O presente trabalho teve como objetivo avaliar a remoção de três concentrações diferentes de microcistina extracelular em diferentes combinações de tratamento de águas para abastecimento, em escala de bancada, que tiveram como sequência básica a clarificação associada ou não aos processos de pré-oxidação com \'K\'MN\'O IND.4\', adsorção em CAP e pós-cloração. Os resultados mostraram que para todas as águas estudadas o permanganato de potássio não interferiu nos mecanismos de coagulação/floculação e ainda mostrou-se uma alternativa segura para realização da pré-oxidação no que tange à formação de THMs. Na Fase 1, com concentração inicial de microcistina extracelular em torno de 1,4 \'mü\'g/L, a clarificação (coagulação, floculação, flotação por ar dissolvido e clarificação final) atendeu ao padrão de potabilidade que determina concentrações de microcistina menores que 1,0 \'mü\'g/L. Já na Fase 2, com concentração inicial microcistina extracelular em torno de 21,7 \'mü\'g/L, para o atendimento à legislação foi necessário associar a clarificação à pré-oxidação, dosando-se 1,0 ou 2,0 mg \'K\'MN\'O IND.4\'/L, e à pós-cloração com 3,0 mg \'CL IND.2\'/L. Na Fase 3, com concentração inicial de microcistina extracelular em torno de 64,1 \'mü\'g/L, a associação da clarificação com a adsorção com 60,0 mg/L de CAP e com a pós-cloração com 3,0 mg \'CL IND.2\'/L proporcionou residuais de microcistina extracelular inferiores à 1,0 \'mü\'g/L. Observou-se ainda, que nas Fases 1 e 3 a presença de matéria orgânica dissolvida interferiu negativamente nas sequências de tratamento ao consumir parte do permanganato de potássio destinado à oxidação da microcistina extracelular. Entretanto, na Fase 2 a demanda do pré-oxidante pelas substâncias húmicas parece ter impedido a lise de parte das células de Microcystis sp. / The present work had as objective to evaluate the removal of three different concentrations of extracellular microcystins in different combinations of water treatment for supplying, in bench scale, that had as basic sequence the clarification associated or not with the processes of pre-oxidation with \'K\'MN\'O IND.4\', adsorption on PAC and post-chlorination. The results showed that for all waters studied the potassium permanganate did not interfere in the mechanisms of coagulation/flocculation and also proved to be a safe alternative for achieving the pre-oxidation with regard to the formation of THMs. In Phase 1, with initial concentration of extracellular microcystin around 1.4 \'mü\'g/L, the clarification (coagulation, flocculation, dissolved air flotation and clarification final) met the World Health Organization drinking water guideline value of 1.0 \'mü\'g/L of microcystin. Already, in Phase 2, with initial concentration extracellular microcystin around 21.7 \'mü\'g/L, to meet the legislation was necessary to involved the clarification with the pre-oxidation, dosing 1.0 or 2.0 mg \'K\'MN\'O IND.4\'/L, and with the post-chlorination with 3.0 mg \'CL IND.2\'/L. In Phase 3, with initial concentration of extracellular microcystin around 64.1 \'mü\'g/L, the association of clarification with the adsorption with 60.0 mg/L of PAC and the post-chlorination with 3.0 mg\'CL IND.2\'/L provided residual extracellular microcystin below 1.0 \'mü\'g/L. It was also observed that in Phases 1 and 3 the presence of dissolved organic matter intervened negatively in the sequence of treatment when consuming part of the potassium permanganate destined to the oxidation of extracellular microcystin. However, in Phase 2 the demand for pre-oxidizing by the humic substances seems to have prevented the lysis of some cells of Microcystis sp.

A produção de mudas via propagação vegetativa é fundamental para se obter os ganhos desejados nos programas de melhoramento genético, bem como garantir o sucesso da implantação florestal. No entanto, existem muitos fatores que impedem a sua utilização de forma abrangente na produção de mudas para algumas espécies florestais, principalmente em relação à baixa taxa de enraizamento. Para atender a essa necessidade, pesquisas com o uso de substâncias que promovam maior taxa de enraizamento de miniestacas e crescimento de mudas vem sendo desenvolvidas, como o uso de reguladores de crescimento e de bioestimulantes à base de substâncias húmicas. Dessa forma o objetivo do presente trabalho é avaliar o efeito de adubos foliares e condicionadores de solo na produção de mudas clonais de híbridos de Pinus caribaea var. hondurensis vs. elliottii var. elliottii e de Pinus tecunumanii vs. caribaea var. hondurensis. Os experimentos foram desenvolvidos em viveiro florestal na cidade de Paranapanema-SP, com delineamento de blocos ao acaso, em arranjo fatorial 4x2, com duração de seis meses. Foram utilizados dois condicionadores de solo, sendo o C1 à base de pescados marinhos e o C2 à base de ácidos húmicos e quatro adubos foliares, sendo AF1 à base de quitosana, AF2 à base de pescados marinhos, AF3 à base de ácido húmico e AF4 extrato da alga Ascoplhyllum nodosum, além da mistura dos adubos M1AF (AF2+AF3+AF4) e o M2AF (AF1+AF3+AF4). Foram instalados dois experimentos: 1) híbrido de P. caribaea var. hondurensis vs. elliottii var. elliottii, testando a combinação dos dois condicionadores de solo e os adubos AF2, AF3, AF4 e M1AF e 2) híbrido de P. tecunumanii vs. carearia var. hondurensis em que a única alteração nos tratamentos foi o AF2 por AF1 e o M1AF por M2AF. As mudas foram avaliadas nas três fases da seguinte forma: 1) casa de vegetação: taxa de enraizamento; 2) casa de sombra: altura, massa seca e verde da parte aérea e radicial e a relação entre elas; e 3) rustificação: avaliadas as mesmas variáveis da casa de sombra, além do estado nutricional das acículas. Para o experimento 1, a taxa de enraizamento com C2 + AF3 foi 46,67% maior quando comparada à testemunha, comprovando o efeito positivo das substâncias húmicas no enraizamento. Já na fase de rustificação, a interação C1 + AF3 promoveu maior crescimento das mudas. Para o experimento 2, não houve diferença nas taxas de enraizamento na casa de vegetação, devido a característica de rápido crescimento do P. tecunumanii. E, na fase de rustificação, o adubo foliar AF4 promoveu maior crescimento somente em altura. Na casa de sombra, os tratamentos testados não promoveram crescimento significativo para ambos os híbridos. Os teores nutricionais analisados nas acículas estão dentro dos níveis adequados para ambos os experimentos. Somente o Mn apresentou baixo teor, mas sem sintomas de deficiência no experimento 2. Os híbridos obtiveram respostas diferentes quando submetidos a tratamentos semelhantes e a determinação do tratamento adequado vai depender do gargalo na produção de mudas, podendo este ser o enraizamento ou o crescimento. / The production of cuttings by vegetative propagation is essential to obtain the desired accomplishment in genetic improvement programs and ensure the success of forest establishment. However there are many factors that prevent their use in a comprehensive manner considering the production of cuttings for some forest species especially in low rooting rate. In order to meet this need research on the use of substances that promote greater rooting rates of minicuttings and growth of cuttings have been developed with the use of growth regulators and biostimulants based on humic substances. Thus the purpose of this study is to evaluate the effect of foliar fertilizers and soil conditioners in the production of Pinus caribaea var. hondurensis vs. elliottii var. elliottii and Pinus tecunumanii vs. caribaea var. hondurensis hybrids cuttings. The experiment was conducted in the city of Paranapanema-SP using cutting nursery with delineation of randomized blocks in a factorial arrangement 4x2, lasting six months. It used two soil conditioners, the C1 based on marine fish and C2 based on humic acids and 4 foliar fertilizers, the AF1 chitosan base, AF2 based on marine fish, AF3 based on humic acid and AF4 by Ascoplhyllum nodosum seaweed extract, besides the mixture of fertilizers M1AF (AF2;AF3;AF4) and M2AF (AF1;AF3;AF4). Two experiments were implemented: 1) hybrid of P. caribaea var. hondurensis vs. elliottii var. elliottii, testing the combination of two soil conditioners as well as fertilizers AF2, AF3, AF4 and M1AF and 2) hybrid of P. tecunumanii vs. caribaea var. hondurensis in which the only change in treatment was the AF2 by AF1 and M1AF by M2AF. Cuttings were evaluated in three phases as follows: 1) greenhouse: rooting rate; 2) shade house: higher, aerial drywet mass and radicial part as well as the relationship between them; 3) hardening: the shade house had the same variables evaluated, in addition with the nutritional status of needles. For the experiment 1, the rooting rate with C2 + AF3 were 46.67% higher compared with the control, this stated the positive effect of humic substances on rooting. Considering the hardening phase C1 + AF3 interaction promoted greater seedling growth. For the experiment 2 there was no difference in rooting rates at greenhouse, because the characteristic of fast growth of P. tecunumanii. In hardening phase, the foliar fertilizer AF4 promoted greater growth only in height. In the shade house treatments did not promote significant growth for both hybrids. Nutritional contents analyzed the needles leaves are within appropriate levels for both experiments. Mn showed only low level, but without deficiency symptoms in the experiment 2. Different answers were obtained on hybrids when subjected to similar treatment and to determine the appropriate treatment will depend on the obstaclecuttings production, which may either rooting or growth.

Este trabalho foi realizado com o objetivo de avaliar o comportamento de um sistema de dupla filtração, utilizando filtro ascendente de pedregulho seguido de filtro rápido descendente na remoção de substâncias húmicas. A parte experimental foi realizada em uma instalação piloto, que utilizou como afluente a água do Ribeirão Feijão na qual foi adicionado extrato de substâncias húmicas, previamente extraído de solo turfoso por meio de extração alcalina, para que a cor verdadeira da água de estudo resultasse entre 90 e 110 uH. As condições de coagulação, como gradiente de velocidade, dosagem e pH, foram definidos em ensaios com jarteste. As taxas utilizadas no filtro ascendente em pedregulho foram de 80 e 120 m3/m2.dia e no sistema de filtração rápida descendente de 80, 120, 150, 180, 220 e 240 m3/m2.dia. As carreiras tiveram duração máxima de 72 horas. A utilização do critério de realização de Descargas de Fundos Intermediárias (DFIs), quando o efluente do Filtro Ascendente de Pedregulho (FAP) atingisse valor maior ou igual 50 uH, não permitiu aumento da cor no efluente final. O sistema de dupla filtração estudado foi eficiente na remoção de cor, atingindo diversas vezes remoção completa; outros parâmetros relativos à concentração de substâncias húmicas, como absorvância (254 nm) e Carbono Orgânico Dissolvido (COD), foram removidos entre 89,1 a 93,6% e 27,5 a 48,5% respectivamente. / The present work was carried out to evaluate the removal of humic substances in a double filtration system, comprising on upflow gravel prefilter followed by a rapid down flow filter. Raw water was abstracted from the influent took to the municipal water treatment Plant 2. Humic substances were extracted from peat through alkaline process. The concentrated solution was pumped to raw water in order to obtain true colour of 90-110 Hu in the influent to the pilot plant. Filtration rates studied were as follows: 80 and 120 m3/m2.day in the upflow filter 80, 120, 150, 180, 220 e 240 m3/m2.day in the down flow filter. Maximum filter run length was fixed in 72 hours. Intermediate down flushes in the upflow filter were performed during the run when the effluent colour reached 50 Hu. It is concluded that the system performed efficiently to remove colour; in most part of the effluent colour remained bellow 1 Hu. Absorbance (254 nm) removal resulted high (between 89,1% and 93,6%). Dissolved organic carbon resulted satisfactory (27,5% to 48,5%).

O presente trabalho teve como objetivos estudar a potencialidade da FAD associada à oxidação química e comparar com a sedimentação também conjugada à oxidação química, em escala de laboratório, além de avaliar a eficiência de uma unidade piloto de FAD lamelar de alta taxa com escoamento horizontal no tratamento de água contendo ferro, manganês e matéria orgânica em concentrações acima dos padrões de potabilidade. Nos ensaios de flotação em escala de laboratório, entre os valores de dosagem de coagulante (cloreto férrico) investigados (na faixa de 15 a 35 mg/L) - o valor de 30 mg/L associado ao pH em torno de 6,2 e à aplicação de 2,7 mg/L de cloro, na forma de hipoclorito de sódio - apresentou os melhores resultados de remoção de cor, turbidez, ferro e manganês. No caso da sedimentação, também em escala de laboratório, dentre os valores de dosagem de coagulante investigados (30 e 45 mg/L), foi o valor de 30 mg/L associado a valor de pH em torno de 8,5 e à aplicação de 2,7 mg/L de cloro, que forneceu os melhores resultados de remoção de turbidez, ferro e manganês. A comparação entre a clarificação por FAD e por sedimentação da água de estudo, consideradas as melhores condições de coagulação e de floculação, mostrou que a flotação apresentou resultados de remoção de turbidez, cor aparente e ferro muito superiores aos obtidos nos ensaios de sedimentação. A unidade piloto de FAD lamelar de alta taxa com escoamento horizontal apresentou elevada eficiência de clarificação da água de estudo após prévia adequação das condições de oxidação química, coagulação e floculação, em escala de laboratório. Essa unidade foi capaz de operar, com excelente desempenho, com taxas de até 39 m/h, desde que fossem fornecidos 4,3 g de ar/m3 de água e tempo de floculação de 20 minutos. Finalmente, após o estudo e adequação das condições de coagulação, floculação e flotação por ar dissolvido, ) o efluente do flotador foi filtrado em unidade de filtração rápida descendente com leito de areia tendo apresentado residuais de turbidez em torno de 0,40 uT, cor aparente menor que 2 uC, ferro em torno de 0,10 mg/L e manganês a 0,02 mg/L, tanto para o efluente com taxa de flotação de 13 m/h quanto para 39 m/h, após 4 horas de filtração. Isto confirma a utilização, com elevada eficiência, da unidade piloto lamelar de alta taxa e escoamento horizontal com taxas de até 39 m/h, como pré-clarificação da água de estudo. / The aim of this research was to study and compare the potentiality of DAF and sedimentation processes associated with chemical oxidation, using lab scale (batch) as well as to assess the efficiency of a high-rate dissolved air flotation piloto unit with horizontal flow followed by a rapid sand bed filtration system, in the treatment of water with high concentration of iron, manganese and humic substances. For the essays in lab scale, among the values of coagulant dosage investigated (ferric chloride, in the range of 15-35 mg/L), the dosage of 30 mg/L associated to a pH value around 6.2 and oxidant dosage 2.7 mg/L of chlorine, in the form of sodium hypochlorite, presented the best results, in terms of color, turbidity, iron and manganese removal. For the sedimentation essays, also performed in lab scale, among the values of coagulant dosage investigated (30-45 mg/L), the dosage of 30 mg/L associated to 2.7 mg/L of chlorine supplied the best removal results for turbidity, iron and manganese. The comparison between dissolved air flotation and sedimentation clarification in lab scale, when the best conditions of coagulation and flocculation were carried out to both processes, showed that the results for flotation were highly better than the results obtained by sedimentation, in terms of turbidity, color and iron removal. The high-rate DAF pilot unit with horizontal flow showed high clarification efficiency after previous adaptation of the conditions of chemical oxidation, coagulation and flocculation, as investigated at the lab essays. The unit operated with excellent performance using high rates up to 39 m/h, since it was supplied 4.3 g of air/m3 of water and flocculation time of 20 minutes. The sand bed unit of rapid filtration showed high performance in removal of turbidity (around 0.40 uT), color (< 2 uC), iron (around 0.10 mg/L) and manganese (0.02 mg/L), with 4 hours of filtration, when rates from 13 to 39 m/h were used in the high-rate DAF pilot unit. This fact confirms that the use of the high-rate DAF pilot unit with rates up to 39 m/h is feasible with high efficiency as a pre-clarification to the water evaluated.

L'organisation des substances humiques à l'échelle moléculaire reste une question largement débattue, et à ce jour, il n'a pas été possible de trancher entre une structure polymérique en pelotte plus ou moins flexible et un assemblage supramoléculaire de molecules hétérogènes associées par des liaisons hydrogènes et des interactions hydrophobes. Dans cette thèse, nous étudions la reconformation induite par l'addition de tensio-actifs cationiques (Chlorure de C n-trimethylammonium) sur une série de substances humiques (acides fulvique et humiques) ainsi que sur de la matière organique naturelle contenue dans des eaux noires. Des mesures de turbidité, de diffusion de lumière, mobilité électrophorétique, tension de surface, spectroscopie de fluorescence, diffusion des neutrons aux petits angles, et cryomicroscopie à transmission, permettent de decrire les complexes formés entre le tensio-actif et la matière humique. L'association matière humique/tensio-actif dépend à la fois d'interactions d'origine électrostatique et hydrophobe. Une série de structures moléculaires, vésicules, disques, globules, pseudo-micelles, est observée en cryomicroscopie selon la concentration en surfactant. La séquence obtenue est cohérente avec un système catanionique, en d'autres termes une partie de la matière humique est amphiphile et s'organise en assemblage supramoléculaire. L'addition de tensio-actif modifie également fortement le spectre de fluorescence de la matière humique, les nouvelles bandes bien résolues présentes sur le spectre indiquant une restructuration majeure de l'assemblage supramoléculaire. / The structural organization of humic nanocolloids remains a matter of harsh debate, and surprisingly, it is yet not possible to decide between an arrangement of the humic matter in the form of randomly coiled macromolecules more or less connected, and a supramolecular organization of small heterogeneous molecules linked by hydrogen bonds and hydrophobic interactions. In this study, we investigate the reconformation induced by the addition of cationic surfactants (C n-trimethylammonium chloride) of varying alkyl chain length with a series of humic substances (HS) and Dissolved Organic matter (DOM) from two blackwater rivers of the Central Amazon. Turbidity measurements, Dynamic light scattering, electrophoretic mobility, surface tension, fluorescence spectroscopy, small angle neutron scattering and cryo-transmission electron microscopy (cryo-TEM), are combined to describe the Humic Substance/Surfactant complexes obtained. The association between the oppositely charged HS and cationic surfactant is driven by both electrostatic and hydrophobic interactions. A variety of molecular structures, unilamellar vesicles, disks, globules, spheroidal micelles, are visualized by cryo-TEM depending on surfactant concentration. Such sequence, consistent with those displayed by catanionic systems, provides an independent confirmation of both the amphiphilic nature of HS and of its supramolecular organization. In addition, the molecular rearrangement was investigated using single-scan fluorescence emission spectra spectroscopy, thus identifying the chemical groups responsible for the fluorescence properties in HS and DOM. The addition of cationic surfactant to HS/DOM unveils an unexpected fine structure of humic-like fluorescence through new emission peaks that are not evidenced in the references HS/DOM. An enhanced protein-like fluorescence indicating major restructuration and structural stacking/de-stacking is observed. All our results support a supramolecular organization of humic substances and DOM.

This diploma thesis is focused on the study of structure and physicochemical properties of organic fractions of humic substances, which were obtained by the method of thin-layer chromatography. Humic substances, which were used in this study, were isolated from a sample of Slovak alginite based on the procedure of the International Humic Substances Society (IHSS). The following analytical techniques were selected for the characterization of isolated humic substances: thermogravimetric and elemental analysis, molecular absorption spectroscopy (UV/Vis), Fourier transform infrared spectroscopy (FTIR) and steady-state fluorescence spectroscopy. Each organic fraction of humic substances were characterized by molecular absorption spectroscopy (UV/Vis) and steady-state fluorescence spectroscopy. Using steady-state fluorescence spectroscopy, humic substances were found to be composed of fluorophores of humic and non-humic (protein) character. Organic fractions corresponding to the humic fluorophores were characterized by a higher content of oxygen substituents on the aromatic nukleus, a higher degree of aromaticity and also a higher molecular weight. The aim of this diploma thesis was to design and optimize the process of organic matter fractionation for the purpose of detailed understanding of the structure and properties of humic substances, which were isolated from the sedimentary rock alginite. Based on this, the practical applicability of the thin layer chromatography method to significantly reduce the molecular heterogenity of the studied humic substances was evaluated.

This thesis is focused on the development and characterization of hydrogels containing humic substances with possible use in cosmetic and pharmaceutical industries. This work follows on the bachelor thesis, theoretical and experimental part is based on already acquired knowledge. The aim of this work was to develop a literature review focusing on the potential use humic gels in practice and also to enhance the consistency of other active ingredients. Based on this literature review, the main aim was to prepare model humic hydrogels with selected active ingredients and their characterization by basic methods of material analysis. These basic methods were especially rheology and visual assessment of consistency during the preparation, then the samples were subjected process of drying and swelling. Experimental results showed considerable influences during the preparation and composition of each sample, which then reflected in their structure and consistency. Furthermore, it was found that the suitable composition and combination of ingredients form hydrogels acceptable characteristics for further use in cosmetic or pharmaceutical applications.

This master thesis deals with the study of thermodynamic and structural aspects of the interactions of humic acids with organic ions. Methylene blue (dye) was used as a model organic ion. The interactions were studied by isothermal titration calorimetry, dissolution calorimetry and by diffusion in diffusion cells.

Norrvatten är den fjärde största dricksvattenproducenten i Sverige. De producerar och distribuerar dricksvatten till 14 kommuner norr om Stockholm. Norrvatten har under en tid studerat alternativa processer för att optimera och öka produktionskapaciteten och effektiviteten i deras dricksvattenreningsverk vid Görvälnverket.  I detta projekt har en pilotanläggning använts för att studera och optimera ett hybridprocessteg bestående av ett koagulerings- och ultrafiltreringssteg med syfte att avlägsna humusämnen från ytvatten. Effekten av pH, reaktionstid och olika matarvattenkvaliteter (Görväln, Fyrisån och sandfiltrat) analyserades genom en serie experiment utförda med pilotanläggningen. Den mest optimala placeringen av ett eventuellt ultrafiltreringssteg i reningsprocessen studerades även.   Resultaten från experimenten påvisade att pH mellan 6.1 och 6.7 inte hade någon effekt på reningen av fDOM. Mer signifikanta skillnader i rening kunde observeras mellan de olika koaguleringsdoserna, vilket indikerar att denna parameter är viktigare än pH. Reaktionstiden hade ingen märkbar effekt på anläggningens reningseffektivitet. Däremot ökade transmembrantrycket tio gånger snabbare under experimenten med den kortare reaktionstiden. Dessa resultat antyder att de bildade flocken var mindre och därmed blev mer tätt packade i ultrafiltret vilket i sin tur lett till det snabbt ökande trycket i membranet. En avskiljning av minst 50 %, men inte mer än 60 %, av det ingående fDOM kunde uppnås med alla matarvatten utom sandfiltratet, som hade en reningseffektivitet på 18 %. Vattnet från Fyrisån visade sig vara en utmaning för anläggningen att hantera, då trycket snabbt byggdes upp i membranet vilket tyder på att anläggningen inte klarar för starkt förorenade vatten. Resultaten från sandfiltratexperimenten visade att ett ultrafiltreringssteg efter sandfiltren skulle kunna vara en möjlig placering av ultrafiltren. Ytterligare studier krävs dock för att med säkerhet kunna bestämma den mest optimala placeringen.   Sammanfattningsvis visar resultaten från experimenten lovande tecken på att en ultrafiltreringsprocess är ett möjligt alternativ för att öka Norrvattens dricksvattenreningsverks effektivitet och kapacitet. / Norrvatten is the fourth largest drinking water producer in Sweden. They produce and distribute drinking water to 14 municipalities north of Stockholm. For some time, Norrvatten has studied alternative processes in order to optimise and increase the production capacity and efficiency of their drinking water treatment plant at Görvälnverket.   In this project, a small-scale pilot plant has been used to study and optimise a coagulation and ultrafiltration hybrid process step in order to remove humic substances from surface water. The effect of pH, reaction time, and different feed water qualities (Görväln, Fyrisån and Görväln full scale sand filtrate) were analysed through a series of experiments performed with the pilot plant. The most optimal placement of an eventual ultrafiltration step was also studied.  The results from the experiments suggested that pH in the range 6.1 to 6.7 had no large effect on the removal efficiency of fluorescent dissolved organic matter (fDOM). Instead, differences in removal efficiency could be observed between coagulant dosages which indicates that this parameter is of more importance than pH. At higher pH (&gt; 7) removal was significantly lower. The reaction time had no effect on the removal efficiency of the plant. However, the transmembrane pressure increased ten times faster during the experiments with a shorter reaction time. These results suggested that the floc formed were smaller and thereby more tightly packed in the ultrafilter which in turn increased the pressure in the membrane. An fDOM removal of at least 50 %, though no more than 60 %, was achieved with all feed waters except for the sand filtrate which had a removal efficiency of 18 %. However, highly concentrated humic waters such as Fyrisån proved to be challenging for the plant to handle since the pressure built up rather quickly in the membrane. The sand filtrate feed water experiments indicated that an ultrafiltration step after a sand filtration process would be effective. However, further studies are required to be able to determine the most optimal placement of the ultrafiltration process.  In conclusion, the results achieved with the pilot plant show promising signs of an ultrafiltration process being a viable alternative for Norrvatten to increase their drinking water treatment plant’s efficiency and capacity.

Motiviert durch die Zunahme der weltweiten Nachfrage nach hochwertigen Humusstoffen wurde am Institut für Holz- und Pflanzenchemie ein neuartiger Humusersatzstoff entwickelt. Dieses N-modifizierte Produkt wird auf Basis eines patentierten Normaldruckverfahrens der oxidativen Ammonolyse (OA) aus ligninhaltigen Ausgangssubstanzen, im vorliegenden Fall Lausitzer Braunkohle, hergestellt. Ziel war, die bisher vorliegenden Erkenntnisse der strukturellen Eigenschaften solcher Humusstoffe zu erweitern. Im Fokus standen die Gehalte und Charakteristik der Huminstofffraktionen (Humine, Humin- und Fulvosäuren). Der Stickstoff und die Art seines Einbaus in die organische Substanz spielt hierbei eine besondere Rolle. Für die Huminstoffisolierung kam die hinsichtlich der Ausbeuten und des Zeitaufwandes optimierte IHSS-Methode zum Einsatz. Wesentliche Merkmale N-modifizierter Substanzen sind erhöhte Huminsäurengehalte, zeitlich differenziert wirksame N-Bindungsformen und damit eine Diversifizierung der Funktionalität. Zusätzlich mit dem geringen Aschegehalt unterscheidet dies N-modifizierte Lausitzer Braunkohle von anderen auf Braunkohlebasis erzeugten Bodenverbesserungsmitteln des Marktes. Es konnte gezeigt werden, dass Huminsäuren hinsichtlich der Bereitstellung von Stickstoff und Funktionalität (z.B. Austauscherplätze) eine Schlüsselrolle einnehmen. Die Veränderungen durch die OA basieren stofflich auf der Bildung regenerierter Huminsäuren und chemisch u.a. auf der oxidativen Ringspaltung von Aromaten an nicht veretherten phenolischer OH-Gruppen von Methoxyphenolstrukturen. Dabei ist diese Reaktion entgegen früherer Annahmen nicht an eine Demethoxylierung gebunden und erfordert auch keine verschärften Reaktionsbedingungen (z.B. erhöhter Druck). Diese und weitere Reaktionsmechanismen führen zu ammoniumartig, amidartig und fest organisch gebundenen N-Bindungsformen. 15N-NMR-Spektroskopische Untersuchungen an einem 15N-angereicherten Produkt, Py-GC/MS-Untersuchungen und nasschemische Experimente zeigen, dass in der Vergangenheit die Bedeutung heterocyclischer, insbesondere heteroaromatischer N-Bindungsformen überschätzt wurde. Amidartiger Stickstoff präsentiert sich dabei als außerordentlich heterogen hinsichtlich seiner Hydrolysestabilität bzw. Pflanzenverfügbarkeit. Für die effektive Beurteilung möglicher Ausgangssubstanzen hinsichtlich ihrer Eignung für die Herstellung von Humusdüngestoffen nach dem Prinzip der OA kann der Huminsäurengehalt herangezogen werden. Er wird mit Hilfe eines degradativen Verfahrens ermittelt. Die mit dem Huminsäurengehalt in Verbindung stehenden Stoffeigenschaften von Kohlen korrelieren gut mit dem N-Einbau. Aus Sicht der Verfahrensführung hängt die Intensität des N-Einbaus eng mit dem Oxidationsregime zusammen. Durch Anwendung von reinem Sauerstoff anstelle von Luft als sehr einfach und günstig zu realisierende Maßnahme kann die Reaktionszeit halbiert werden. / The development of a novel artificial humus material at the Institute of Wood- and Plant Chemistry was accounted by the increasing demand for high grade humic matter. This N-modified product base on a patented ambient pressure technology of the oxidative ammonolysis. of lignin containing substances, in particular Lusitian lignite. Objective of the work was to broadening the current knowledge of structural properties with focus on the contents and characteristics of humic substances fractions (humins, humic acids, fulvic acids). Especially attention was given to nitrogen and its way of incorporation into organic matter. For isolating humic substances the IHSS method was used. The procedure was adapted in order to increase the yield of humic acids and decrease time needed. Main characteristics of N-modified substances are higher contents of humic acids and subtly differenciateted effective N-binding forms with leads to higher diversity of the chemical functionality. This and the low ash content makes the differences to other brown coal based soil improving agents available on the marked. It has been shown that humic acids give the main part providing nitrogen and functionality (e.g. cation exchange capacity). The oxidative ammonolysis leads to regenerated humic acids as well as e.g. the clevage of aromatic structures by reactions of free phenolic groups. In contrast to former assumptions the cleavage is not strongly related to demethoxylation or strong reaction conditions like high pressure. This and other reactions lead to short, middle, and long lasting N-binding forms. 15N-NMR-spectroscopic investigations on a 15N-enriched product, Py-GC/MS-investigations and conventional investigations show an overestimation of heterocyclic, in particular heteroaromatic N-binding forms up to now. Consequently amide like nitrogen reveals as extraordinary according to its persistent behaviour to hydrolysis and plant availability respectively. Corresponding the correlation of the N-incorporation and humic acid content of raw materials the latter can be used for evaluating possible raw material for its usage for N-modification. It can be easy obtained in a degratadive way. From the process engineering point of view the success of N-incorporating is strongly correlated to the oxidation conditions during processing. Using pure oxygen instead of air shorts the needed reaction at 50%.