Fosforutsläpp kan leda till övergödning i vattenrecipienten om kritiska nivåer överskrids. De enskilda avloppen står idag för en relativt stor andel av Sveriges fosforutsläpp jämfört med de kommunala avloppen. Detta kan sättas i bakgrund av att staten, alltsedan 1970-talet, har lagt ner stora resurser på att reducera utsläppen hos kommunala avlopp, medan en motsvarande satsning på de enskilda avloppen uteblivit. Merparten av dagens enskilda avlopp utgörs av markbaserade reningssystem, det vill säga avloppslösningar där avloppsvattnet får passera genom markmaterial för att renas. Fosforreningen i markbaserade reningssystem har forskningshistoriskt sett inte varit en prioriterad fråga, vilket har lett till kunskapsbrist inom området. Naturvårdsverket har i och med miljöbalkens införande skärpt sina krav på fosforreningen hos enskilda avlopp. Trots att Naturvårdsverket nu har satt upp exakta kravgränser på fosforutsläpp, exempelvis att en normal skyddsnivå motsvarar en rening på 70 %, saknas dock råd för hur gemene man, inför byggandet av ett markbaserat reningssystem, ska kunna uppskatta fosforreningsförmågan i markmaterialet. Emellertid rekommenderar Naturvårdsverket att man inför byggandet ska uppskatta markmaterialets hydrauliska konduktivitet, en uppskattning som ofta utförs genom att mäta markmaterialets kornstorleksfördelning. Det finns även forskning som tyder på att kornstorleksfördelningen skulle kunna ha samband med fosforreningen. Syftet med detta examensarbete var framförallt att utvärdera om kornstorleks- fördelningen kan användas som ett mått på fosforreningen. Som ett sidospår till detta utvärderades även om den hydrauliska konduktiviteten kan bestämmas ur kornstorleks- fördelningen. Empiriska formler har vid tidigare studier etablerats för detta, men frågan är om dylika empiriska formler gäller för de undersökta markbaserade reningssystemen. Undersökningens resultat tydde på ett samband mellan kornstorlek och hydraulisk konduktivitet medan det inte kunde påvisas något samband mellan kornstorleks- fördelning och fosforrening. Det är därmed önskvärt att finna ett annat mått på fosforreningen i markbaserade reningssystem. Kan vi inte uppskatta hur mycket de markbaserade reningssystemen bidrar till övergödningen kan vi inte heller väga denna negativa miljöpåverkan mot de markbaserade systemens fördelar, såsom relativt låg energiförbrukning och relativt små utsläpp av växthusgaser. / Release of phosphorus is one of the contributing factors of eutrophication in aquatic recipients. In Sweden, on-site wastewater treatment represents large emissions of phosphorous per person in comparison to municipal wastewater treatment. This can be put in the context of the Government’s large investments for reducing phosphorus in municipal wastewater treatment plants, while no corresponding investment has yet been made in the field of on-site wastewater treatment. In Sweden, the on-site wastewater treatment systems of today mainly consist of WSAS (Wastewater soil absorption systems), i.e. systems where wastewater is cleaned by passing though soil material. During the history of research about WSAS issues of phosphorous removal have not been first priority, which has led to a considerable lack of knowledge regarding these issues. Since 1999, when the Swedish regulations of environmental law were established, the SEPA (Swedish Environmental Protection Agency) has tightened up their demands of phosphorus removal in on-site wastewater treatment systems, for instance by stating that a phosphorous removal of 70% shall be reached to accomplish a “normal level of protection”. Despite this fact, there are no recommendations of how to estimate phosphorus removal in the soil material. However, the SEPA recommends estimation of hydraulic conductivity before building WSAS. This estimation is usually made by measuring grain size distribution in the soil material. One interesting fact is that there, according to some scientists, might be a connection between grain size distribution and phosphorus removal. The aim of this thesis was mainly to investigate if measure of grain size distribution can be used in order to estimate phosphorus removal. The aim was also to evaluate if grain size distribution is a good indicator of hydraulic conductivity in the investigated WSAS. It was concluded that grain size distribution is a suitable indicator of hydraulic conductivity, but not a suitable indicator of phosphorus removal. Thus, we still need to find an easy way to estimate the phosphorus removal in WSAS. If we do not know the extent of impact on eutrophication by WSAS, we cannot weigh this negative impact against the positive aspects of relatively low energy usage and low release of green house gases compared to other on-site wastewater treatment systems.

Open-framework inorganic materials constitute an important area of study in materials chemistry, because of their potential applications in areas such as sorption and catalysis. After the discovery of nanoporous aluminium phosphates by Flanigen et al in 1982, there has been a tremendous growth in the area of porous solids. Most of them are based upon oxygen containing materials especially phosphates, and they exhibit fascinating architectures with unusual bonding and coordination environment. Besides metal phosphates and phosphites, inorganic-organic hybrids constitute an important family of open-framework structures. In this thesis, results of investigations of a variety of open-framework metal phosphates, metal phosphites, as well as a new family of phosphite-oxalates are presented. More importantly, studies directed towards the synthesis and understanding of the magnetic properties of various transition metal phosphates, phosphites, phosphite-oxalates and the upconversion behavior of uranium phosphites are discussed at length. In Chapter 1 of the thesis an overview of inorganic open-framework materials is presented. In Chapter 2 and 3, the synthesis, structure of open-framework zinc (Part A of both Chapters) and synthesis, structure and magnetic properties of open-framework iron (Part B of both Chapters) are presented. Some of these compounds show unusual structure and interesting properties. For example, two-dimensional iron phosphate exhibits ferrimagnetism whereas three-dimensional iron phosphate with SBU-6 and SBU-2 is antiferromagnetic. The three-dimensional iron phosphite exhibits small polarization at low field. In Chapter 4, we present a new family of organically templated hybrid materials synthesized by partially substituting the phosphite by the oxalate ion in manganese, iron and cobalt phosphites. These exhibit a wide range of structures in which the oxalates play an unusual dual role. Some of these compounds show interesting magnetic properties. For example, manganese phosphite-oxalate shows magnetic polarizations on application of high field at low temperatures and iron phosphite-oxalate exhibit ferromagnetism at very low temperature. While a large number of organically templated transition and main-group element phosphites have been synthesized, research on lanthanide and actinide phosphites has been rare. Most of the reported open-framework phosphate and phosphite compounds of uranium possess uranium in +6 oxidation state. The possibility of building open architectures of uranium phosphites has been explored in Chapter 5. The results have been rewarding and both layered and three-dimensional structures have been prepared. Two of them contain uranium in +4 state and exhibit upconversion behavior.

No description available.

Η χρήση των βιοϋλικών ως εμφυτεύματα στην Ουρολογία και ιδιαίτερα στις ενδοουρολογικές επεμβάσεις είναι πράξη ρουτίνας τις τελευταίες δεκαετίες. Παρ’ όλα αυτά τα προβλήματα που προκύπτουν από την ευρεία χρήση τους μπορεί να θέσουν σε κίνδυνο τη υγεία του ασθενή που τις φέρει (λοιμώξεις ή και επανεπεμβάσεις). Αναφορικά με τις επικαθίσεις δυσδιάλυτων αλάτων στην επιφάνεια των ενδοπροθέσεων αυτών υπάρχει εκτεταμένο πεδίο έρευνας αλλά οι μηχανισμοί του φαινομένου δεν έχουν διαλευκανθεί πλήρως. Ο βασικός στόχος της παρούσας διατριβής είναι η προσομοίωση του φαινομένου στο εργαστήριο με ασταθή διαλύματα συνθετικών ούρων υπέρκορα ως προς το οξαλικό ασβέστιο καθώς και η μελέτη της κινητικής και των θερμοδυναμικών παραμέτρων του φαινομένου. Το πειραματικό πρότυπο που χρησιμοποιήθηκε κρίνεται ικανοποιητικό για την κινητική μελέτη των επικαθίσεων (εναποθέσεων) σε βιοϋλικά του ουροποιητικού συστήματος. Η γραφική παράσταση της συνάρτησης της αρχικής ταχύτητας κρυστάλλωσης του μονοένυδρου οξαλικού ασβεστίου με το γινόμενο των ιοντικών ενεργοτήτων ασβεστίου και οξαλικών στην παρούσα διατριβή είναι γραμμική και σε καλή συμφωνία με αποτελέσματα από τη βιβλιογραφία. Η επιφάνεια του καθετήρα καταλύει την πυρηνογένεση ενώ οι χαμηλές τιμές επιφανειακής ενέργειας που υπολογίστηκαν υποδηλώνουν μηχανισμό ετερογενούς πυρηνογένεσης. Η αντίδραση για τον γυάλινο καθετήρα φαίνεται να ελέγχεται από την διάχυση δομικών μονάδων από το διάλυμα των συνθετικών ούρων ενώ για τους καθετήρες Foley ισχύουν διεργασίες επιφανειακής διάχυσης. Δεν φαίνεται να υπάρχει σημαντική διαφοροποίηση μεταξύ του γυαλιού και του καθετήρα Foley όσον αφορά στην επιφανειακή ενέργεια του σχηματιζόμενου στερεού. Η συμβατότητα των πυρήνων του μονοένυδρου οξαλικού ασβεστίου (COM) οι οποίοι αναπτύσσονται στους αντίστοιχους κρυσταλλίτες με τις επιφάνειες των καθετήρων Foley και των γυάλινων καθετήρων (control) – γωνία θ- βρέθηκε ότι ήταν παραπλήσια. Οι μικρές διαφοροποιήσεις στην επιφανειακή ενέργεια των υλικών τα οποία μελετήθηκαν, υποδεικνύουν ότι υλικά με μεγάλη επιφανειακή ενέργεια της αναπτυσσόμενης φάσης μπορούν να αναστείλουν τον σχηματισμό επικαθίσεων σε ενδοπροθέσεις. Η ποιοτική ανάλυση των επικαθίσεων των δυσδιάλυτων αλάτων μέσω της φασματοσκοπίας υπερύθρου είναι σημαντική για τη λήψη πληροφοριών σχετικά με τις συνθήκες σχηματισμού καθώς και του ρυθμού ανάπτυξής τους. Σε όλα τα πειράματα που πραγματοποιήθηκαν, από την ανάλυση των στερεών που ελήφθησαν διαπιστώθηκε ότι καταβυθίζεται αποκλειστικά μονοένυδρο οξαλικό ασβέστιο (COM). Η ηλεκτρονική μικροσκοπία σάρωσης μας παρείχε πληροφορίες για τη μορφολογία των στερεών. Παρατηρείται αλλαγή της μορφολογίας των κρυστάλλων του μονοένυδρου οξαλικού ασβεστίου παρουσία συνθετικών ούρων σε σχέση με τη μορφολογία του κρυστάλλου απουσία των συνθετικών ούρων. Η ποιοτική ταυτοποίηση 63 ουρητηρικών καθετήρων (stents) ανέδειξε πιο συχνά απαντώμενη την επικάθιση του μονοένυδρου οξαλικού ασβεστίου μόνη ή σε συνδυασμό με άλλες (36,5%). Στους καθετήρες κύστης (12) ήταν πιο συχνές οι επιμολύνσεις και οι επικαθίσεις στρουβίτη-απατίτη. Από τον μεταβολικό έλεγχο των ούρων όλων των παραπάνω ασθενών βρέθηκε σε υψηλό ποσοστό συνύπαρξη υποκιτρικουρίας (50 - 85,71%) καθώς και άλλες μεταβολικές διαταραχές όπως υπεροξαλουρία και υπομαγνησιουρία. Είναι πιθανό τέτοιοι μεταβολικοί παράγοντες να υπεισέρχονται στους μηχανισμούς ανάπτυξης των κρυσταλλικών επικαθίσεων. Τέλος, χρησιμοποιήθηκε το λογισμικό Phreeqc Interactive v 2.6 για τον υπολογισμό του υπερκορεσμού των ούρων ασθενών όσον αφορά στο μονοένυδρο οξαλικό ασβέστιο, στον υδροξυαπατίτη και στον βρουσίτη με ικανοποιητικά αποτελέσματα. Δεδομένου ότι ο υπερκορεσμός είναι μία αναγκαία αλλά όχι και ικανή συνθήκη για την καταβύθιση ενός άλατος η βάση δεδομένων του λογισμικού χρήζει τροποποιήσεων ώστε να έχει ακριβέστερη εφαρμογή στην βασική έρευνα και στην κλινική λιθίαση. Η ανάλυση των επικαθίσεων δυσδιάλυτων αλάτων σε βιοϋλικά του ουροποιητικού συστήματος είναι σημαντική για τη λήψη πληροφοριών σχετικά με τις συνθήκες σχηματισμού καθώς και του ρυθμού ανάπτυξής των. Οι πληροφορίες για τη διαδικασία σχηματισμού εναποθέσεων είναι σημαντικές για το σχεδιασμό νέων βιοϋλικών ανθεκτικών στα φαινόμενα των εναποθέσεων οργανικού υλικού (biofilm), μικροοργανισμών, και δυσδιάλυτων αλάτων. / The use of biomaterials as devices in Urology and particularly in endourological interventions is an ordinary practice in the last decades. Unfortunately problems that result from their wide use can get patient’s health into risk (with infections or even reoperation). There is an extensive field of research concerning encrustations (deposits) from undissolved salts in the surface of the endourological devices (stents, catheters) but the mechanisms of this phenomenon has not been cleared up completely till now. The main objective of the present study is the simulation of the phenomenon in the laboratory dealing with unstable solutions of synthetic urine supersaturated with respect to calcium oxalate monohydrate as well as the study of kinetics and thermodynamic parameters of the phenomenon. The experimental model that was used was characterised satisfactory for the kinetic study of salt deposits in biomaterials of the urinary system. The graphic representation of the function of initial rate of crystallization of calcium oxalate monohydrate with ion activity product of calcium oxalate monohydrate in the present study is linear and in accordance with results from the bibliography. The surface of catheter catalyses the formation of the nuclei of crystals while the low values of surface energy that were calculated imply mechanism of heterogeneous nucleation. The reaction in the surface of the glass catheter seems to be depended upon the diffusion of structural units from the solution of synthetic urine but the one in the Foley catheters suggests a surface diffusion mechanism. There is no important differentiation between the glass catheter and Foley catheter with respect to the surface energy of the formatted solid phase. The compatibility of calcium oxalate monohydrate nuclei which developed on the surfaces of Foley catheters and glass catheters (control) was found to be similar. The small differentiations concerning the surface energy of the materials were studied, indicate that materials with high surface energy of the developing solid phase could minimize the formation of encrustations in endourological devices. The qualitative analysis of salt encrustations via infrared spectroscopy is important for informing the conditions of nucleation as well as the rate of nuclei growth. The analysis of the solid phase took place in all experiments show exclusively calcium oxalate monohydrate formation(COM). The Scanning Electron Microscopy (SEM) provided us information about the morphology of the solid phase developed in the biomaterials surface. There was a differentiation on the crystal morphology of calcium oxalate monohydrate in the presence of synthetic urine comparing with other solutions in the bibliography. Presenting results from 11 samples– stents and catheters- was found that calcium oxalate monohydrate (COM) was the undissolved salt identified more often in such deposits. The qualitative identification of other 53 stents also showed increased calcium oxalate monohydrate deposits alone or in combination with other salts (36,5%). In 11 bladder catheters studied, the bacterial colonization was more often and the crystalline deposits were consisted mostly of struvite or apatite. Metabolic evaluation of urine of all above patients showed the coexistence of hypocitruria in high percentage (50-85,71%) as well as other metabolic disturbances such as hyperoxaluria and hypomagnesuria. It is supposed that such metabolic factors inside into the mechanisms of growth of crystal deposits. Finally, software Phreeqc Interactive v 2.6 was used for the calculation of patients’ urine supersaturation. The results were satisfactory with respect to calcium oxalate monohydrate, brushite and apatite. Since supersaturation is a necessary but not the unique factor for a salt precipitation seems that this software database requires modifications so that it has more sophisticated applications in basic research and clinical urolithiasis in future. The analysis of encrustations of undissolved salts in biomaterials used in the urinary system is important for collecting information concerning the conditions of crystal formation as well as their crystal growth. This is also important for planning new materials could resist in the phenomenon of deposits of either organic material (biofilm) and microorganisms or salts.

Currently at the Savannah River Site (SRS), there are fifteen single-shell, 3.6-million liter tanks containing High Level Waste. To close the tanks, the sludge must be removed. Mechanical methods have had limited success. Oxalic acid cleaning is now being considered as a new technology. This research uses sample results and chemical equilibrium software to develop a preferred flowsheet and evaluate the acceptability of the system impacts. Based on modeling and testing, between 246,000 to 511,000 l of 8 wt% oxalic acid were required to dissolve a 9,000 liter Purex sludge heel. For SRS H-Area modified sludge, 322,000 to 511,000 l were required. To restore the pH of the treatment tank slurries, approximately 140,000 to 190,000 l of 50 wt% NaOH or 260,000 to 340,000 l of supernate were required. When developing the flowsheet, there were two primary goals to minimize downstream impacts. The first was to ensure that the Resultant oxalate solids were transferred to DWPF, without being washed. The second was to transfer the remaining soluble sodium oxalates to the evaporator drop tank, so they do not transfer through or precipitate in the evaporator pot. Adiabatic modeling determined the maximum possible temperature to be 73.5°C and the maximum expected temperature to be 64.6°C. At one atmosphere and at 73.5°C, a maximum of 770 l of water vapor was generated, while at 64.6°C a maximum 254 l of carbon dioxide were generated. Although tank wall corrosion was not a concern, because of the large cooling coil surface area, the corrosion induced hydrogen generation rate was calculated to be as high as 10,250 l/hr. Since the minimum tank purge exhaust was assumed to be 5,600 l/hr, the corrosion induced hydrogen generation rate was identified as a potential concern. Excluding corrosion induced hydrogen, trending the behavior of the spiked constituents of concern, and considering conditions necessary for ignition, energetic compounds were shown not to represent an increased risk Based on modeling, about 56,800 l of Resultant oxalates could be added to a washed sludge batch with minimal impact on the number of additional glass canisters produced. For each sludge batch, with 1 to 3 heel dissolutions, about 60,000 kg of sodium oxalate entered the evaporator system, with most collecting in the drop tank, where they will remain until eventual salt heel removal. For each 6,000 kg of sodium oxalate in the drop tank, about 189,000 l of Saltstone feed would eventually be produced. Overall, except for corrosion-induced hydrogen, there were no significant process impacts that would forbid the use of oxalic acid in cleaning High Level Waste tanks. / MATHEMATICAL SCIENCES / M. Tech. (Chemical Engineering)

Submitted by Edileide Reis (leyde-landy@hotmail.com) on 2013-04-23T13:47:47Z No. of bitstreams: 1 Silvia Rocha.pdf: 838054 bytes, checksum: 4b1ce47b2cf6d9f32b6b110adf7bcfd4 (MD5) / Made available in DSpace on 2013-04-23T13:47:47Z (GMT). No. of bitstreams: 1 Silvia Rocha.pdf: 838054 bytes, checksum: 4b1ce47b2cf6d9f32b6b110adf7bcfd4 (MD5) Previous issue date: 2009 / O espinafre produzido e mais consumido no Brasil, denominado como espinafre da Nova Zelândia (Tetragonia expansa), difere significativamente do espinafre verdadeiro (Spinacia oleracea) produzido em muitos países do hemisfério norte. As diferenças ocorrem não apenas na classificação botânica, mas em muitas das características químicas dos vegetais. No presente trabalho, foram avaliados os teores de alguns nutrientes e antinutrientes contidos no espinafre comercializado na Bahia, sendo avaliados quatro diferentes procedimentos de digestão das amostras de espinafre com ácido nítrico em sistema aberto. Os resultados obtidos a partir dos diversos procedimentos de pré-tratamento da amostra foram comparados para os vários analitos investigados (Al, Ca, Fe, Cu, Zn, Mn, Mg) e indicaram vantagens da inserção de uma etapa de pré-digestão. Adicionalmente, foram realizados testes de extração dos metais sob investigação em água e em soluções com diferentes níveis de acidez na presença e ausência de agente quelante (ácido etilenodiaminotetracético – EDTA) para avaliação do nível de interação dos metais com o vegetal e, por conseguinte, a disponibilidade destes minerais. Os resultados levaram a acreditar que as interações de Mg(II), Cu(II) e Mn(II) com o espinafre seco eram fracas, enquanto que as interações com Al(III), Ca(II) e Fe(III) eram mais intensas, devido a condições mais drásticas (acidez da solução ou presença de quelante) foram necessárias para maximizar a extração destes metais. Ao considerar informações previamente reportadas sobre os elevados teores de oxalato em espinafre e seus efeitos antinutricionais, foram investigados os teores de oxalato em amostras secas oriundas de amostras de espinafre verdadeiro e espinafre da Nova Zelândia cultivado na Bahia, empregando permanganometria. Para tanto foram realizados estudos sobre as melhores condições para extração de oxalato variando a acidez da solução extratora e os resultados obtidos foram comparados com os apresentados na literatura. Finalmente, foram realizados testes para avaliação da possibilidade de enriquecimento de espinafre com íons metálicos a partir de sucessivas etapas de extração (dessorção) e concentração (sorção) do íon no vegetal. Pôde ser constatado que os maiores níveis de sorção (18 ± 3 mg g-1) e repetitividade foram obtidas para íons cálcio, possivelmente devido ao oxalato existente nos espinafres. / Salvador

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Previous data from the literature have shown that some Krebs cycle intermediates could act as antioxidant in several models, both in vitro and in vivo. However, the mechanism(s) involved in the antioxidant effect of Krebs cycle intermediates are not fully understood. Additionally, there are scarce data in the literature taking into account the in vitro effect of Krebs cycle intermediates during oxidative stress conditions. Thus, the aim of this study was to determine the effect of some Krebs cycle intermediates on lipid peroxidation induced in vitro by different pro-oxidant agents, and the mechanism(s) by which they act. Furthermore, it was necessary elucidate the mechanisms by which the different pro-oxidants acts under in vitro conditions. The present results showed that the malonate-induced TBARS production was not changed by potassium cyanide or MK-801. However, the pro-oxidant effect of quinolinic acid was significantly prevented by MK-801. In addition we found that both malonate and oxalate were able to form complexes with iron ions (Fe2+). Based on the presented results, we conclude that malonate pro-oxidant activity in vitro seems to be independent of the secondary excitotoxicity via indirect NMDA receptors activation. Additionally, we suggest that both the malonate and oxalate effect, in these experimental conditions, is due to its ability to form complexes with iron ions, thus modulating an adequate ratio Fe2+/Fe3+ that could cause an increase in free radicals generation. In contrast, the quinolinic acid effect seems to be dependent of the NMDA receptors activation. However, we can not rule out the involvement of iron ions in quinolinic acid toxicity under our assay conditions. Another objective of this study was to investigate the effect of some Krebs cycle intermediates against either basal or induced TBARS production, using rat brain S1 preparations and the mechanism(s) by which they act. The results showed that oxaloacetate, citrate, succinate, and malate were able to significantly prevent both basal and quinolinic acid-, iron- or malonate-induced TBARS production. On the other hand, fumarate prevented only malonate-induced TBARS production, without effect under basal conditions. However, α-ketoglutarate induced per se a significant increase in basal TBARS production. The antioxidant activity of fumarate and succinate were completely abolished when S1 was submitted to heat-treatment at 100ºC during 10 min. Likewise, potassium cyanide completely abolished the antioxidant effect of succinate. The effect of other Krebs cycle intermediates studied was unchanged with respect to heat-treatment, or cyanide. Except for succinate and fumarate, all intermediates used in this study were able to form complexes with iron (Fe2+) ions, however only oxaloacetate and α-ketoglutarate significantly prevented deoxyribose degradation induced by hydrogen peroxide. Based on the results presented, we concluded that oxaloacetate, malate, succinate, fumarate and citrate could act as antioxidants under such conditions, whereas α-ketoglutarate acts as a pro-oxidant agent per se. The mechanism(s) by which citrate, malate, and oxaloacetate acts seems to be related to their ability to form complexes with iron (Fe2+) ions, thus modulating the iron redox cycle. In contrast, the succinate and fumarate antioxidant effect seems to be dependent of the some enzymatic system. / Dados prévios da literatura têm mostrado que alguns intermediários do ciclo de Krebs podem agir como antioxidantes em diversos modelos, tanto in vitro, quanto in vivo. Porém, o(s) mecanismo(s) através dos qual(is) esses intermediários exercem suas atividades antioxidantes não são completamente entendidas. Considerando a escassez de dados na literatura a respeito do efeito dos intermediários do ciclo de Krebs durante situações de estresse oxidativo, o presente trabalho teve por objetivo determinar o efeito desses sob a peroxidação lipídica induzida por diferentes agentes pró-oxidantes in vitro, bem como investigar o(s) mecanismo(s) de ação dos mesmos. Além disso, faz-se necessário caracterizar o(s) mecanismos(s) pelo(s) qual(is) os diferentes pró-oxidantes agem nos sistemas in vitro. Os resultados dessa tese mostraram que a atividade pró-oxidante in vitro do malonato não foi modificada pela adição de cianeto de potássio, nem pelo MK-801. Por outro lado, o efeito pró-oxidante do ácido quinolínico foi significativamente prevenido pelo MK-801. Observamos ainda que o malonato, e também o oxalato foram capazes de formar complexos com íons ferrosos. Portanto, com base nos resultados encontrados, concluímos que o efeito pró-oxidante do malonato in vitro parece ser independente da excitotoxicidade secundária, conseqüência da ativação indireta dos receptores NMDA. Os resultados sugerem que o efeito do malonato e do oxalato nessas condições experimentais deve-se principalmente a sua capacidade de interagir com íons ferro, modulando uma razão Fe2+/Fe3+ que favorece a geração de radicais livres. Por outro lado, o efeito do ácido quinolínico parece ser devido à ativação dos receptores NMDA. Porém, não podemos excluir a participação dos íons ferro para a toxicidade do mesmo nessas condições. Outro foco deste estudo foi investigar o efeito de alguns intermediários do ciclo de Krebs na produção de TBARS basal ou induzida por diferentes pró-oxidantes em S1 de cérebro de ratos in vitro, bem como investigar o(s) mecanismo(s) de ação dos mesmos. Os resultados mostraram que o oxaloacetato, o citrato, o sucinato e o malato foram capazes de reduzir significativamente a produção de TBARS basal, bem como a induzida por ácido quinolínico, ferro ou malonato. O fumarato, por sua vez, teve efeito antioxidante somente sobre a produção de TBARS induzida. Por outro lado, o α-cetoglutarato foi capaz de induzir per se um significativo aumento na produção de TBARS. O efeito antioxidante do fumarato e do sucinato foi completamente abolido quando o S1 foi submetido a um prétratamento por 10 min a 100ºC, enquanto que o efeito dos demais intermediários permaneceu inalterado. Da mesma forma, a adição de cianeto de potássio aboliu completamente o efeito antioxidante do sucinato sem interferir significativamente no efeito dos demais intermediários estudados. Todos os intermediários estudados, exceto o sucinato e o fumarato, foram capazes de quelar íons ferro, porém somente o oxaloacetato e o α- cetoglutarato foram capazes de prevenir a degradação da desoxirribose induzida por peróxido de hidrogênio. Com base nos resultados obtidos, podemos concluir que o oxaloacetato, o malato, o sucinato, o fumarato e o citrato agem como antioxidantes sob determinadas condições, enquanto que o α-cetoglutarato age como um agente pró-oxidante per se. O mecanismo pelo qual o citrato, o malato e o oxaloacetato exercem seus efeitos antioxidantes parece ser devido à capacidade desses em interagir com íons ferro modulando o ciclo redox desse. Por outro lado, o efeito do sucinato e do fumarato parece ser devido a alguma atividade enzimática.

Made available in DSpace on 2015-03-26T13:51:51Z (GMT). No. of bitstreams: 1 texto completo.pdf: 1278229 bytes, checksum: eed1e8ad3234857f397ab4b1785eb2b1 (MD5) Previous issue date: 2010-07-07 / Fundação de Amparo a Pesquisa do Estado de Minas Gerais / Ectomycorrhizal fungi associated with eucalypt roots may induce the storage of calcium in the form of calcium oxalate crystals in the root system of the host plant. Despite of the great demand for calcium by the plants of this genus and the low calcium availability in Brazilian soils, little is known about the calcium storage capacity and organic acids efflux displayed by ectomycorrhizal depending on the availability of this element. Thus, this study aimed to characterize calcium crystals in ectomycorrhizas of Eucalyptus sp., their distribution, morphology and chemical composition, and to assess the ability of ectomycorrhizal fungi to accumulate calcium and produce organic acids when grown under different concentrations of calcium in the growth medium. In ectomycorrhizas of Eucalyptus sp., the crystals were observed inside root cortical cells. Three different distribution patterns were observed and classified as regular, irregular or smooth. The scanning electron microscopy combined with energy dispersive X-ray microprobe analysis allowed to classify the morphologies of the predominant crystals as granules and concretions, although other morphological types have also been highlighted. Calcium, oxygen and carbon are the major constituents of these crystals, which were characterized as calcium oxalate crystals. In general, ectomycorrhizal fungi exhibited a pattern of calcium accumulation in mycelium responding positively to the increase of the element concentration in the growth medium. However, the concentration of calcium in the medium does not seem to influence the production of fungal biomass. Under conditions of lower calcium concentration in the medium, the isolates had higher calcium utilization efficiency. The acetic/gluconic, butyric, oxalic and citric acids were detected in the growth medium of ectomycorrhizal isolates evaluated. The concentration of calcium in the medium influenced exudation of acids acetic/gluconic, butyric and oxalic by the isolate Pisolithus sp. PT06, which also showed the highest production of these compounds in comparison to others. This, may be related to lower accumulation of fungal biomass exhibited by this isolate. The concentration of butyric acid in the growth medium of isolate Pisolithus tinctorius PTFRA was higher when the concentration of calcium was smaller, similar to isolate Pisolithus sp. PT06. This is the first report about the detailed morphology and chemical constitution of predominant crystals in ectomycorrhizal of eucalypts. Moreover, the results corroborate the role of ectomycorrhizal fungi in calcium acquisition from soil and suggest that different isolates may have different capacities of cycling calcium, either by biomass accumulation or efflux of organic acids. / Fungos ectomicorrízicos associados à raízes de eucalipto podem induzir o armazenamento de cálcio sob a forma de cristais de oxalato de cálcio no sistema radicular da planta hospedeira. Apesar da grande demanda por cálcio pelas plantas desse gênero e a baixa disponibilidade em solos brasileiros, pouco se sabe sobre as capacidades de armazenamento de cálcio e efluxo de ácidos orgânicos exibidas por fungos ectomicorrízicos em função da disponibilidade do elemento. Sendo assim, este trabalho teve por objetivo caracterizar cristais de cálcio presentes em ectomicorrizas de Eucalyptus sp., quanto a sua distribuição, morfologia e composição química, além de avaliar a capacidade de fungos ectomicorrízicos em acumular cálcio e produzir ácidos orgânicos quando cultivados sob diferentes concentrações do elemento. Nas ectomicorrizas de Eucalyptus sp., os cristais foram evidenciados no interior de células corticais radiculares. Três diferentes padrões de distribuição foram observados e classificados como regular, irregular ou homogêneo. A Microscopia Eletrônica de Varredura associada a microssonda de análise de energia dispersiva de raios-X permitiu classificar as morfologias predominantes dos cristais como grânulos e concreções, embora outros tipos morfológicos também tenham sido evidenciados. Cálcio, oxigênio e carbono são os principais elementos constituintes desses cristais, que diante de todos os resultados obtidos foram seguramente caracterizados como cristais de oxalato de cálcio. De modo geral, fungos ectomicorrízicos exibiram um padrão de acúmulo de cálcio no micélio respondendo positivamente ao aumento da concentração do elemento no meio de cultivo. Contudo, a dose de cálcio no meio parece não influenciar a produção de biomassa fúngica. Sob condições de menor concentração de cálcio no meio, os isolados apresentaram maior eficiência de utilização de cálcio. Os ácidos acético/glucônico, butírico, oxálico e cítrico foram detectados no meio de cultivo dos isolados ectomicorrízicos avaliados. A dose de cálcio no meio de cultivo influenciou a exsudação dos ácidos acético/glucônico, butírico e oxálico pelo isolado Pisolithus sp. PT06, que também apresentou a maior produção desses compostos em comparação aos demais e isso pode estar relacionado ao menor acúmulo de biomassa fúngica exibido por esse isolado. A concentração do ácido butírico no meio do isolado Pisolithus tinctorius PTFRA foi influenciada pela dose de cálcio, sendo maior onde a concentração de cálcio era menor, padrão semelhante ao do isolado Pisolithus sp. PT06. Este é o primeiro relato sobre a morfologia detalhada e constituição química de cristais predominantes em ectomicorrizas de eucalipto. Além disso, os resultados apresentados corroboram o papel de fungos ectomicorrízicos na aquisição de cálcio do solo e sugerem que diferentes isolados podem apresentar capacidades distintas de atuação nos processos envolvendo a ciclagem do cálcio, seja pelo efluxo de ácidos orgânicos e/ou acúmulo na biomassa.

Made available in DSpace on 2015-03-26T13:52:02Z (GMT). No. of bitstreams: 1 01 - capa_abstract.pdf: 368389 bytes, checksum: 8d0c846bf65c6ee5345758d74d1a07f8 (MD5) Previous issue date: 2007-04-04 / This work aimed at evaluating the role of the ectomycorrhizal fungi in the uptake and storage of calcium in Eucalyptus sp., grown for 2.5 years, in a mountainous area in the region of Viçosa, MG. Abundant accumulation of oxalate crystals as grains or druses was observed in 73.7 % of the ectomycorrhizas and fine lateral roots studied. The conspicuous presence of CaOx was observed in 56.2% of the ectomycorrhizae and in 17.5% of the nonmycorrhizal lateral fine roots, evidencing the role of the ectomycorrhizal association in the storage of calcium in the roots of Eucalyptus sp. The highest mycorrhizal colonization was observed in the Slope area that presented limited availability of nutrients and high Al saturation. Oxalic acid concentrations decreased in the following order, in mg Kg -1: leaves, 162.3 > ectomycorrhizas, 118.2 > non-mycorrhizal fine lateral roots, 116.0. Oxalic acid concentrations in the soil were higher in ectomycorhizospheric soil with 91.8 mg Kg-1, followed by the rhizospheric soil, with 67.2 mg Kg-1, and, finally, by the non-rhizospheric soil with 38 mg Kg-1. In the ectomycorrhizas collected in the Top area, the higher concentrations of oxalic acid and P, 173.3 mg Kg-1 and 6.35 mg Kg-1, respectively, probably resulted from nutrient solubilization by the ectomycorrhizal fungi associated with the host plants. The larger fraction of the litter layer corresponded to that showing the most advanced level of decomposition, being composed of dark fragments of leaves and branches in direct contact with the soil. Generally, nutrient content in the forest litter, in ka ha-1, decreased as follows: Ca (32.4) > Mg (5.4) > K (4.2) > P (1.7). Ca content in the litter and its low concentration in the soil shows the importance of the litter layer as a Ca reservoir for eucalypts. The highest concentrations and contents of P in the litter were verified in the Top position, however, the activity of acid phosphatases of ectomycorrhizas did not differ among the topographical positions evaluated. Fruit bodies of Laccaria, Pisolithus, Scleroderma, and of an unidentified fungus were observed in the area under study. The examination of the most decomposed litter layer and of the interface soil-litter showed an intense colonization by eucalypt roots, with eight distinct ectomycorrhizal morphotypes, hyphae, rhizomorphs, and basidiomes This work demonstrate that ectomycorrhizal fungi participate in the cycling of the eucalypt forest litter and in the storage of Ca when associated to eucalypt roots. / Este trabalho teve como objetivo determinar o papel dos fungos ectomicorrízicos na absorção e armazenamento de Ca por plantas de Eucalyptus sp., cultivado por 2,5 anos em área com topografia típica em meia laranja de vertente côncavo-convexa da região de Viçosa, MG. Em 73,7 % das ectomicorrizas e raízes observadas, observou-se abundante acúmulo de cristais de oxalato de cálcio (CaOx) nas células do córtex radicular, na forma de drusas e grânulos. A presença conspícua de CaOx foi observada em 56,2% das ectomicorrizas e em 17,5% das raízes laterais finas não-colonizadas, evidenciando o papel das micorrízas no acúmulo de cálcio em Eucalyptus sp. As maiores percentagens de colonização micorrízica foram observadas na área de Encosta, que apresenta limitada disponibilidade de nutrientes e alta saturação por Al. As concentrações de ácidos orgânicos foram quantificadas em diversas frações, a saber, em mg kg-1: folhas (162,3) > ectomicorrizas (118,2) > raízes laterais finas não-colonizadas (116). Os teores de ácido oxálico foram maiores no solo ectomicorrizosférico (91,8 mg kg-1), seguido pelo solo rizosférico (67,2 mg kg-1) e, finalmente, pelo não-rizosférico (38 mg kg-1). Nas ectomicorrizas da área Topo, os teores mais elevados (p<0,05) de ácido oxálico e P, 173,3 e 6,35 mg kg-1, respectivamente, possivelmente resultaram da solubilização de nutrientes pelos fungos ectomicorrízicos associados. A fração que mais contribuiu para a massa de serapilheira foi a em avançado grau de decomposição, sendo constituída de fragmentos de folhas e galhos escuros em contato com o solo. Em geral, a ordem de acúmulo de nutrientes na serapilheira correspondeu a, em kg ha-1: Ca (32,4) > Mg (5,4) > K (4,2) > P (1,7). O conteúdo de Ca na serapilheira e a baixa concentração do elemento no solo revelam a importância da manta orgânica como reservatório de Ca para o eucalipto. A maior concentração e conteúdo de P na serapilheira foram verificados na posição Topo, no entanto, a atividade das fosfatases ácidas nas ectomicorrizas não diferiu entre as amostras das posições topográficas avaliadas. Observaram-se basidiocarpos de Laccaria, Pisolithus, Scleroderma e de fungo ectomicorrízico não-identificado. A existência de densa camada de raízes de eucalipto na fração mais decomposta da serapilheira e na interface desta com o solo revelou intensa colonização da manta orgânica por raízes de eucalipto, com a presença de oito morfotipos distintos de ectomicorrizas, além de hifas, rizomorfos e basidiocarpos. O trabalho demonstra que os fungos ectomicorrízicos participam na ciclagem da serapilheira e no armazenamento de cálcio quando associados a raízes de eucalipto.

Made available in DSpace on 2014-12-17T14:13:36Z (GMT). No. of bitstreams: 1 SilviaRS_TESE.pdf: 1377136 bytes, checksum: 8255e0cbf50a79a12b6f6b0f3965241e (MD5) Previous issue date: 2010-10-08 / Lithiasis is considered a public health issue due to its high prevalence and rates of recurrence. Objective: To identify risk factors for lithiasis in kidney stone patients from Fortaleza, Brazil. In the first stage of the study, the medical records of 197 patients with urinary lithiasis covering the period 1996 2006 were analyzed with regard to clinical and metabolic data. In the second stage, 340 kidney stones were submitted to morphological examination under 10x magnification. According to the external morphology and the cut surface, the stones were classified as pure or mixed, and major and minor components were identified. In addition, the stone fragments of 25 patients treated with lithotripsy were submitted to morphological analysis. In the third stage, a subsample of 50 stones was used in a double-blind comparison of morphological and chemical findings. Results were expressed as concordant, partly concordant (discordant for minor components) or discordant (discordant for major components). The average age of first symptoms was 35.8?13.3 years, with no significant difference between the genders. The male/female ratio was 1:1.7. Recurrence was reported in 53.3% of cases. The main metabolic changes observed were hypernatriuria (80.7%), hypercalciuria (48.7%), low urine volume (43.7%), hyperoxaluria (30.5%) and hyperuricosuria (17.3%). Pure stones represented 34.7% of the total sample of 340 stones. The most common route of elimination was spontaneous for pure stones (49.1%) and surgical for mixed stones (50.5%). Pure stones consisted most frequently of calcium oxalate (OxCa) (59.3%) and uric acid (UA) (23.7%), the former prevalent in women, the latter prevalent in men. The most frequently observed component in mixed stones was OxCa (67.1%), followed by carbapatite (11.2%) and struvite (7.9%). The main components were OxCa and UA for men, and carbapatite and struvite for women. Nearly half (48%) the 25 analyzed fragments were pure, consisting of calcium oxalate dihydrate (COD) (56%), calcium oxalate monohydrate (COM) (48%), phosphate (32%) and UA (20%). Four patients (16%) had infectious stones. In the chemical analysis of the subsample of 50 stones, the most 64 frequently observed major components were calcium (70%), oxalate (66%), ammonium (56%), urate (28%) and carbonate (24%). In the morphological analysis, the main components were calcium and magnesium phosphate (32%), COM (24%), UA (20%), COD (18%) and cystine (6%). Morphological and chemical findings were totally concordant for 38% of the stones, partly concordant in 52% and discordant in 10%. Conclusion: The risk factors for lithiasis in kidney stone patients from Fortaleza (Brazil) were hyperoxaluria, hypercalciuria with or without hypernatriuria, hyperuricosuria and low urine volume / A lit?ase urin?ria ? um problema de sa?de p?blica pela elevada preval?ncia e recorr?ncia. Objetivo: O objetivo do presente estudo foi determinar os fatores litog?nicos em pacientes com lit?ase urin?ria de Fortaleza, Cear?. O estudo foi dividido em tr?s fases: na primeira, realizouse estudo documental de prontu?rios de 197 pacientes com lit?ase urin?ria atendidos entre 1996 e 2006, para a an?lise de dados cl?nicos e avalia??o metab?lica. Na segunda fase foi realizada uma avalia??o morfol?gica de 340 c?lculos urin?rios, classificando-os como puro ou misto e os componentes em majorit?rios ou minorit?rios. Foi tamb?m avaliado fragmentos de c?lculos de 25 pacientes tratados com litotripsia. Na terceira fase utilizou-se uma amostra de 50 c?lculos para um estudo duplo-cego comparando a an?lise morfol?gica e a an?lise qu?mica. Os resultados foram considerados como concordantes, parcialmente concordantes (componentes minorit?rios discordantes) ou discordantes (componentes majorit?rios discordantes). A m?dia de idade dos 197 pacientes no primeiro sintoma foi 35,8 ? 13,3 anos, n?o houve diferen?a entre os g?neros. A rela??o homem:mulher foi de 1:1,7, 53,3% eram recorrentes. As principais altera??es metab?licas foram hipernatri?ria (80,7%), hipercalci?ria (48,7%), volume urin?rio baixo (43,7%), hiperoxal?ria (30,5%) e hiperuricos?ria (17,3%). Entre os 340 c?lculos analisados, 34,7% foram puros. A via de elimina??o mais comum dos c?lculos puros foi a espont?nea (49,1%) e a dos mistos foi a cir?rgica (50,5%). Os c?lculos mais freq?entes foram o oxalato de c?lcio (OxCa=59,3%) e ?cido ?rico (AU=23,7%), sendo o primeiro mais comum nas mulheres e o segundo nos homens. Entre os c?lculos mistos, o OxCa foi o principal componente (67,1%), seguido da carbapatita (11,2%) e estruvita (7,9%). Os principais componentes nos homens foram o OxCa e AU, enquanto que nas mulheres foram a carbapatita e estruvita. Entre os 25 fragmentos de c?lculos analisados, 48% foram puros. Os componentes encontrados foram: OxCa dihidratado-COD (56%), OxCa monohidratado-COM (48%), fosfato (32%), AU (20%). Quatro pacientes (16%) apresentaram c?lculo de infec??o. Na an?lise qu?mica dos 50 c?lculos urin?rios os principais componentes majorit?rios foram c?lcio (70%), xvi oxalato (66%), am?nio (56%), urato (28%) e carbonato (24%), enquanto que na morfol?gica foram fosfato de c?lcio e magnesiano (32%), COM (24%), AU (20%), COD (18%) e cistina (6%). Concord?ncia total foi observada em 38%, parcial em 52% e discord?ncia em 10%. Conclus?o: Os fatores de risco litog?nicos na regi?o de Fortaleza foram hiperoxal?ria, hipercalci?ria com ou sem hipernatri?ria, hiperuricos?ria e volume urin?rio reduzido