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 (> 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%.

The main aim of doctoral thesis is the study on physicochemical properties of humic substances (HS) by modern instrumental techniques. The subject of the study were HS isolated from South Moravian lignite, South Bohemian peat, forest soil Humic Podzol and finally extract from brown sea algae Ascophyllum nodosum. With respect on determination of structure and reactivity of these unique “biocolloids”, standard samples (Leonardite HA, Elliott Soil HS and Pahokee Peat HS) were also studied. These samples were obtained from International Humic Substances Society (IHSS). All mentioned substances were characterized by elemental analysis (EA), molecular absorption spectroscopy in ultraviolet and visible region (UV/Vis), infrared spectroscopy with Fourier transformation (FTIR), nuclear magnetic resonance spectroscopy of carbon isotope 13C (LS 13C NMR), steady-state and time resolved fluorescence spectroscopy. Obtained fluorescence, UV/Vis and 13C NMR spectra were used for calculation of fluorescence and absorption indexes, values of specific absorbance and structural parameters respectively, which were used for fundamental characterization of these “biocolloidal” compounds. Infrared spectroscopy with Fourier transformation was utilized for the identification of functional groups and structural units of HS. Evaluation of infrared spectra is quiet complicated by overlapping of absorption bands especially in fingerprint region. This problem was overcome by Fourier self-deconvolution (FSD). Steady-state fluorescence spectroscopy was used for deeper characterization of HS with respect to origin, structural units, amount of substituents with electron-donor and electron-acceptor effects, content of reactive functional groups, “molecular” heterogeneity, the degree of humification, etc. Parameters of complexation of samples Elliott Soil with heavy metal ions (Cu2+, Pb2+ and Hg2+) were obtained by using modified Stern-Volmer equation. These ions were chosen purposefully, because the interaction of HS with these ions is one of the fundamental criteria for the assessment of the reactivity of HS. Key part of the whole doctoral thesis is time-resolved fluorescence spectroscopy. It is able to determine the origin of emission of HS by method Time-Resolved Area Normalized Emission Spectra (TRANES). The viscosity of micro medium about excited fluorophores of HS was determined by Time-Resolved Emission Spectra (TRES).

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%.

Este projeto nasceu inserido num contexto de crescentes pesquisas em direção à construção de um cabedal de conhecimento acerca das ciências ambientais que tratam e estudam a dinâmica dos reservatórios de carbono e suas contribuições para o Efeito Estufa. Extrapolações de novos mapas digitalizados de solos sugerem que os espodossolos hidromórficos da Amazônia podem estar com uma contagem de carbono subestimada em até 12,3 Pg de C e trabalhos anteriores mostram que o carbono imobilizado neste perfil pode sofrer mineralização devido ao corte na rede de drenagem ou rebaixamento do nível freático, podendo assim contribuir em grande parte para o aumento de emissão dos Gases do Efeito Estufa. Nesta circunstância, coube a este trabalho, caracterizar espectroscopicamente, a matéria orgânica estocada em profundidade em 9 perfis de solo da região de São Gabriel da Cachoeira - AM, na floresta amazônica. Foram analisadas 127 amostras em quantidade de carbono e por fluorescência induzida por laser (FIL). A partir destas análises preliminares, foi possível selecionar 12 amostras de 2 perfis para análise mais detalhada através da extração das substâncias húmicas. Foram realizadas análises para obtenção da textura destes perfis, análise dos ácidos húmicos como relação C/N, espectroscopia de infravermelho com transformada de Fourier (FTIR), RMN de 13C no estado sólido, fluorescências bidimensional e tridimensional com aplicação do método estatístico análise dos fatores paralelos (PARAFAC) e também análise dos ácidos fúlvicos como carbono orgânico total (TOC), espectroscopia na região do ultra-violeta e visível e fluorescência 3D associada ao PARAFAC. Em geral, as amostras se dividiram em 3 grupos diferentes, onde a matéria orgânica em superfície se mostrou lábil e recente, a matéria orgânica nos horizontes B húmicos se mostraram com características recalcitrantes e a matéria orgânica contida nos horizontes onde existia água livre (lençol freático), se mostraram com características diferentes, indicando não serem tão jovens quanto as em superfície, porém mais jovens do que a armazenada no Bh, devido a uma possível migração por movimentos laterais do lençol freático. A correlação entre os resultados mostrou que a textura do solo é importante para o acúmulo da matéria orgânica e conseqüentemente sua humificação. Os resultados de fluorescência corroboraram a interpretação dos dados de RMN, FTIR e textura, apontando que o Perfil 4 (mais próximo ao rio) por ter C2 maior nos horizontes intermediários, contém maior quantidade de exsudatos microbianos frescos. Para o Perfil 5, que é uma mancha de Espodossolo dentro de um Latossolo e encontra-se mais longe do rio, os fluoróforos mais representativos são oriundos de anéis aromáticos mais antigos e conseqüentemente mais humificados, devido às maiores intensidades de C1 e C3. Vale ressaltar que esta interpretação se alinha com os resultados de datação do 14C desta região. Foi notório que a humificação ocorre a partir do começo do horizonte Bh e que seu acúmulo pode ocorrer tanto nos horizontes intermediários (Bh) quanto mais os profundos (úmidos). Dessa forma, pode-se concluir que uma drenagem excessiva das bordas dos rios nesta região que acumula carbono em profundidade, poderá expor a MO guardada e estocada a longo tempo, contribuindo para o aumento da temperatura global e por conseguinte catalisando um desequilíbrio no clima da sua maior reguladora no mundo: a Floresta Amazônica. / This project was born inserted in a context of increasing research towards building knowledge about environmental science that treat and study the dynamics of carbon reservoirs and their contribution to the greenhouse. Extrapolation of new digital soil maps suggests that Amazonian hydromorphic Spodosols may be with a carbon accounting underestimated by up to 12.3 Pg of C and previous work show that the carbon fixed in this profile may suffer mineralization due to the cut in the drainage network or lowering of the water level and can contribute largely to the increased emission of greenhouse gas. In this circumstance, it was instructed to this work, the spectroscopic characterization, of the stored organic matter in depth at 9 soil profiles of São Gabriel da Cachoeira - AM, in the Amazon rainforest. 127 samples were analyzed for amount of carbon and laser-induced fluorescence (LIF). From these preliminary analyzes, it was possible to select 12 samples of 2 profiles for humic substances extraction and further detailed analysis. Analyzes were conducted to obtain the texture of these profiles, analysis of humic acids as C/N ratio, Fourier Transform Infrared Spectroscopy (FTIR), solid state 13C NMR, two and three dimensional fluorescence with applying of the Parallel factors analysis (PARAFAC) statistical method and also fulvic acid analysis as Total Organic Carbon (TOC), ultra-violet and visible region spectroscopy and 3D fluorescence associated with PARAFAC. In general, the samples were divided into 3 different groups, wherein the surface organic matter evinced labile and recent. The B humic horizons organic matter proved recalcitrant characteristics and organic matter contained in horizons which had free water (groundwater), showed different characteristic, indicating they are not so young as the surface, but younger than stored in Bh, because of possible migration by lateral movements of the water table. The correlation between the results showed that soil texture is important for the accumulation of organic matter and therefore its humification. The fluorescence results confirmed the interpretation of the NMR, FTIR and texture datas, indicating that the profile 4 (closest to the river), presenting major C2 in intermediate horizons, contains larger amount of fresh microbial exudates. To profile 5, which is a Spodosol spot within a Ferrasol and is thither from the river, the most representative fluorophores came from older aromatic rings and therefore is more humified, due to higher intensities C1 and C3. It is noteworthy that this interpretation is in accord with the results of 14C dating of samples from this region. It was clear that the humification occurs from the beginning of the Bh horizon and their accumulation can occur both in the intermediate horizons (Bh) and in deeper (wet). Thus, it can be concluded that excessive drainage of the edges of rivers in this region that collects carbon in depth, may expose the OM stored for long time, contributing to increase the overall temperature and therefore catalyzing an imbalance in the climate of the biggest regulatory of it in the world: the Amazon rainforest.

Este projeto nasceu inserido num contexto de crescentes pesquisas em direção à construção de um cabedal de conhecimento acerca das ciências ambientais que tratam e estudam a dinâmica dos reservatórios de carbono e suas contribuições para o Efeito Estufa. Extrapolações de novos mapas digitalizados de solos sugerem que os espodossolos hidromórficos da Amazônia podem estar com uma contagem de carbono subestimada em até 12,3 Pg de C e trabalhos anteriores mostram que o carbono imobilizado neste perfil pode sofrer mineralização devido ao corte na rede de drenagem ou rebaixamento do nível freático, podendo assim contribuir em grande parte para o aumento de emissão dos Gases do Efeito Estufa. Nesta circunstância, coube a este trabalho, caracterizar espectroscopicamente, a matéria orgânica estocada em profundidade em 9 perfis de solo da região de São Gabriel da Cachoeira - AM, na floresta amazônica. Foram analisadas 127 amostras em quantidade de carbono e por fluorescência induzida por laser (FIL). A partir destas análises preliminares, foi possível selecionar 12 amostras de 2 perfis para análise mais detalhada através da extração das substâncias húmicas. Foram realizadas análises para obtenção da textura destes perfis, análise dos ácidos húmicos como relação C/N, espectroscopia de infravermelho com transformada de Fourier (FTIR), RMN de 13C no estado sólido, fluorescências bidimensional e tridimensional com aplicação do método estatístico análise dos fatores paralelos (PARAFAC) e também análise dos ácidos fúlvicos como carbono orgânico total (TOC), espectroscopia na região do ultra-violeta e visível e fluorescência 3D associada ao PARAFAC. Em geral, as amostras se dividiram em 3 grupos diferentes, onde a matéria orgânica em superfície se mostrou lábil e recente, a matéria orgânica nos horizontes B húmicos se mostraram com características recalcitrantes e a matéria orgânica contida nos horizontes onde existia água livre (lençol freático), se mostraram com características diferentes, indicando não serem tão jovens quanto as em superfície, porém mais jovens do que a armazenada no Bh, devido a uma possível migração por movimentos laterais do lençol freático. A correlação entre os resultados mostrou que a textura do solo é importante para o acúmulo da matéria orgânica e conseqüentemente sua humificação. Os resultados de fluorescência corroboraram a interpretação dos dados de RMN, FTIR e textura, apontando que o Perfil 4 (mais próximo ao rio) por ter C2 maior nos horizontes intermediários, contém maior quantidade de exsudatos microbianos frescos. Para o Perfil 5, que é uma mancha de Espodossolo dentro de um Latossolo e encontra-se mais longe do rio, os fluoróforos mais representativos são oriundos de anéis aromáticos mais antigos e conseqüentemente mais humificados, devido às maiores intensidades de C1 e C3. Vale ressaltar que esta interpretação se alinha com os resultados de datação do 14C desta região. Foi notório que a humificação ocorre a partir do começo do horizonte Bh e que seu acúmulo pode ocorrer tanto nos horizontes intermediários (Bh) quanto mais os profundos (úmidos). Dessa forma, pode-se concluir que uma drenagem excessiva das bordas dos rios nesta região que acumula carbono em profundidade, poderá expor a MO guardada e estocada a longo tempo, contribuindo para o aumento da temperatura global e por conseguinte catalisando um desequilíbrio no clima da sua maior reguladora no mundo: a Floresta Amazônica. / This project was born inserted in a context of increasing research towards building knowledge about environmental science that treat and study the dynamics of carbon reservoirs and their contribution to the greenhouse. Extrapolation of new digital soil maps suggests that Amazonian hydromorphic Spodosols may be with a carbon accounting underestimated by up to 12.3 Pg of C and previous work show that the carbon fixed in this profile may suffer mineralization due to the cut in the drainage network or lowering of the water level and can contribute largely to the increased emission of greenhouse gas. In this circumstance, it was instructed to this work, the spectroscopic characterization, of the stored organic matter in depth at 9 soil profiles of São Gabriel da Cachoeira - AM, in the Amazon rainforest. 127 samples were analyzed for amount of carbon and laser-induced fluorescence (LIF). From these preliminary analyzes, it was possible to select 12 samples of 2 profiles for humic substances extraction and further detailed analysis. Analyzes were conducted to obtain the texture of these profiles, analysis of humic acids as C/N ratio, Fourier Transform Infrared Spectroscopy (FTIR), solid state 13C NMR, two and three dimensional fluorescence with applying of the Parallel factors analysis (PARAFAC) statistical method and also fulvic acid analysis as Total Organic Carbon (TOC), ultra-violet and visible region spectroscopy and 3D fluorescence associated with PARAFAC. In general, the samples were divided into 3 different groups, wherein the surface organic matter evinced labile and recent. The B humic horizons organic matter proved recalcitrant characteristics and organic matter contained in horizons which had free water (groundwater), showed different characteristic, indicating they are not so young as the surface, but younger than stored in Bh, because of possible migration by lateral movements of the water table. The correlation between the results showed that soil texture is important for the accumulation of organic matter and therefore its humification. The fluorescence results confirmed the interpretation of the NMR, FTIR and texture datas, indicating that the profile 4 (closest to the river), presenting major C2 in intermediate horizons, contains larger amount of fresh microbial exudates. To profile 5, which is a Spodosol spot within a Ferrasol and is thither from the river, the most representative fluorophores came from older aromatic rings and therefore is more humified, due to higher intensities C1 and C3. It is noteworthy that this interpretation is in accord with the results of 14C dating of samples from this region. It was clear that the humification occurs from the beginning of the Bh horizon and their accumulation can occur both in the intermediate horizons (Bh) and in deeper (wet). Thus, it can be concluded that excessive drainage of the edges of rivers in this region that collects carbon in depth, may expose the OM stored for long time, contributing to increase the overall temperature and therefore catalyzing an imbalance in the climate of the biggest regulatory of it in the world: the Amazon rainforest.

Soil organic matter (OM) is a complex mixture of compounds, mainly derived from plants and microbes at various states of decay. It is part of the global carbon cycle and is important for maintaining soil quality. OM protection is mainly attributed to its association with minerals. However, clay minerals preferentially sorb specific OM structures, and clay sorption sites become saturated as OM concentrations increase. Therefore, it is important to examine how OM structures influence their association with soil minerals, and to characterize other protection mechanisms. Several techniques, which provide complementary information, were combined to investigate OM composition: Biomarker (lignin phenol, cutin-OH acid, and lipid) analysis, using gas chromatography/mass spectrometry; solid-state 13C nuclear magnetic resonance (NMR) spectroscopy; and an emerging method, solution-state 1H NMR spectroscopy. OM composition of sand-, silt-, clay-size, and light fractions of Canadian soils were compared. It was found that microbial-derived and aliphatic structures accumulated in clay-size fractions, and lignin phenols in silt-size fractions may be protected from further oxidation. Therefore, OM protection through association with minerals may be structure-specific. OM in soils amended with maize leaves, stems, and roots from a biodegradation study were also examined. Over time, lignin phenol composition, and oxidation; and aliphatic structure contribution changed less in soils amended with leaves compared to soils amended with stems and roots. Compared to soils amended with leaves and stems, amendment with roots may have promoted the more efficient formation of microbial-derived OM. Therefore, plant chemistry influenced soil OM turnover. Synthetic OM-clay complexes and soil mineral fractions were used to investigate lignin protection from chemical oxidation. Coating with dodecanoic acid protected lignin from chemical oxidation, and overlying vegetation determined the relative resistance of lignin phenols in clay-size fractions from chemical oxidation. Therefore, additional protection from chemical oxidation may be attributed to OM composition and interactions between OM structures sorbed to clay minerals. Overall, these studies suggest that while association with minerals is important, OM turnover is also influenced by vegetation, and protection through association with clay minerals was modified by OM structure composition. As well, OM-OM interaction is a potential mechanism that protects soil OM from degradation.

Soil organic matter (OM) is a complex mixture of compounds, mainly derived from plants and microbes at various states of decay. It is part of the global carbon cycle and is important for maintaining soil quality. OM protection is mainly attributed to its association with minerals. However, clay minerals preferentially sorb specific OM structures, and clay sorption sites become saturated as OM concentrations increase. Therefore, it is important to examine how OM structures influence their association with soil minerals, and to characterize other protection mechanisms. Several techniques, which provide complementary information, were combined to investigate OM composition: Biomarker (lignin phenol, cutin-OH acid, and lipid) analysis, using gas chromatography/mass spectrometry; solid-state 13C nuclear magnetic resonance (NMR) spectroscopy; and an emerging method, solution-state 1H NMR spectroscopy. OM composition of sand-, silt-, clay-size, and light fractions of Canadian soils were compared. It was found that microbial-derived and aliphatic structures accumulated in clay-size fractions, and lignin phenols in silt-size fractions may be protected from further oxidation. Therefore, OM protection through association with minerals may be structure-specific. OM in soils amended with maize leaves, stems, and roots from a biodegradation study were also examined. Over time, lignin phenol composition, and oxidation; and aliphatic structure contribution changed less in soils amended with leaves compared to soils amended with stems and roots. Compared to soils amended with leaves and stems, amendment with roots may have promoted the more efficient formation of microbial-derived OM. Therefore, plant chemistry influenced soil OM turnover. Synthetic OM-clay complexes and soil mineral fractions were used to investigate lignin protection from chemical oxidation. Coating with dodecanoic acid protected lignin from chemical oxidation, and overlying vegetation determined the relative resistance of lignin phenols in clay-size fractions from chemical oxidation. Therefore, additional protection from chemical oxidation may be attributed to OM composition and interactions between OM structures sorbed to clay minerals. Overall, these studies suggest that while association with minerals is important, OM turnover is also influenced by vegetation, and protection through association with clay minerals was modified by OM structure composition. As well, OM-OM interaction is a potential mechanism that protects soil OM from degradation.