The crisis of freshwater has been a big concern worldwide. Water contamination that occurs through the discharge of toxic pollutants from different natural and anthropogenic sources have worsened the situation. Adsorption has emerged as a simple and economical water treatment procedure although the challenge is to find the right adsorbent that can efficiently remove the target contaminant followed by their easy recovery from the reaction vessel. In this dissertation, I have focused on the synthesis, characterizations and applications of environmentally compatible and magnetic humic acid coated magnetite nanoparticles (HA-MNP) as a potential adsorbent for water purification. Phosphate is an essential nutrient for many plants and organisms in the environment. However, it can also cause water pollution when present in excess amounts. The adsorption experiments showed that the laboratory synthesized nanoparticles (HA-MNP) can remove more than 90% of phosphate from water mainly through the mechanism of chemisorption. The overall removal process is spontaneous, endothermic and favorable. Water contamination by arsenic is considered one of the biggest natural disasters in human history. In the study, HA-MNP has been applied for the successful trapping and separation of two highly toxic inorganic As species, As(III) and As(V) from water. The removal of As(V) was faster than As(III) for the same initial arsenic concentration and HA-MNP loading. The binding of As species is mainly attributed to three different phases, rapid surface association, intraparticle diffusion and equilibrium adsorption. Selenium is a micronutrient for humans that can be toxic at modest concentrations. The remediation of toxic selenium species, Se(IV) and Se(VI) by using HA-MNP has been found effective under a variety of environmental conditions except at highly alkaline pH and the presence of sulfate and phosphate in aqueous solution. Selenite or Se(IV) forms strong inner sphere complexes while Se(VI) forms relatively weaker outer sphere complexes with the adsorbent sites. The oxidation and adsorption of As(III) is explored by using the photocatalytic and adsorptive behavior of HA-MNP. The higher removal efficiency is attained through the reactive oxygen species mediated photo-conversion As(III) to As(V). Combination of oxygen and 350 nm light provides the best results.

Humic substances are macromolecules that naturally occur in all environments in which vegetation matter are present. In general, humic acid is part of humic substances which form the major fraction of the dissolved organic matters in surface water and represents 90% of dissolved organic carbon. Humic acid plays a fundamental role in many ecosystems since it interacts with toxic metal ions present in the system, resulting in a decrease in the bio-availability of such ions. Moreover, the availability of humic acid in water can react with other chemical compounds, such as chlorine to form trihalomethanes (including chloroform) and causes an increasing risk of cancer and may be linked to heart, lung, kidney, liver, and central nervous system damage. Therefore, humic acid removal in water treatment processes is very important in order to achieve the drinking water standards. Heavy metals are significant contaminants in aqueous system. All heavy metals can produce toxicity when ingested in sufficient quantities, but there are several important ones such as lead, mercury, copper, cadmium, arsenic, nickel and silver. These heavy metals are so pervasive and produce toxicity at low concentrations. Moreover, they may build up in biological systems and become a significant health hazard. / Adsorption is approved as an effective and simple method for water and wastewater treatment process. Many adsorbents then are developed for use in adsorption process such as montmorillonite, peat, activated carbon, etc. In this research, humic acid and heavy metals were mainly selected for adsorption study. In the sorption experiment, several adsorbents such as synthesised zeolite (SZ), natural zeolite (NZ), powdered activated carbon (PAC) and fly ash (FA), were selected to examine the application of HA and heavy metals both in individual and simultaneous adsorption, The characteristics and interactions of the adsorbents with HA and heavy metals were systematically studied by batch laboratory experiments. In the beginning, the adsorption of HA onto SZ, NZ, PAC and FA was investigated and their adsorption capacity was compared. The equilibrium adsorption of HA on SZ, NZ, PAC and FA was found to be 84.1, 67.8, 81.2 and 34.1 mg/g, respectively, at 30 oC and pH 5.0. Dynamic adsorption data show that these adsorbents could reach their adsorption equilibrium after 50 hours. From pH analysis, HA adsorption is favoured at low pH and an increase in pH will lead to the reduction of HA adsorption. SZ and NZ adsorption capacity were affected by the changing of solution temperature; however, in PAC and FA sorption study, there was no significant effect observed. Two heavy metal ions (Cu, Pb) removal by the adsorbents was then conducted. The results showed that the equilibrium sorption capacity of Cu and Pb ions on SZ, NZ, PAC and FA were 43.5, 24.2, 19.7, 28.6 and 190.7, 129.0, 76.8 mg/g, respectively at 30 oC and a pH value of 5. The appropriate pH for Cu and Pb removal was found to be 5 and 6. In most dynamic cases, these adsorbents needed at least 50 hours to reach the adsorption equilibrium. Only adsorption on FA required more than 150 hours to reach the equilibrium. / In simultaneous adsorption experiments, the influences of HA and heavy metal concentration (in the range of 10 to 50 mg/L for HA and 10 to 30 mg/l for heavy metals) on the HA-heavy metal complexation were investigated. The results demonstrated that increasing HA concentration mostly affected Cu adsorbed on SZ, FA and PAC and Pb adsorbed on SZ, NZ and PAC. For HA adsorption, the adsorption rate decreased rapidly with increased initial metal ion concentration. Moreover, the adsorption of heavy metals increased with increased heavy metals concentration in the presence of HA. In the presence of heavy metal ions, the order of HA adsorption followed PAC > FA > SZ > NZ. According to the results, the individual and simultaneous adsorption of HA and heavy metals on each adsorbent achieved a different trend. It mainly depended on the adsorption property of both adsorbates (HA and heavy metals) and adsorbents (SZ, NZ, PAC and FA) and also the operation factors such as pH, concentration, temperature and operation time. Even though this experiment could not obtain high adsorption performance, especially in coadsorption, as compared with other adsorbents, the adsorbents in this study represented a higher adsorption capacity and provide the potential for further development.

Abstract not available

The storage of nuclear waste in deep geological formations is discussed worldwide as the main strategy for nuclear waste management. To ensure the confinement of the nuclear waste, a multiple barrier system which consists of engineered, geo-engineered, and geological barriers will be applied. Thereby, in Germany the definition of the isolating rock zone represents an important safety function indicator. Clay rock is internationally investigated as potential host rock for a repository and represents a part of the geological barrier. In the present work, the natural clay rock Opalinus Clay from the Mont Terri rock laboratory, Switzerland, was studied. In Germany, the direct disposal of the spent nuclear fuel without the reprocessing of the spent fuel is preferred. In case of water ingress, radionuclides can be released from the nuclear waste repository into its surroundings, namely the host rock of the repository. Humic acids, ubiquitous in nature, can be found associated with the inorganic components in natural clay rock (1.5×10–3 wt.% in Opalinus Clay). They can be released under certain conditions. Due to their variety of functional groups, humic acids are very strong complexing agents for metal ions. They have inherent redox abilities and a colloidal conformation in solution. Because of these characteristics, humic acids can affect the mobility of metal ions such as actinides. Furthermore, in the near-field of a repository elevated temperatures have to be considered due to the heat production resulting from the radioactive decay of the various radionuclides in the nuclear waste. This work focuses on the interaction of uranium, as main component of spent nuclear fuel, with Opalinus Clay and studies the influence of humic acid and elevated temperature on this interaction. For investigation of the retention behavior of the clay and the mobility of U(VI) in the system, batch sorption and diffusion experiments were performed. To clarify which U(VI) and humic acid species were present under the applied conditions, aqueous speciation modeling was used. Additionally, the U(VI) speciation in solution and on the clay surface was investigated by spectroscopic methods. Prior to the investigation of the ternary system U(VI) / humic acid / clay, the applied batches of Opalinus Clay were characterized (e.g., specific surface area, carbon content, cation exchange capacity, elemental composition, particle size distribution). Leaching studies with Opalinus Clay in synthetic Opalinus Clay pore water (pH 7.6, It = 0.34 mol/L) and in NaClO4 (pH 3 – 10, I = 0.1 mol/L) were performed to identify the competing ions and their concentrations in the background electrolytes. These data were used to calculate the U(VI) and humic acid speciation in solution. Calcium and carbonate ions are present under pore water conditions as well as in 0.1 mol/L NaClO4 from pH 7 to 8.5, due to dissolution of calcite (mineral fraction in Opalinus Clay). Thus, the U(VI) speciation is dominated by the aquatic Ca2UO2(CO3)3 complex. In the case of pore water, Ca2UO2(CO3)3(aq) is also the dominant U(VI) species in the presence of humic acid, which was corroborated by time-resolved laser-induced fluorescence spectroscopic measurements. A significantly changed speciation was found in 0.1 mol/L NaClO4 in the presence of humic acid. At pH > 7, the negatively charged UO2(CO3)2HA(II)4– complex determines the U(VI) speciation, thus repressing the Ca2UO2(CO3)3(aq) complex. In addition, the speciation of humic acid is influenced from ions leached out from Opalinus Clay. The CaHA(II) complex is the dominating humic acid species in solution. Batch sorption experiments in 0.1 mol/L NaClO4 showed that Opalinus Clay has the strongest retardation effect on U(VI) in the pH range from pH 4.5 to 7. However, under environmentally relevant conditions (pH > 7), the sorption of U(VI) onto Opalinus Clay is very weak. Under pore water conditions, a distribution coefficient (Kd) of 0.0222 ± 0.0004 m3/kg was determined, which was shown to be independent of solid-to-liquid ratios ≥ 60 g/L. In addition, in pore water, the U(VI) sorption onto Opalinus Clay is not influenced by humic acid, which is supported by the speciation results. Extended X ray absorption fine-structure investigations confirmed this batch sorption result. The U(VI) diffusion experiments performed in pore water at 25 °C with Opalinus Clay bore core samples confirmed the Kd value obtained by batch sorption experiments. In the diffusion experiments at 60 °C, a change in the U(VI) speciation occurred. Beside Ca2UO2(CO3)3(aq), a colloidal U(VI) species was formed. Almost equivalent apparent diffusion coefficient (Da) values were determined for the diffusion of the aqueous U(VI) species at 25 and 60 °C through Opalinus Clay. Thus, based on the investigations in the present study the breakthrough of U(VI) through Opalinus Clay is expected to be independent of the temperature and should occur nearly at the same time. Modeling calculations showed that it would take about 10 years until a detectable amount of 233U(VI) (1×10–9 mol/L) migrates through an 11 mm thick Opalinus Clay sample. Two distinct humic acid size fractions – a large- and a small-sized colloid fraction – diffused through the Opalinus Clay samples. Within three months, the high molecular size humic acid colloids migrated only about 500 µm into the clay, whereas the low molecular size fraction diffused through the entire Opalinus Clay samples and were consequently detected in the receiving reservoirs. These findings demonstrate a filtration effect of the compacted clay. The diffusion experiments revealed that the effect of humic acid on U(VI) diffusion is negligible and, under the studied conditions, independent of temperature. The obtained results contribute to data bases used for modeling of interaction and migration processes in uranium / clay rock systems. Thus, the collected sorption and diffusion data are not only relevant for safety assessment of nuclear waste repositories but also for any clay-containing system present in the environment, where the geochemical interaction with uranium contaminated water plays a role. Concerning the suitability of Opalinus Clay as host rock for a nuclear waste repository, it can be concluded, that Opalinus Clay has a relatively high retardation potential for U(VI). In case of water ingress U(VI) as part of the nuclear waste is released into the clay formation. Under near-neutral pH conditions, it will be complexed by calcium and carbonate ions leached out from Opalinus Clay, whereby Ca2UO2(CO3)3(aq) is formed. This complex is only weakly retarded by sorption onto the clay, which can contribute to an enhanced mobility of U(VI) in the host rock. However, the U(VI) migration through the clay rock is governed by molecular diffusion. This decelerates the migration of Ca2UO2(CO3)3(aq) through Opalinus Clay and thus it represents the decisive retardation process in the investigated system. Additionally, under environmentally relevant conditions, humic acid has no significant influence on U(VI) / Opalinus Clay interaction even at an elevated temperature of 60 °C. This was shown by speciation, sorption, as well as diffusion experiments. / Eine weltweit diskutierte Strategie zum Umgang mit radioaktiven Abfällen ist deren Endlagerung in tiefen geologischen Formationen. Zur Abschirmung der Umwelt vor den schädlichen Einflüssen des radioaktiven Abfalls soll ein Multibarrierensystem bestehend aus technischen, geotechnischen und geologischen Barrieren im Endlager dienen. Dabei ist in Deutschland die Definition des einschlusswirksamen Gebirgsbereichs ein wichtiger sicherheitstechnischer Indikator. Tongestein wird als potentielles Endlagerwirtsgestein und Teil der geologischen Barriere international erforscht. In der vorliegenden Arbeit wurde das natürliche Tongestein Opalinuston aus dem Mont Terri Felslabor, Schweiz, untersucht. In Deutschland wird die direkte Endlagerung des abgebrannten Kernbrennstoffes ohne Wiederaufarbeitung des Brennstoffs favorisiert. Bei Wassereinbruch können Radionuklide aus dem Abfall in die Umgebung des Endlagers freigesetzt werden, d. h. sie können in Kontakt mit dem Wirtsgestein kommen. Ubiquitär in der Natur vorkommende Huminsäuren können mit den anorganischen Komponenten des natürlichen Tongesteins vergesellschaftet sein (1.5×10–3 Gew.-% in Opalinuston). Unter bestimmten Bedingungen können die Huminsäuren freigesetzt werden. Ihre Struktur enthält eine Vielzahl von funktionellen Gruppen, was sie zu starken Komplexbildnern für Metallionen macht. Sie besitzen Redoxeigenschaften und bilden in Lösung eine kolloidale Konformation aus. Aufgrund dieser Charakteristika können sie die Mobilität von Metallionen wie den Actinoiden beeinflussen. Weiterhin sind im Nahfeld eines Endlagers erhöhte Temperaturen zu erwarten, welche aus der Wärmefreisetzung beim radioaktiven Zerfall der verschiedenen Radionuklide im radioaktiven Abfall resultieren. Die vorliegende Studie konzentriert sich auf die Untersuchung der Wechselwirkung von Uran, als Hauptkomponente des endgelagerten abgebrannten Kernbrennstoffs, mit Opalinuston und untersucht dabei den Einfluss von Huminsäure und erhöhter Temperatur. Um das Rückhaltevermögen des Tongesteins gegenüber U(VI) und die U(VI)-Mobilität im System zu ermitteln, wurden Sorptions- und Diffusionsversuche durchgeführt. Zur Klärung, welche U(VI)- und Huminsäurespezies unter den untersuchten Bedingungen vorliegen, wurde die aquatische Speziation berechnet. Zusätzlich wurde die U(VI)-Speziation in Lösung und an der Tonoberfläche mit spektroskopischen Methoden untersucht. Vor der Untersuchung des ternären Systems U(VI) / Huminsäure / Ton wurden die eingesetzten Opalinuston-Chargen charakterisiert (z. B. spezifische Oberfläche, Kohlenstoffgehalt, Kationenaustauschkapazität, elementare Zusammensetzung, Partikelgrößenverteilung). Anschließend wurden Auslaugungsversuche mit Opalinuston in synthetischem Opalinustonporenwasser (pH 7.6, It = 0.34 mol/L) und in NaClO4 (pH 3 – 10, I = 0.1 mol/L) durchgeführt, um relevante Konkurrenzionen zu identifizieren und deren Konzentration in den Hintergrundelektrolyten zu bestimmen. Die erhaltenen Daten wurden zur Berechnung der U(VI)- und Huminsäurespeziation in Lösung verwendet. Unter Porenwasserbedingungen sowie in 0.1 mol/L NaClO4 von pH 7 bis 8.5 liegen, durch die Auflösung von Calcit (Mineralphase im Opalinuston), Calcium- und Carbonationen in Lösung vor. Dadurch wird die U(VI)-Speziation von dem aquatischen Ca2UO2(CO3)3-Komplex dominiert. Im Falle des Porenwassers ist Ca2UO2(CO3)3(aq) auch in Gegenwart von Huminsäure die dominierende U(VI)-Spezies. Dies wurde durch zeitaufgelöste laserinduzierte fluoreszenzspektroskopische Messungen nachgewiesen. Eine signifikante Änderung der U(VI)-Speziation tritt in 0.1 mol/L NaClO4 in Gegenwart von Huminsäure auf. Bei pH > 7 bestimmt der negativ geladene UO2(CO3)2HA(II)4–-Komplex die U(VI)-Speziation, wobei der Anteil von Ca2UO2(CO3)3(aq) zurückgedrängt wird. Auch die Huminsäurespeziation wird durch die vom Opalinuston ausgelaugten Ionen beeinflusst. So ist der CaHA(II)-Komplex die dominierende Huminsäurespezies in Lösung. Sorptionsversuche in 0.1 mol/L NaClO4 zeigten, dass Opalinuston gegenüber U(VI) den stärksten Retardationseffekt im pH-Bereich 4.5 bis 7 aufweist. Unter umweltrelevanten Bedingungen hingegen (pH > 7) ist die U(VI)-Sorption an Opalinuston sehr schwach. Unter Porenwasserbedingungen wurde ein Verteilungskoeffizient (Kd) von 0.0222 ± 0.0004 m3/kg ermittelt, der von Fest-Flüssig-Verhältnissen ≥ 60 g/L unabhängig ist. Außerdem wird die U(VI)-Sorption an Opalinuston in Porenwasser nicht von Huminsäure beeinflusst. Dies wird durch die Ergebnisse aus den Speziations-rechnungen unterstützt. Röntgenabsorptionsspektroskopische Untersuchungen bestätigten ebenfalls dieses Sorptionsergebnis. Die U(VI)-Diffusionsexperimente in Porenwasser bei 25 °C unter Verwendung von Opalinustonbohrkernstücken bestätigten den Kd-Wert der Sorptionsexperimente. In den Diffusionsexperimenten bei 60 °C trat eine Änderung in der U(VI)-Speziation auf. Neben Ca2UO2(CO3)3(aq) wurde eine kolloidale U(VI)-Spezies gebildet. Für die Diffusion der aquatischen U(VI)-Spezies durch Opalinuston bei 25 und 60 °C wurden annähernd gleiche scheinbare (apparente) Diffusionskoeffizienten (Da) bestimmt. Das bedeutet, der Durchbruch von U(VI) durch Opalinuston ist unabhängig von den hier untersuchten Temperaturen und wird deshalb etwa zum gleichen Zeitpunkt erwartet. Modellierungen zeigten, dass es etwa zehn Jahre dauern würde, bis eine detektierbare Menge an 233U(VI) (1×10–9 mol/L) durch ein 11 mm-dickes Opalinustonbohrkernstück migrieren würde. Zwei verschiedene Huminsäuregrößenfraktionen diffundierten durch die Opalinustonproben – eine große und eine kleine kolloidale Größenfraktion. Innerhalb von drei Monaten migrierten die hochmolekularen Huminsäurekolloide nur 500 µm in den Ton, während die niedermolekularen Huminsäurekolloide durch die gesamten Opalinustonproben diffundierten und dadurch im Auffangreservoir detektiert werden konnten. Diese Resultate demonstrieren den Filtrationseffekt des Tongesteins. Die Diffusionsversuche zeigten, dass der Einfluss von Huminsäure auf die U(VI)-Diffusion, unabhängig von der in dieser Arbeit verwendeten Temperatur, vernachlässigbar ist. Die erhaltenen Ergebnisse tragen zu Datenbanken bei, die für die Modellierung von Wechselwirkungs- und Migrationsprozessen in Uran / Tongestein-Systemen genutzt werden. Das bedeutet, die gesammelten Sorptions- und Diffusionsdaten sind nicht nur für den Langzeitsicherheitsnachweis eines Endlagers für radioaktive Abfälle von Relevanz, sondern auch für jedes tonhaltige System in der Umwelt, bei dem die geochemische Wechselwirkung mit urankontaminierten Wässern eine Rolle spielt. Bezüglich der Eignung von Opalinuston als Wirtsgestein für ein Endlager radioaktiver Abfälle lässt sich schlussfolgern, dass Opalinuston ein relativ hohes Retardationspotential bezüglich U(VI) aufweist. Wenn U(VI) als Bestandteil des radioaktiven Abfalls bei Wassereinbruch im Endlager in die Umgebung freigesetzt wird, wird es unter umweltrelevanten Bedingungen von Calcium- und Carbonationen, welche aus dem Opalinuston herausgelöst werden, komplexiert. Dabei bildet sich Ca2UO2(CO3)3(aq). Dieser Komplex wird nur schwach durch Sorption am Tongestein zurückgehalten, was zu einer erhöhten U(VI)-Mobilität im Wirtsgestein führen kann. Im untersuchten System wird die U(VI)-Migration durch das Tongestein jedoch durch molekulare Diffusion bestimmt. Sie verzögert die Migration von Ca2UO2(CO3)3(aq) durch Opalinuston und stellt somit den maßgeblichen Retardationsprozess im System dar. Huminsäure hat keinen signifikanten Einfluss auf die U(VI) / Opalinuston-Wechselwirkung, sogar bei einer erhöhten Temperatur von 60 °C. Dies wurde mittels Speziationsmodellierungen sowie durch Sorptions- und Diffusionsversuche gezeigt.

An investigation was conducted focusing on how NOM affects coagulation in a United States south eastern coastal surface water. Current water treatment practice at Savannah Water I and D was investigated to determine the efficacy of NOM removal using existing coagulation methods. A robust assessment of alum and ferric sulfate for use as coagulants in the removal of disinfection byproduct (DBP) precursor material was conducted using composite water created from sample sites within the SWID watershed. Both coagulants were optimized for the removal of NOM. Pragmatic methods of NOM size analysis and its reactivity with chlorine was investigated. UF membranes were used in conjunction with a permeation coefficient model (PCM) to determine an apparent molecular weight distribution of NOM present in the watershed. Individual size classes were assessed for their potential to form trihalomethanes (THMs) upon chlorination. Coagulation using alum and ferric sulfate was assessed to determine removal efficiency of individual NOM size classes under various coagulation scenarios. Finally, UV254 absorbance (UVA) was assessed to determine its potential use as an indicator of DOC concentration in raw and treated water at SWID. Additionally, an investigation into the relationship between specific UVA (SUVA) and THM formation potential (THM-FP) was conducted.

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.

F�r die Therapie und Prophylaxe von Fischkrankheiten stehen nur wenige geeignete und zugelassene Medikamente zur Verf�gung. Daher kommt der Suche nach wirksamen und f�r Tier, Verbraucher und Umwelt sicheren Alternativen in der Fischhaltung eine besondere Bedeutung zu. �ber positive Effekte beim oralen Einsatz von Huminstoffen an landwirtschaftlichen Nutztieren, Zootieren und Heimtieren liegen eine Vielzahl von Berichten vor. Deshalb sollten in der vorliegenden Studie Huminstoffe (HS) in der �u�erlichen Anwendung bei Zierfischen und in der oralen Verabreichung �ber das Futter bei Nutzfischen n�her untersucht werden. Dazu wurden zwei Versuche (B I: Dauer 4 Tage; B II: Dauer 12 Tage) an Goldfischen (Carassius auratus) unter teichwirtschaftlichen Bedingungen, zwei Aufzuchtversuche (F I: Kv bis K3, Dauer: 1.000 Tage: F II: K0 bis K1, Dauer: 150 Tage) an Karpfen (Cyprinus carpio) in der Teichwirtschaft und ein Aufzuchtversuch (F III: vorgestreckte Brut bis 30 g Lebendmasse, 166 Tage) an Regenbogenforellen (Oncorhynchus mykiss) unter Laborbedingungen durchgef�hrt. Als Versuchsparameter dienten Mortalit�t und Morbidit�t, Wachstum und Futteraufwand in den Aufzuchtversuchen, pathologisch anatomische (einschlie�lich histologischer Befunde in B I und F II), parasitologische, bakteriologische und virologische Kriterien. Die Wasserqualit�t wurde regelm��ig ermittelt. In den Versuchen B I und B II wurde eine 10%ige Na-Humat-L�sung (HS vom Typ WH 67 SNa der Fa. Pharmawerk Weinb�hla) dem H�lterungswasser so zugesetzt, dass eine Na-Humat-Konzentration von 10 mg L-1 entstand. Zweij�hrige, multifaktoriell erkrankte Goldfische (B I: N=2 x 322, B II: N=2 x 100) wurden dem Na-Humat-Bad t�glich f�r die Dauer einer Stunde (B I) bzw. von 1,5 bis 2 Stunden (B II) ausgesetzt. Die HS-Badehandlungen f�hrten in beiden Versuchen zu einer Senkung der Verluste (Mortalit�tsrate in B I: 0,6 versus 4,7 %, p<0,0005; B II: 8 versus 16 %, p<0,05). Bei Versuchsende war in den Versuchsgruppen (Na-Humat-Bad) der Gesundheitszustand, beurteilt nach �u�erlich sichtbaren Ver�nderungen an Haut, Flossen und Kiemen, deutlich verbessert (B I: p<1�10-16; B II: p<0,001). So waren (Signifikanzangaben nur f�r B II) vor allem H�morrhagien der Haut und der Flossen (p<0,05), Flossenrand- und Kiemennekrosen (p<0,05) sowie akute Kiemenentz�ndungen (p<0,02) verringert. Die Badebehandlungen bewirkten weiter eine geringere Auspr�gung integument�rer Mykosen der Haut, Flossen und Kiemen durch Pilze der Gattung Saprolegnia (p<0,05). Der Befall von Haut und Kiemen mit vorrangig protozo�ren Ektoparasiten konnte insgesamt ebenso vermindert werden (p<0,01) wie der Befall der Kiemen mit Ichthyophthirius sp. (p<0,05). Aus der beobachteten Milderung von Krankheitssymptomen umweltbedingter, bakterieller, ektoparasit�rer und mykotischer Genese nach Na-Humat-B�dern bei Goldfischen kann auf einen gewebeprotektiven, antiphlogistischen, antimykotischen und antiparasit�ren Effekt der Na-Humat-Behandlung geschlossen werden. In der Aufzucht von Karpfen (F I) und Regenbogenforellen (F III) wurden dem Futter 5 % Humocarb, formuliert� (HS vom Typ WH 67 A), im Karpfenversuch F II 5 % Cellu-Ligno-Karbon-Isolat (HS vom Typ WH 67 G, beide Produkte: Fa. Pharmawerk Weinb�hla) zugesetzt. In F I und F III wurde ein gleiches pelletiertes Alleinfutter f�r Forellen, in F II ein pelletiertes Alleinfutter f�r Karpfen eingesetzt. In Versuch F I (Besatzdichte der beiden Teiche (0,2 ha) jeweils 35.000 Kv ha-1) wiesen die Karpfen der Versuchs- gegen�ber der Kontrollgruppe h�here mittlere K�rpermassen auf. Der Unterschied zwischen den Gruppen bewegte sich mit einer Ausnahme (zu geringer Stichprobenumfang) zwischen p<0,05 (65 versus 45 g, 114. Tag) und p<0,0001 (1.146 versus 855 g, Versuchsende 1000. Tag). Der um die HS-Aufnahme bereinigte Futteraufwand des ersten Versuchsjahres war durch HS um 34 % verbessert. Die Futterquotienten in der zweiten und dritten Aufzuchtperiode waren durch die subjektive Futterzumessung (Nichtber�cksichtigung zwischenzeitlicher Verluste) verf�lscht. In Versuch F II (Besatzdichten der 2 x 3 Teiche (0,25 ha) 20.000, 30.000 bzw. 40.000 K0 ha-1) erhielten die Br�tlinge �ber die ersten zwei Wochen kein zus�tzliches Futter (nur Naturnahrung), anschlie�end wurde Weizenschrot zugef�ttert, erst ab dem 63. Tag das Versuchs- bzw. Kontrollfutter f�r 87 Tage. Bei Versuchsende war in den Gruppen der h�chsten Besatzdichte die Mortalit�t durch HS um ca. 20 % verringert (p<0,0001). Die Abfischungsmassen waren bei geringer Besatzdichte ann�hernd gleich, bei mittlerer Besatzdichte war die Kontrollgruppe, bei h�chster Besatzdichte die Versuchsgruppe favorisiert (statistische Pr�fung wegen des Fehlens von Einzeldaten nicht m�glich). Der um die HS-Aufnahme bereinigte Futteraufwand war in den HS-Gruppen bei geringer bzw. h�chster Besatzdichte um 5 bzw. 17 % verringert. In beiden Versuchen, F I und F II, wurde eine deutliche Verringerung des Gehaltes der inneren Organe Leber, Niere und Milz an fakultativ pathogenen Aeromonas- und Pseudomonas spp. nachgewiesen (p<0,05). Bei der Aufzucht von Regenbogenforellen (F III; N=2 x 25) trugen die durch den HS-Zusatz bedingten Ver�nderungen der Konsistenz von Futter und Kot zur Verminderung einer starken Belagbildung (Bewuchs aus Algen und anderen Mikroorganismen) sowie zur Vermeidung von Wassertr�bungen in den Aquarien, insbesondere bei h�heren Temperaturen, bei. Signifikante Unterschiede in den Kenndaten von Wachstum und Futteraufwand wurden nicht beobachtet. Insgesamt gesehen erscheint aber der Zusatz von 5 % HS zum Futter als zu hoch gew�hlt, da sich der Futteraufwand in den HS-Gruppen bei Ber�cksichtigung der Gesamtfuttermenge (einschlie�lich des 5%igen HS-Zusatzes) �berwiegend ung�nstiger gestaltete. Die Effekte der oralen Applikation von 5 % HS im Futter sind damit weit weniger augenf�llig als nach �u�erlicher Anwendung. Die zootechnischen Parameter waren �berwiegend mehr oder weniger unver�ndert; allein in Versuch F I war die K�rpermasse in der HS-Gruppen im Versuchsverlauf (Stichproben und Abfischung) in der Regel signifikant h�her als in der Kontrollgruppe. Von k�nftiger Bedeutung f�r die Aquarienhaltung von Fischen (und m�glicherweise in Klein- und Zierteichen) k�nnte die beobachtete Wasserkl�rung und die Verminderung einer Belagbildung aus Algen und anderen Mikroorganismen sein. Eine intestinale Wirkung der HS wird insoweit unterstellt, als in beiden Karpfenversuchen die inneren Organe einen verminderten Befall an beweglichen Aeromonaden und Pseudomonaden aufwiesen. / Prophylactic and therapeutic use of brown coal-derived humic substances of the type WH 67 in finfish and ornamental fish farming On the market, there is a limited number of suitable and approved drugs available for therapy and prophylaxis of fish diseases. The search for alternatives which are both effective and safe for animals, consumers and environment is therefore of special importance. There are numerous reports on positive effects of orally administered humic substances (HS) on agricultural livestock, zoo animals and pets. Therefore, the present study aimed on effects of HS for both external treatment of ornamental fish and oral application on culture fish via feed. Two experiments on goldfish (Carassius auratus) (exp. B I: 4 days; exp. B II: 12 days), and on common carp (Cyprinus carpio) (exp. F I: 1,000 days, fry to 3-year-old fish ; exp. F II: 150 days, fry to young-of-the-year size) were carried out under pond culture conditions. Additionally, one experiment on rainbow trout (Oncorhynchus mykiss) was carried out in the laboratory (exp. F III: 166 days, fingerlings up to 30 g body weight). The following parameters were examined: mortality, morbidity, growth, feed conversion ratio (exp. F I, F II, F III only), pathologic anatomical criteria (including histological examination of fish from B I and F II), parasitological investigation, bacteriological and virological state. Water quality was regularly examined as well. In the experiments B I and B II, a 10% sodium-humate solution (type WH 67 SNa, Pharmawerk Weinb�hla) was mixed into the water until a sodium-humate concentration of 10 mg L-1 was reached. Two-year old, multifactorially diseased goldfish (B I: N= 2 x 322; B II: N= 2 x 100) were daily exposed to this water for a period of one (B I) and 1.5-2 (B II) hours, respectively. In both experiments the treatment of fish reduced in mortality (B I: 0.6 vs. 4.7 %, p<0.0005; B II: 8 vs. 16 %, p<0.05). Moreover, at the end of the experiments the sodium-humate treated fish showed a significantly improved health state (B I: p<10-16; B II: p<0.001) as indicated by externally visible changes of the skin, fins and gills. Specifically, reductions in haemorrhage of skin and fins (B II: p <0.05), and fin and gill necroses (B II: p<0.05), and gill inflammations (B II: p<0.02) were noted. Additionally, the sodium-humate treatment reduced integumental mucoses of skin, fins and gills (p<0.05) caused by Saprolegnia sp. The infection of skin and gills with protozoan parasites was reduced (p<0.01) as well. Ichthyophthirius sp. infections of the gills dropped significantly (p<0.05) in the treated fish groups as compared to the controls. Due to the observed mitigation of disease symptoms of environmental, bacterial, parasitic and fungal origin after a sodium-humate bath treatment of goldfish, a tissue protective, antiphlogistic, antimycotic and antiparasitic effect of sodium-humate can be concluded. For rearing of carp (F I) and rainbow trout (F III), 5 % Humocarb, formuliert� (type WH 67 A, Pharmawerk Weinb�hla) was mixed among the feed, while for the experiment F II 5 % Cellu-Ligno-Carbon-Isolat (type WH 67 G, Pharmawerk Weinb�hla) was added. In F I and F III a complete feed for trout was applied whereas for F II a complete feed for carp was used. In experiment F I (stocking density of both ponds 35,000 carp fry per ha) test fish revealed a higher mean body weight compared to the controls. With one exception (sample size to small), the difference between the groups was either significant (day 114: 65 vs. 45 g, p<0.05) or highly significant (day 1000: 1,146 versus 855 g, p<0.0001). The feed conversion ratio of the first experimental year (expurgated by HS-uptake) improved by 34 % due to HS application. Feed conversion ratio of the second and third year were falsified because of subjective feeding (which does not consider occurring losses). In experiment F II (stocking density of the 2 x 3 ponds (0,25 ha) were 20,000, 30,000 and 40,000 individuals per ha, respectively) no additional feed was given to the hatched fry during the first two weeks so that all the fish lived on natural feed items. Afterwards, bruised wheat grain was given until from day 63 either test or control feed was applied for a total of 87 days. At the end of the experiment, at the highest stocking density the mortality was significantly (p<0.0001) decreased by 20% in the test group supplied with HS. At low stocking density the total weight of fish at harvest was not different between the test and control group. However, at medium stocking density the average body weight was higher in the control whereas reverse conditions were observed at the highest stocking density (due to a loss of data no statistical analysis was possible). The feed conversion ratio (expurgated by the uptake of humic substances) was decreased in the test groups of low (5 %) and high (17 %) density. In both experiments (F I and F II) significantly reduced infections of the internal organs liver, kidney and spleen with potentially pathogenic Aeromonas and Pseudomonas spp. were detected. In the rainbow trout rearing (F III; N = 2 x 25), the HS-caused changes in consistency of feed and faeces impaired the formation of heavy algal films and large microorganism populations, and contributed to less turbid water turbidity in the aquaria, particularly at high temperatures. Significant differences in growth and feed conversion ratio could not be observed. In general, the addition of 5 % HS to the feed is regarded as being too high because the total amount of feed given (inclusive 5 % HS) is considered. The feed conversion ratio was higher in most of the HS-groups. Effects of oral application of 5 % HS in feed were thus less obvious than the bath treatment. Zootechnical parameters, in general, did not change. Merely in experiment F I the body weight of the HS-groups was significantly higher than that of the controls. In aquaria and small ponds used for ornamental fish breeding the observed cleaning of water and reduced formation of algal films and microorganism populations caused by HS could be of future importance. Intestinal effects of HS are assumed as internal organs revealed a reduced infection with both motile aeromonads and pseudomonads.

Mémoire (M.Ress.Renouv.)-- Université du Québec à Chicoutimi, 1994. / Document électronique également accessible en format PDF. CaQCU

A aplicação de substâncias húmicas (SH) em misturas com ureia pode aumentar a eficiência do uso de N (EUN) em soqueiras e também melhorar a produtividade de cana-de-açúcar por favorecer a atividade de proteínas relacionadas ao processo de absorção de nutrientes. Neste sentido, experimentos de laboratório, casa-de-vegetação e de campo foram desenvolvidos com os seguintes objetivos: (i) Avaliar e caracterizar SH extraídas de turfa em misturas com soluções de N-ureia, quantificando teores de N-mineral e a volatilização de NH3. (ii) Quantificar a produtividade de colmos e atributos tecnológicos da cana-de-açúcar adubados com doses de SH, doses de ureia e misturas de doses ureia+SH em experimentos de campo. (iii) Estudar a eficiência de recuperação do 15N-ureia em misturas com SH e ácidos húmicos (AH) aplicados às folhas de cana-de-açúcar. (iv) Estimar a biomassa, acúmulo de nutrientes (N, P, K), particionamento (folhas secas, colmo e ponteiros) e a relação (N:P, N:K) destes nutrientes nas soqueiras de cana-de-açúcar com diferentes níveis de produtividade. Em experimento de laboratório, após a extração, purificação e caracterização das SH, foram preparadas as misturas com doses crescentes de ureia. Constatou-se a hidrólise de parte do N-amídico, transformando-o em N-NH4+ e que a concentração de ureia nas misturas pode interferir na hidrólise da mesma. A mistura da solução de ureia com SH (15% de N), com o pH corrigido (pH=7), possibilitou a redução nas perdas de NH3 por volatilização do solo. Em estudos de campo, com doses de N-ureia (0, 25, 50, 75 e 100 kg ha-1), doses de SH (0, 100, 200, 300 e 400 L ha-1) e mistura destas doses: ureia+HS, verificou-se que em três áreas estudadas, duas houve resposta aos fertilizantes nitrogenados ureia e misturas ureia+SH. Em geral, as doses de ureia+SH promoveram aumento significativo de 6% de rendimento de colmos (TCH) e incremento de 4,5% da produção de açúcar (Mg ha-1) comparando somente com a aplicação de doses de ureia. Em dois experimentos de casa-de-vegetação foram realizadas aplicações às folhas de cana-de-açúcar de ureia, ureia+AH e ureia+SH. Na média dos dois experimentos, a recuperação de 15N (EUN) foi maior para a ureia + SH (49%) em comparação com ureia + AH (43%) e apenas ureia (37%). A fertilização foliar com ureia + SH aumentou o valor total de proteína (7, 24, 17 e 93%) quando comparado com aplicação somente de ureia após 96, 192, 360 e 720 horas da aplicação foliar, respectivamente. O particionamento dos nutrientes (N, P e K) nos órgãos da cana-de-açúcar (folha seca, ponteiros e colmos) indicam que maiores produtividades de colmo foram obtidas com elevados acúmulos desses nutrientes no ponteiro e maior equilíbrio da relação de N:P (6:1) e N:K (0,5:1). A mistura de ureia com SH é uma estratégia viável que promove aumento de rendimento de colmos, maior produção de açúcar e ainda aumento da EUN. No entanto, para sistemas com altas produtividades é necessário observar a relação e o equilíbrio dos nutrientes principalmente nos componentes com alta atividade fotossintética (ponteiros de cana-de-açúcar). / Humic substances (HS) in mixture with urea can improve N use efficiency (NUE) and sugarcane yield when applied in ratoon. In this regard, lab experiments, greenhouse and field studies have been developed with the following goals: (i) Evaluate and characterize HS extracted from peat in mixtures with urea solutions, quantifying N-mineral content and NH3 volatilization. (ii) Quantify sugarcane yield and technological attributes of sugarcane ratoon fertilized with HS rates, urea rates and mixtures of the fertilizers: HS+urea on field experiments. (iii) Evaluate the recovery efficiency of 15N-urea mixture with HS and humic acid (HA) applied on sugarcane leaf. (iv) To estimate the biomass, nutrient uptake (N, P, K), partitioning (dry leaves, stem and tops) and the ratio (N:P,N:K) of these nutrients in the sugarcane ratoon with different levels of productivity. In the lab, after extraction, purification and characterization of HS, mixtures with rates of urea were performed. It was observed that this mixture was promoted by urea hydrolysis transforming into N-NH4+ and concentration of N-urea may interfere in the hydrolysis. The experiment to evaluate the volatilization was observed that the mixture of HS and urea solution with a fixed pH (pH = 7) led to the reduction in losses by volatilization of NH3. In field studies, N-urea rates (0, 25, 50, 75 and 100 kg ha-1), HS rates (0, 100, 200, 300 and 400 L ha-1) and mixing these doses: urea + HS. In two of the three studies there were response to the urea nitrogen fertilizers, urea and mixtures HS+urea. In general, urea doses + HS promoted significant increase of 6% yield of stalks (TCH) and 4.5% increase in sugar production (Mg ha-1) compared only with the application of urea. In greenhouse experiments applications were performed via foliar urea, urea+HA and urea+HS. The average of the two experiments, the recovery of 15N (NUE) was added to the HS + urea (49%) compared with HA+urea (43%) and only urea (37%). The foliar application of urea+HS increased the total protein value (7, 24, 17 and 93%) compared with the application of urea for only 96, 192, 360 and 720 hours following fertilizer application, respectively. In addition, there was a nutrient partitioning study (N, P and K) in the components of sugarcane (dry leaf, tops and stems). It was observed for nutrient partitioning process that dry leaves had lower nutrient content (N, P, and K) and broader N:P/N:K ratios when compared with tops and stalks. Greater sugarcane yield and narrowed N:P ratio (6:1) were documented for tops of sugarcane when increasing both N and P content. However, for high systems yields it is necessary check the ratio and balance of nutrients in the components with high photosynthetic activity (tops of sugarcane).

Conselho Nacional de Desenvolvimento Científico e Tecnológico / In the first study examined ammonia, urea, creatinine, protein, nitrite, nitrate, and phosphorus (P) excretion at different water hardness, humic acid or pH levels in silver catfish (Rhamdia quelen) juveniles. The fish were exposed to different levels of water hardness (4, 24, 50, or 100 mg CaCO3 L-1), humic acid (0, 2.5 or 5.0 mg L-1) or pH (5.0, 6.0, 7.0, 8.0, or 9.0) for 10 days. The overall measured nitrogen excretions were 88.1% (244 423 μmol kg-1 h-1) for ammonia, 10.9% (30 52 μmol kg-1 h-1) for creatinine, 0.02% (0.05 0.08 μmol kg-1 h-1) for protein, 0.001% (0.002 0.004 μmol kg-1 h-1) for urea, 0.5% (0.64 3.6 μmol kg-1 h-1) for nitrite, and 0.5% (0.0 6.9 μmol kg-1 h-1) for nitrate, and these proportions were not affected by water hardness or humic acid levels. The overall P excretion in R. quelen was 0.14 2.97 μmol kg-1 h-1. Ammonia excretion in R. quelen usually was significantly higher in the first 12 h after feeding, and no clear effect of water hardness, humic acid levels and pH on this daily pattern of ammonia excretion could be observed. Water hardness only affected the ammonia and P excretion of R. quelen juveniles in the initial and fifth days after transfer, respectively. The exposure of this species to humic acid decreased ammonia excretion after 10 days of exposure but did not affect P excretion. An increase in pH decreased ammonia and increased creatinine excretion but did not change P excretion in R. quelen. Therefore, when there is any change on humic acid levels or pH in the culture of this species nitrogenous compounds must be monitored because their excretion rates are variable. On the other hand, P excretion rates determined in the present study are applicable to a wide range of fish culture conditions. The aim of the second study was to determine the preferred pH in silver catfish Rhamdia quelen acclimated to different water hardness and the effect of shelters and infection by Ichthyophthirius multifiliis. Fish were acclimated for two weeks at different water hardness levels (4, 24, 50, or 100 mg CaCO3 L-1) and then transferred to a polyethylene tube with a pH gradient ranging from 3.5 to 11.7. The position of the fish in the pH gradient was observed at 1, 2, 4, 6, 8, 10, and 12 h after transference. Acclimation to different water hardness did not change pH preference of uninfected silver catfish (pH 7.30-7.83), and the presence of a shelter at the preferred pH or outside this preferred pH did not change the chosen pH range, either. Consequently silver catfish favored the acid-base regulation over shelter seeking tendency. Juveniles infected with I. multifiliis acclimated to water hardness of 24 mg CaCO3 L-1 preferred alkaline pH (9.08-9.79). This choice is not explained by the higher Na+ levels at alkaline pH compared to neutral pH because infected and uninfected fish choose the same waterborne Na+ levels in a Na+ gradient with the same pH. / No primeiro estudo analisou-se a excreção de amônia, ureia, creatinina, proteína, nitrito, nitrato e fósforo (P) em diferentes níveis de dureza da água, ácido húmico ou pH em juvenis de jundiás (Rhamdia quelen). Os peixes foram submetidos a diferentes níveis de dureza da água (4, 24, 50 ou 100 mg CaCO3 L-1), ácido húmico (0, 2,5 ou 5,0 mg L-1) ou pH (5,0, 6,0, 7,0, 8,0 ou 9,0) durante 10 dias. A excreção nitrogenada global medida foi de 88,1% (244 423 μmol kg-1 h-1) para amônia, 10,9% (30 52 μmol kg-1 h-1) para creatinina, 0,02% (0,05 0,08 μmol kg-1 h-1) para proteína, 0,001% (0,002 0,004 μmol kg-1 h-1) para ureia, 0,5% (0,64 3,6 μmol kg-1 h-1) para nitrito e 0,5% (0,0 6,9 μmol kg-1 h-1) para nitrato, e estas proporções não foram afetadas pelos níveis de dureza da água ou ácido húmico. A excreção global de P em R. quelen foi 0,14 2,97 μmol kg-1 h-1. A excreção de amônia em R. quelen, em geral, foi significativamente maior nas primeiras 12 horas após a alimentação e nenhum efeito claro dos níveis de dureza da água, ácido húmico e do pH pode ser observado sobre este padrão diário de excreção de amônia. A dureza da água afetou apenas a excreção de amônia e de P de juvenis de R. quelen no primeiro e quinto dias após a transferência, respectivamente. A exposição desta espécie ao ácido húmico diminuiu a excreção de amônia após 10 dias de exposição, mas não afetou a excreção de P. Um aumento no pH diminuiu a excreção de amônia e aumentou a excreção de creatinina, mas não alterou a excreção de P em R. quelen. Portanto, quando houver qualquer alteração nos níveis de ácido húmico ou pH na cultura desta espécie os compostos nitrogenados devem ser monitorados, pois suas taxas de excreção são variáveis. Por outro lado, as taxas de excreção de P determinados no presente estudo são aplicáveis a uma ampla gama de condições na cultura de peixes. O objetivo do segundo estudo foi determinar o pH preferido em jundiá Rhamdia quelen aclimatados a diferentes durezas da água e o efeito de abrigos e infecção por Ichthyophthirius multifiliis. Os peixes foram aclimatados durante duas semanas em diferentes níveis de dureza da água (4, 24, 50 ou 100 mg de CaCO3 L-1) e então transferidos para um tubo de polietileno com um gradiente de pH de 3,5 a 11,7. A posição do peixe no gradiente de pH foi observada 1, 2, 4, 6, 8, 10 e 12 h após a transferência. A aclimatação a diferentes durezas da água não afetou o pH preferido de jundiás não infectados (pH 7,30-7,83) e a presença de um abrigo no pH preferido ou fora deste pH também não alterou a faixa de pH preferida. Portanto, jundiás favorecem a regulação ácido-base em detrimento a uma tendência de procurar abrigo. Em juvenis infectados com I. multifiliis aclimatados à dureza da água de 24 mg de CaCO3 L-1 o pH preferido é alcalino (9,08-9,79). Esta escolha não é explicada pelos maiores níveis de Na+ em pH alcalino que em pH neutro porque peixes infectados e não infectados escolheram os mesmos níveis de Na+ na água em um gradiente de Na+ com o mesmo pH. Palavras-chave: piscicultura, gradiente de pH, ácido húmico, dureza da água