As limitações ao uso de antibióticos promotores de crescimento vêm aumentando a procura por aditivos substitutos para manter a performance animal, a saúde intestinal e a resposta imune de frangos de corte. Este experimento foi conduzido para comparar o efeito e a dose resposta do produto Ava Cid P (composto por substância húmica, butirato de sódio 30% protegido e uma pequena porção de acidificantes) suplementado na dieta, sobre a performance, resposta imune e saúde intestinal de frangos de corte. O experimento seguiu um design inteiramente casualizado, envolvendo um arranjo fatorial 2 x 5 (2 sexos e 5 tratamentos) com 7 repetições de 15 aves por tratamento. Os tratamentos seguiram a suplementação em diferentes fases de 1 a 49 dias: 1) Controle: dieta basal sem nenhuma suplementação; 2) AVA1-21: aves receberam 0,91 kg/t de Ava Cid P de 1 a 21 d; 3) AVA1-35: 0,91 kg/t de Ava Cid P de 1-21 d e 0,45 kg/t de 22-35 d; 4) AVA1-42: 0,91 kg/t de Ava Cid P de 1 a 21 d e 0,45 kg/t de 22- 42 d; 5) AVA1-49: 0,91 kg/t de Ava Cid P de 1 a 21 d, 0,45 kg/t de 22-35 d e 0,23 kg/t de 36-49 d. A suplementação com Ava Cid P não influenciou a performance de machos e fêmeas, nem mesmo a densidade de células caliciformes (P > 0,05). No entanto, o Ava Cid P foi capaz de modificar a morfometria intestinal, aumentando a altura de vilosidades aos 9 e 35 d (P < 0,05). A área superficial aparente dos vilos e altura de vilos, nas aves que receberam Ava Cid P durante todas as fases experimentais, foi superior à das aves suplementadas somente na fase inicial. No íleo, a área superficial aparente dos vilos também foi superior nas aves suplementadas aos 9 d. Além disso, a expressão do gene para mucina 2 (MUC2) e para o fator de necrose tumoral (TNF-α) diminuiu nas aves recebendo Ava Cid P aos 21 d (P < 0,05), mas não foram observadas diferenças estatísticas para interleucina-1 beta e interleucina-10. Os resultados sugerem que Ava Cid P pode alterar a expressão de mRNA de algumas citocinas e MUC2 e a morfometria intestinal de frangos de corte, aumentando a superfície aparente e a altura dos vilos, o que demonstra a potencialidade do produto como alternativa aos antibióticos promotores de crescimento. / The limitations of the antibiotic growth promoter’s (AGP) usage have been increasing the search for new products to improve poultry performance, gut healthy and immune response. This experiment was conducted to compare the effect and dose response of Ava Cid P (consisted of a humic substance, coated sodium butyrate 30% and a small acidifier portion) diet supplementation on performance, immune response and gut health of broilers. Five dietary regimens were used: 1) birds didn’t receive Ava Cid P in any phase (Control), 2) birds received 0.91 kg/t of Ava Cid P from 1 to 21 d (AVA1-21), 3) 0.91 kg/t of Ava Cid P from 1 to 21 d and 0.45 kg/t from 22 to 35 d (AVA1-35), 4) 0.91 kg/t of Ava Cid P from 1 to 21 d and 0.45 kg/t from 22 to 42 d (AVA1-42), 5) 0.91 kg/t of Ava Cid P from 1 to 21 d, 0.45 kg/t from 22 to 35 d and 0.23 kg/t from 36 to 49 d (AVA1-49). They were applied in a completely randomized design, involving a 2 × 5 factorial arrangement with 2 sex and 5 levels of inclusion, and 7 replications with 15 birds each. The supplementation with Ava Cid P showed no influence on males and females growth performance and goblet cell density (P > 0.05). However, it modified the gut morphometry, increasing jejunum villi height at 9 and 35 days (P < 0.05). The apparent villus surface area and villi height on birds fed with Ava Cid P during all phases also increased in relation to those who received only in the early phase. The expression of mucin 2 (MUC2) and tumor necrosis factor-alpha (TNF-α) decreased on birds that received Ava Cid P at 21 days (P < 0.05), but no differences were seen for interleukin-1beta (IL-1β) and interleukin-10 (IL-10). The results suggest that Ava Cid P can alter the mRNA expression of some inter-leukins, MUC2 and intestinal morphometry in broilers, increasing apparent villus surface area and villi height, which demonstrates the product potential as an alternative growth promoter.

Abstract: Certain cultures present especification in the assimilation of some ions, that are or not in available ways in the soil. The minerals have fundamental paper in the presence of those elements that, a lot of times, they are together originating from of the processes of meteorization of the rocks with the decomposition of the organic matter. This work had for objective to study the extraction and/or solubilization of some present chemical elements in the studied minerals and in a red latosoil, for the action of some organic acids produced starting from the decomposition of the matter ligno-cellulousic, through the microbial action, hoping to contribute in some way in the understanding of the mechanisms of fertility of the soil and, consequently, in the mineral nutrition of plants. The used minerals were: manganite [MnO(OH)], hematite (Fe2O3), pirolusite (MnO2), caolinite [Al2Si2O5(OH)4], goethite (HFeO2), bentonite [Na3(Al,Mg)2 2(Si4O10)(OH)2.H2O] e magnetite(Fe3O4), that commonly happen in areas humid intertropicals and a red latosoil, of sandy texture that, it represents more that 20% of the area of the State of Saint Paulo. The minerals and LV were triturated and drizzled in 0,05mm mesh, separately. After having examined with relationship your structure for Difratometric of Ray-X (XRD), 1g of those minerals and LV were conditioned, separately, in glass flasks. Some samples were only treated with distilled water and other with solution 0,02 mol.L-1 of the following acids: acetic, butyric, citric, carbolic, lactic, malic, oxalic, propionic and tannic, separately, for 53 days, with weekly agitations and conditions aerobics. After the digestion of the samples, they were certain the litio concentrations, sodium, potassium, magnesium, calcium, barium, vanadium, cromium, molibdenium, manganese, iron, cobalt, nickel, copper, zinc, cadmium, mercury, boron, aluminum, silicio, tin, lead, match... (Complete abstract click electronic access below) / Orientador: Ademércio Antonio Paccola / Coorientador: Pedro de Magalhães Padilha / Banca: Silas Macedo Silva / Banca: Paulo Sergio R. de Oliveira / Banca: Antonio Francisco Godinho / Banca: Rosana Cavalcante dos Santos / Doutor

As limitações ao uso de antibióticos promotores de crescimento vêm aumentando a procura por aditivos substitutos para manter a performance animal, a saúde intestinal e a resposta imune de frangos de corte. Este experimento foi conduzido para comparar o efeito e a dose resposta do produto Ava Cid P (composto por substância húmica, butirato de sódio 30% protegido e uma pequena porção de acidificantes) suplementado na dieta, sobre a performance, resposta imune e saúde intestinal de frangos de corte. O experimento seguiu um design inteiramente casualizado, envolvendo um arranjo fatorial 2 x 5 (2 sexos e 5 tratamentos) com 7 repetições de 15 aves por tratamento. Os tratamentos seguiram a suplementação em diferentes fases de 1 a 49 dias: 1) Controle: dieta basal sem nenhuma suplementação; 2) AVA1-21: aves receberam 0,91 kg/t de Ava Cid P de 1 a 21 d; 3) AVA1-35: 0,91 kg/t de Ava Cid P de 1-21 d e 0,45 kg/t de 22-35 d; 4) AVA1-42: 0,91 kg/t de Ava Cid P de 1 a 21 d e 0,45 kg/t de 22- 42 d; 5) AVA1-49: 0,91 kg/t de Ava Cid P de 1 a 21 d, 0,45 kg/t de 22-35 d e 0,23 kg/t de 36-49 d. A suplementação com Ava Cid P não influenciou a performance de machos e fêmeas, nem mesmo a densidade de células caliciformes (P > 0,05). No entanto, o Ava Cid P foi capaz de modificar a morfometria intestinal, aumentando a altura de vilosidades aos 9 e 35 d (P < 0,05). A área superficial aparente dos vilos e altura de vilos, nas aves que receberam Ava Cid P durante todas as fases experimentais, foi superior à das aves suplementadas somente na fase inicial. No íleo, a área superficial aparente dos vilos também foi superior nas aves suplementadas aos 9 d. Além disso, a expressão do gene para mucina 2 (MUC2) e para o fator de necrose tumoral (TNF-α) diminuiu nas aves recebendo Ava Cid P aos 21 d (P < 0,05), mas não foram observadas diferenças estatísticas para interleucina-1 beta e interleucina-10. Os resultados sugerem que Ava Cid P pode alterar a expressão de mRNA de algumas citocinas e MUC2 e a morfometria intestinal de frangos de corte, aumentando a superfície aparente e a altura dos vilos, o que demonstra a potencialidade do produto como alternativa aos antibióticos promotores de crescimento. / The limitations of the antibiotic growth promoter’s (AGP) usage have been increasing the search for new products to improve poultry performance, gut healthy and immune response. This experiment was conducted to compare the effect and dose response of Ava Cid P (consisted of a humic substance, coated sodium butyrate 30% and a small acidifier portion) diet supplementation on performance, immune response and gut health of broilers. Five dietary regimens were used: 1) birds didn’t receive Ava Cid P in any phase (Control), 2) birds received 0.91 kg/t of Ava Cid P from 1 to 21 d (AVA1-21), 3) 0.91 kg/t of Ava Cid P from 1 to 21 d and 0.45 kg/t from 22 to 35 d (AVA1-35), 4) 0.91 kg/t of Ava Cid P from 1 to 21 d and 0.45 kg/t from 22 to 42 d (AVA1-42), 5) 0.91 kg/t of Ava Cid P from 1 to 21 d, 0.45 kg/t from 22 to 35 d and 0.23 kg/t from 36 to 49 d (AVA1-49). They were applied in a completely randomized design, involving a 2 × 5 factorial arrangement with 2 sex and 5 levels of inclusion, and 7 replications with 15 birds each. The supplementation with Ava Cid P showed no influence on males and females growth performance and goblet cell density (P > 0.05). However, it modified the gut morphometry, increasing jejunum villi height at 9 and 35 days (P < 0.05). The apparent villus surface area and villi height on birds fed with Ava Cid P during all phases also increased in relation to those who received only in the early phase. The expression of mucin 2 (MUC2) and tumor necrosis factor-alpha (TNF-α) decreased on birds that received Ava Cid P at 21 days (P < 0.05), but no differences were seen for interleukin-1beta (IL-1β) and interleukin-10 (IL-10). The results suggest that Ava Cid P can alter the mRNA expression of some inter-leukins, MUC2 and intestinal morphometry in broilers, increasing apparent villus surface area and villi height, which demonstrates the product potential as an alternative growth promoter.

Submitted by Cássia Santos (cassia.bcufg@gmail.com) on 2016-10-05T10:29:36Z No. of bitstreams: 2 Dissertação - Lucas Morais Lôbo - 2015.pdf: 1058045 bytes, checksum: 36335f32e71fcf45a95a64517ccd5f37 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2016-10-05T10:59:13Z (GMT) No. of bitstreams: 2 Dissertação - Lucas Morais Lôbo - 2015.pdf: 1058045 bytes, checksum: 36335f32e71fcf45a95a64517ccd5f37 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2016-10-05T10:59:13Z (GMT). No. of bitstreams: 2 Dissertação - Lucas Morais Lôbo - 2015.pdf: 1058045 bytes, checksum: 36335f32e71fcf45a95a64517ccd5f37 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2015-03-31 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Processes of phosphorus adsorption in soil diminish the availability of this nutrient to plants. Humic and fulvic acids present in humic substances (SH) can block the phosphorus adsorption sites in the soil. Thus, this study aimed to verify the effect of adding doses of a SH, availability of P in two types of soils with different adsorption capacities. The treatments consist of four levels of SH (0, 100, 200 and 400 kg.ha-1), two phosphorus sources (Triple superphosphate – SFT and Natural Reactive phosphate – FNR), and three assessment time (7, 14 and 28 days) in two soil types (Red Latosol – LV and Quartzipsamment – NQ). The application of SH altered the availability of P in different soils. Statistical analysis of the data showed a significant difference (P<0,05) for all factors. In LV the P availability increased for both sources, with increasing SH dose up to 14 days. At 28 days the P-available decreases, with no significant difference between doses, but remains superior to treatment without addition of SH. In the NQ the P-available decreases from the addition of the doses of 200 and 400 kg ha-1 of SH up to 14 days of incubation. After 28 days with the degradation of SH values of P-available for these doses begin to increase. These results indicate that the use of SH is effective in increasing the availability of phosphorus in different soils. / Os processos de adsorção de fósforo (P) no solo diminuem a disponibilidade deste nutriente para as plantas. Os ácidos húmicos e fúlvicos presentes nas substâncias húmicas (SH) podem bloquear os sítios de adsorção de fósforo no solo. Desta forma, este estudo teve como objetivo verificar o efeito da adição de doses de SH, na disponibilidade de P em dois tipos de solos com diferentes capacidades de adsorção. Os tratamentos são constituídos de quatro doses de SH (0, 100, 200 e 400 kg ha-1), duas fontes de fósforo (Superfosfato triplo – SFT e Fosfato Natural Reativo – FNR), e três épocas de avaliações (7, 14 e 28 dias), em dois tipos de solos (Latossolo Vermelho – LV e Neossolo Quartzarênico – NQ). A aplicação de SH alterou a disponibilidade de P nos diferentes solos. A análise estatística dos dados mostrou que houve diferença significativa (P<0,05) para todos os fatores. No LV a disponibilidade de P aumentou, para ambas as fontes, com o aumento da dose de SH até aos 14 dias. Aos 28 dias o P-disponível diminui, não havendo diferença significativa entre as doses, porém permanece superior ao tratamento sem adição de SH. No NQ o P-disponível diminui a partir da adição das doses de 200 e 400 kg ha-1 de SH até aos 14 dias de incubação. Aos 28 dias com a degradação da SH os valores de P-disponível para estas doses começam a aumentar. Estes resultados indicam que a utilização de SH é eficiente no aumento da disponibilidade de P em diferentes solos.

This diploma thesis is focused on changes of stability in organic matter by extraction in different agents. Two soils of a different type and isolated humic acids were used for stability determination. Extraction agents were selected usually used for soil metal extraction, and a changes in the structure of the organic matter was observed. Samples were characterized using FTIR analysis and elemental analysis, the extracts were measured by UV-VIS spectroscopy, absorption ratios E2/E3, E4/E6 were discovered, dynamic light scattering were determined for particle size distributions. Next part of the thesis was the assessment of the change of thermal stability using thermogravimetric analysis and differential scanning calorimetry, degradation temperatures of the extracted samples were discovered and compared with the original samples.

This diploma thesis deals with humic acid gels and their ability to bind metallic ions on their surface. In the thesis, there was studied the adsorption of copper ions on the provided gels. The gels were prepared by dissolving the humic acid in sodium hydroxide or sodium tripolyphosphate and then precipitated with hydrochloric acid or metal chlorides. Adsorption was studied at different concentrations of the copper (II) chloride and measured on UV-VIS spectrophotometer. It was proved from measuring that gels made from sodium tripolyphosphate are adsorbing less copper ions than the ones prepared by sodium hydroxide. Also, the copper ions are bound with smaller force on gels prepared with polyphosphate. Gels precipitated with magnesium chloride adsorb much more than gels precipitated with acid, thus in the case of gels sequestered metal ions extracted higher.

The interaction behavior of humic acids with uranium(VI) and the influence of humic substances on the migration behavior of uranium was investigated. A main focus of this work was the synthesis of four different humic acid model substances and their characterization and comparison to the natural humic acid from Aldrich. A radiometric method for the determination of humic acid functional groups was applied in addition to conventional methods for the determination of the functionality of humic acids. The humic acid model substances show functional and structural properties comparable to natural humic acids. Modified humic acids with blocked phenolic OH were synthesized to determine the influence of phenolic OH groups on the complexation behavior of humic acids. A synthesis method for 14C-labeled humic acids with high specific activity was developed. The complexation behavior of synthetic and natural humic acids with uranium(VI) was investigated by X-ray absorption spectroscopy, laser-induced fluorescence spectroscopy and FTIR spectroscopy. The synthetic model substances show an interaction behavior with uranium(VI) that is comparable to natural humic acids. This points to the fact that the synthetic humic acids simulate the functionality of their natural analogues very well. For the first time the influence of phenolic OH groups on the complexation behavior of humic acids was investigated by applying a modified humic acid with blocked phenolic OH groups. The formation of a uranyl hydroxy humate complex was identified by laserspectroscopic investigations of the complexation of Aldrich humic acid with uranium(VI)at pH 7. The migration behavior of uranium in a sandy aquifer system rich in humic substances was investigated in column experiments. A part of uranium migrates non-retarded through the sediment, bound to humic colloids. The uranium migration behavior is strongly influenced by the kinetically controlled interaction processes of uranium with the humic colloids. The influence of humic acids on the sorption of uranium(VI) onto phyllite was investigated in batch experiments using two different humic acids. The uranium(VI) sorption onto the rock phyllite is influenced by the pH-dependent sorption behavior of the humic acids.

Das Verfahren zur Bestimmung von Koc-Werten nach OECD Richtlinie 121 ist zur Abschätzung der Sorptionskoeffizienten einzelner Stoffklassen gut geeignet. Die komplexen Wechselwirkungen eines Stoffes mit einer Matrix bei dem Sorptionsprozess konnten durch die Erweiterung des Kalibrierdatensatzes und den zusätzlichen stationären Phasen besser dargestellt werden. Die empirische Annahme der Kapazitätsfaktorensumme aus Cyano-Phase, Diol-Phase und Amino-Phase berücksichtigt die Wechselwirkungen von polaren Stoffen mit polaren Phasen und kann zur Bestimmung des Sorptionskoeffizienten weiterer Stoffklassen (z.B.: Amine, Alkohole) unter OECD-Bedingungen angewendet werden. Der Vorteil dieser Bestimmungsmethode ist, dass der Sorptionskoeffizient Koc unter umweltrelevanten Versuchsbedingungen ermittelt wurde und weitere Parameter wie zum Beispiel die pH-Wert-Abhängigkeit untersucht werden können. Auch eine hohe Reproduzierbarkeit des Verfahrens ist gewährleistet, da die verschiedenen HPLC-Säulen kommerziell erhältlich sind. Ein großer Nachteil der Bestimmungsmethode ist die einfache Struktur der Sorbensmatrizes, welche die Komplexität der Umwelt- bzw. Bodenmatrix nur bedingt wiedergeben können. Weiterhin ist die Bestimmung des Sorptionskoeffizienten mittels der drei unterschiedlichen HPLC-Säulen zeitaufwendiger als Sorptionsversuche mit einem Sorbensmaterial. Aus diesem Grund wurde in weiteren Sorptionsversuchen ein Sorbens gesucht, welches die natürlichen Sorptionsprozesse besser abbildet. Für das Beurteilen des Sorptionsverhaltens von organischen Verbindungen an natürlichen Sorbentien wurden in Batchversuchen die Sorptionskoeffizienten bestimmt. Mit dem Festlegen der Sorptionsparameter (z.B.: Sorptionskinetik, Sorbensmenge, Extraktionszeit) liegt ein valides Verfahren zur Aufnahme von Sorptionsisothermen vor. Von den verschiedenen Sorptionsmatrizes bilden die Huminsäuren den Sorptionsprozess von organischen Stoffen an natürlichen Böden am besten ab. Die Aldrich-Huminsäure wurde als Sorbens für die Durchführung von Säulenversuchen ausgewählt, da für diese Sorptionsmatrix die Sorptionskoeffizienten mit Literaturdaten am besten übereinstimmen. Für die Anwendung eines weiteren Analysenverfahrens wurde die Säulenmethode mit einer immobilisierten Aldrich-Huminsäure-Silikagel-HPLC-Säule durchgeführt. Die Aldrich-Huminsäure-immobilisierte-stationäre-Phase wurde durch eine mehrstufige organische Synthese unter inerten Bedingungen hergestellt. Zur Verifizierung der eingesetzten Huminsäure-Säule wurden die Stabilität der Matrix mit der theoretischen Bodenzahl N, des Säulendrucks und der Kapazitätsfaktor eines Kontrollstoffes erfolgreich überprüft. Die Porösität der Säulenmatrix, der organische Anteil des Sorbens und die Leitfähigkeit der mobilen Phase wurden als weitere Versuchsparameter überprüft, und es wurde darauf geachtet, dass umweltrelevante Bedingungen bei den Sorptionsversuchen vorliegen. Das HPLC-Verfahren wurde durch die hohe Übereinstimmung zwischen experimentellen Koc-Werten der Aldrich-Huminsäure und den Koc-Literaturwerten aus Batchversuchen mit Böden für neutrale organische Stoffe verifiziert. Auch beim Vergleich der Sorptionsergebnisse von verschiedenen Huminstoff-Matrizes besitzt die Aldrich-Huminsäure die Koc-Werte mit der größten Übereinstimmung mit Literaturdaten. Zur Beurteilung des Sorptionsverhaltens eines Stoffes in der Umwelt wurde die Einteilung von Höltig erweitert. Zum Treffen einer Aussage über das Sorptionsverhaltens eines Stoffes wurde neben dem log Kow auch der log Koc verwendet und für ionische Stoffe in Sorptionsklassen eingeteilt. Für 30 umweltrelevante und toxische Stoffe ohne Sorptionskoeffizient wurde ein Koc-Wert ermittelt und das Sorptionsverhalten nach dem erweiterten Hölting-Modell abgeschätzt. Dabei zeigten 2,6-Di-t-butyl-p-benzochinon, Epoxiconazol und Chalconepoxid nach dem Modell ein relevantes Sorptionsverhalten (log Koc= 2,39 bis 3,18). Für einen Koc-Datensatz von 85 Stoffen wurde mit dem Aldrich-Huminsäure-Säulenverfahrens ein Abraham-Modell aufgestellt. Das Modell liefert die signifikanten Phasenparameter e, s, b, v und und hohe Regressionskoeffizienten (r2=0,91, q2cv= 0,89). Demnach ist das aufgestellte Abraham-Modell für 16 Stoffklassen sehr gut geeignet, die Sorptionskoeffizienten vorherzusagen. Auch der Vergleich mit dem Abraham-Modell von Nyguyen (2005) zeigt, dass die Aldrich-Huminsäure die Sorptionseigenschaften von Böden sehr gut abbilden kann. Für eine Vielzahl an Stoffen lagen keine Literaturwerte vor, so dass mit Hilfe der HPLC-Säulenmethode zeitnah weitere Stoffklassen in das Abraham-Modell implementiert werden können. Für 40 organische Basen mit einem pKs-Bereich von 0,50 bis 10,69 und einem logKow- Bereich von -0,02 bis 5,51 wurde der Sorptionskoeffizient bei 3 pH-Werten ermittelt. Für 9 organische Basen, welche im untersuchten pH-Wertbereich ausschließlich neutral vorliegen, wurde kein signifikanter Einfluss des pH-Werts auf den Sorptionskoeffizienten ermittelt. Für kationisch vorliegende organische Basen wurde mit steigendem pH-Wert ein zunehmender Sorptionskoeffizient bestimmt. Eine Erhöhung des Sorptionskoeffizienten bei pH 5 und pH 7 beruht auf zusätzlichen ionischen Molekül-Matrix-Wechselwirkungen zwischen organischen Basen und Sorbens. Auch für die organischen Basen, welche im pH-Bereich von 3 bis 7 mit beiden Spezies vorliegen, konnte bei dem pH-Wert 5 oder pH-Wert 7 die größten Sorptionskoeffizienten ermittelt werden. Die starke Zunahme der Sorptionskoeffizienten kann neben hydrophoben Wechselwirkungen auf dem Maximum an ionischen Bindungen bei pH 5 oder pH 7 zwischen der kationischen Spezies der Base und den anionischen Carboxyl-Gruppen der Aldrich-Huminsäure basieren. Für 16 organische Basen, welche im pH-Wertbereich bei pH 7 neutral und bei pH 3 ionisch vorliegen, wurde ein linearer Zusammenhang zwischen log Koc.n und log Koc.ion aufgestellt. Für die Annahme, das für einen Stoff der Sorptionskoeffizient einer Spezies ermittelt wurde, gilt die Näherung dass mindestens 90 Prozent der Spezies vorliegen müssen. Das Modell zur Berechnung des pH-abhängigen Sorptionskoeffizienten beruht auf 55 log Koc(pH)-Werten von organischen Basen. Für die Anwendung des Modells muss eine organische Base im untersuchten pH-Wertbereich als neutrale Spezies vorliegen. Bei einem Vergleich der experimentellen Sorptionskoeffizienten mit den berechneten Werten von Franco stellte sich heraus, dass das Literaturmodell zur Vorhersage des Koc(pH) nur bedingt geeignet ist. In zukünftigen Arbeiten kann das erstellte Abraham-Modell für eine noch bessere praxisbezogene Anwendung auf weitere umweltrelevante Stoffklassen erweitert werden. Zur Erstellung eines Gesamtmodells für ionisch und neutral vorliegende organische Basen müssen pH-abhängige Sorptionskoeffizienten weiterer Basen ermittelt werden.

The growing development of nanotechnology has resulted in an increased use of nanoparticles (NPs) in various applications ranging from medicine, military, to daily consumer products. There is a concern that NPs can be dispersed into the environment in various ways, for example to air and water during manufacture, use, incineration or recycling of products and thus pose a risk to health and the environment. Risk assessments of NPs are hence necessary. One property of NPs, which may make them very useful and at the same time potentially harmful, is their small size (in nanometer range) and hence high surface area per NP mass.This study forms part of the National Mistra Environmental Nanosafety Research Program. The program provides an interdisciplinary platform for researchers from e.g. nanoscience, medicine, chemistry, material science, life cycle analysis, and social science. Specific aspects of this program involve characterization of NPs in different environmental settings, toxicity studies of aquatic organisms, integrated risk assessment of NPs, and societal dimensions of nanosafety. The contribution of this thesis within the program includes studies of stability and mobility of metal NPs and their extent of transformation/dissolution upon environmental interaction. Environmental risk assessments of NPs require a detailed understanding of how they change in terms of physical and chemical properties (charge, size, and surface oxide composition), important aspects for their stability, mobility, and reactivity in the environment. Generated data is highly relevant for the other activities of the Mistra Environmental Nanosafety program, e.g. to gain an improved understanding and design of particle dispersions and ecotoxicity studies, as any environmental interaction will result in the transformation/dissolution of the NPs and change the surface chemistry (e.g. adsorption of natural organic matter, changes in surface oxide properties), aspects that largely influence their speciation and potential toxicity.Common sonication protocols exist to prepare particle dispersions for different in vitro studies. The influence of key parameters stipulated by these protocols on the particle size, transformation/dissolution, and extent of sedimentation was investigated for bare metal NPs. Improved knowledge on these aspects is crucial for design and interpretation of results of NP-related investigations. Reactive metal NPs such as Cu and Mn NPs started to dissolve and release metals already during the probe sonication step of the stock solution, and that the presence of bovine serum albumin (often added as a stabilizing agent) enhanced this process. Even though prolonged sonication time i.e. increased delivered acoustic energy, reduced the size of formed agglomerates, sedimentation was still significant. As a consequence, administered doses from pipetted stock solutions were significantly lower (30-70%) than the nominal doses. The main reason behind the significant extent of agglomeration, with concomitant sedimentation, is related to the strong van der Waals forces prevailing between metal NPs. It is hence essential to determine the administrated dose of metallic NPs in e. g. nanotoxicological testing.Interactions between metallic NPs and natural organic matter (NOM) were studied in terms of stability, mobility and metal dissolution in order to mimic a potential exposure scenario. NOM was represented by humic acid (HA), a main component of organic matter in the environment, and by dihydroxybenzoic acid (DHBA), a small degradation product of NOM. Sedimentation of the Cu, and the Al NPs were slower in the presence of NOM in freshwater compared with freshwater only, whereas the effect of NOM was small for the Mn NPs. Stabilization was related to surface adsorption of NOM, which increased the steric repulsion between the particles, and in the case of HA also increased the magnitude of the zeta potential (resulting in increased electrostatic repulsion). Slight initial increase in particle stability wasobserved in freshwater containing DHBA, but after 24 h, sedimentation of the NPs was comparable to the conditions in freshwater only. The presence of HA (at a concentration of 20 mg/L) was found to stabilize the NPs in freshwater for more than 24 h. However, both the lower and higher HA concentration (2 and 40 mg/L) resulted in agglomeration of the Cu and Al NPs already within a few hours. Mn NPs were more stable in terms of sedimentation in freshwater at all three humic acid concentrations. This concludes that the concentration and type of NOM largely influence the stability of the studied metal NPs in solution. In contrast, SiO2 NPs were not influenced by the presence of NOM in terms of stability, most probably predominantly related to smaller attractive van der Waals forces and larger electrostatic repulsion (due to higher surface charge) compared with the metal NPs.Metal release from the Cu and Al NPs was enhanced in the presence of NOM, whereas no significant influence was observed for the Mn NPs. All metal NPs were dissolved relatively fast; 10% or more of the particle mass was dissolved within 24 h. Speciation predictions revealed rapid complexation between released Cu and Al in solution and NOM, reducing the bioavailability, whereas less complexation was evident for released Mn (as ions). In all, rapid agglomeration and sedimentation imply that any risks associated with the environmental dispersion of these metal NPs will be limited to the vicinity of their source. Mn NPs, having lower sedimentation rates than the Cu and Al NPs, and lack of solution complexation of released ions will likely have a relatively higher probability to be mobile and transported to other aquatic settings.

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