento consorciado em estações de tratamento de esgoto (ETE). No entanto, são poucos os estudos que avaliam a eficácia desse procedimento. Um dos questionamentos sobre o tratamento biológico diz respeito à remoção do material orgânico dificilmente biodegradável, representado principalmente pelas substâncias húmicas e, dentro dessa classe, destaca-se a fração de ácidos húmicos no lixiviado. Nesse contexto, o presente trabalho teve como objetivo verificar a tratabilidade das soluções contendo lactose, lactose com ácidos húmicos, lactose com 2% em volume de lixiviado de aterro sanitário bruto e lactose com 2% em volume de lixiviado pré-tratado por \"air stripping\", quando submetidas ao tratamento biológico em reatores de lodos ativados em escala de bancada. Assim, buscou-se verificar se essa tecnologia de tratamento é capaz de estabilizar, ainda que parcialmente, compostos orgânicos de difícil biodegradação presentes no lixiviado. A quantificação das substâncias de difícil biodegradação antes e após o tratamento foi realizada pelo método tentativo do \"Equivalente em Ácidos Húmicos\" que se encontra em fase de estudo. Os resultados demonstraram que houve uma remoção parcial dessas substâncias. As análises de espectroscopia na região do infravermelho indicaram que não ocorreu a adsorção dos ácidos húmicos no lodo, o que pode ser uma evidencia de que a redução da concentração dessas substâncias é de fato devida ao seu consumo e não pela precipitação no lodo. Além disso, a adição de 2% em volume do lixiviado não ocasionou redução da população de microrganismos no sistema. / Leachate from sanitary landfills is a type of effluent with high concentrations of COD, BOD, ammonia, heavy metal traces and hardly biodegradable organic compounds such as humic and cellulosic substances (lignin). Thus this effluent needs to be collected and treated in order to prevent damages to the environment and to human health. A common practice in Brazilian cities is to destine the leachate to a sewage treatment plant (STP). However, there are few studies that assess the efficiency of this procedure. One of the questions regarding the biological treatment concerns its efficiency in removing hardly biodegradable organic compounds, represented in the most part by the humic substances, given the high levels of humic acid in the leachate. Within this context, the present study had the objective to verify the treatability of solutions containing lactose, lactose with humic acids, lactose with 2% (in volume) of untreated sanitary landfill leachate, and lactose with 2% of leachate pre-treated by air stripping, submitted to biological treatment in laboratory-scale activated sludge reactors. Thus this paper assessed if such treatment technology can stabilize, even if only partially, the hardly biodegradable organic compounds found in leachate. The quantification of these substances prior to and after treatment was made by using a tentative method called Humic Acids Equivalent, which is still in the phase of studies. The results show that there was a partial removal of these substances. The spectroscopy analyses on the infrared region indicated that there was no adsorption of humic acids onto the sludge, which evidences that the decrease in the levels of these substances was due to their consumption and not precipitation onto the sludge. Also, the addition of 2% of leachate did not reduce the population of microorganisms in the system.

The Diploma thesis deals with humic acids and their ability to adsorb metal ions on their surface. Humic acids are aromatic polycyclic compounds which contain carboxylic and fenolic functional groups on their sidechains. Thanks to these functional groups humic acids can form complexes with metal ions of different stability and assist the partial immobilization of pollutants in the nature. In this thesis, the sorption of Pb2+ and Zn2+ ions on humic acids was studied by relatively new electroanalytic method called galvanostatic stripping chronopotentiometry. Experimental data were described by Freundlich and Langmuir isotherms. The results show that the amount of examined metal ions increases with their increasing concentration. Furthermore it was determined that Pb2+ ions are adsorbed better on humic acids than Zn2+ ions. Both metals are adsorbed better from solution containing only one metal ion than in presence of four metals at the same time (Cd, Cu, Zn and Pb) where the sorption of these metals is not influenced by the presence of other metals.

This thesis deals with bond strength of metal ions in humic gels. Several samples of humic acids were studied to consider influence of samples isolation process and their consequent characteristics on bond strength of metal ions in their complexes. Some functional groups was blocked by methylation at some samples. Amount of active functional groups in individual samples was determined by standard titration methods. Metal ions bound in humic complexes were divided into several fractions by extraction with different reagents (distilled water, 1M MgCl2, 1M HCl and 0,025M NH4EDTA). Two extraction methods were used: sequential and fractional. During the fractional extraction leaching of metal ions always proceeds in single agents from original komplex, whereas during the sequential extraction leaching proceeds gradually in all extraction agents in order according to rising afinity of agents, i.e. bond strength of metal ions in samples. Amount of metal ions in leaches after extractions was analysed by UV-VIS spektrometry.

Presented diploma thesis focuses on the study of diffusion of cupric ions in humic acid hydrogels. A total of eight different hydrogels were prepared by dissolving the humic acids with sodium hydroxide and sodium triphosphate. For the purpose of precipitation and cross linking, hydrochloric acid and chlorides of magnesium, calcium and iron were used during a modified preparation of gels. Different gel-forming interactions were achieved by modifying the preparation of hydrogel systems. The aim of the thesis was to assess the effect of gel preparation procedure on the transport properties of the gels. Therefore, diffusion coeficients were determined for all samples. Two different methods - constant-source diffusion and instantaneous planar source diffusion - were used to assign the diffusion coefficients. Methods differ in source concentrations of cupric ions and are suitable for assessing the impact of the concentration on the diffusion coefficient. Both these methods were based on monitoring temporal evolution of diffusion profiles of cupric ions and on assigning the overall diffusion flow. Copper ions were elected as diffusing medium because of their high affinity and strong binding to humic acids. Measurements show that gels prepared using polyphosphate allow slightly faster diffusion of cupric ions and that the constant-source method provides higher diffusion coefficients in comparison to instantaneous planar source method.

The main aim of this thesis is the utilization of simple diffusion techniques for the study on transport properties of copper ions in the systems containing humic acids with respect to the other parameters, which can affect the process (the structure of diffusion environment, the interactions between transported specie and diffusion matrices, selective blocking of binding sites of humic acids). The first part of experimental works was focused on characterization of studied materials (humic acids, humic sol and humic hydrogel). The main part of the thesis was dealing with the optimization of simple diffusion techniques, which were suitable for the study on transport of copper ions in matrices containing humic acids, taking into account the mutual interactions between studied components in the system. The obtained diffusion characteristics were compared to the data determined using sorption experiments. Consequently, the minor goal of the experimental works of this thesis was also the assessment of the influence of basic physico-chemical parameters of studied materials on transport phenomenon.

Presented diploma thesis focuses on the study of diffusion of cupric ions in humic acid gels. A total of fifth different standards of humic acids and one sample humic acid prepared from same source as in bachelor's thesis, on which this thesis continues, were used for preparation solutions of humic acids. Thereafter, these solutions were used for preparation of agarose hydrogels, which were necessary in following diffusion experiments. The objective of the work was to compare transport properties of humic standards between themselves and then compare standards with humic acid prepared from same source as in bachelor's thesis. Measure, which was used to determine the transport properties, was comparison of effective diffusion coefficients. Method of instantaneous planar source diffusion was used to compare them. This method was based monitoring temporal evolution of diffusion profiles of cupric ions in humic hydrogels. Copper ions were selected as diffusing medium because of their high affinity and strong bonds to humic acids.