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To improve the properties of thermochemical heat storage materials, salt mixtures were evaluated for their heat storage capacity and cycle stability as part of the innovation incubator project “Thermochemical battery” of the Leuphana university Lüneburg. Based on naturally occurring compound minerals, 16 sulfates, 18 chlorides and 5 chloride multi-mixtures, 18 bromides and 5 intermixtures between sulfates, chlorides and bromides were synthesized either from liquid solution or by dry mixing for TGA/DSC screening before continuing the heat storage evaluation with five different measurement setups at a laboratory scale. The TGA/DSC analysis served as a screening process to reduce the number of testing materials for the upscaled experiments. The evaluation process consisted of a three-cycle dehydration/hydration measurement at Tmax = 100°C and Tmax = 200°C. In case of the bromide samples a measurement of hydration conditions with Tmax = 110°C and a water flow at e = 18.68mbar, were added to the procedure to detect the maximum water uptake temperature. Also, a single dehydration to a temperature of Tmax = 500°C was implemented to observe melting behavior and to easier calculate the samples’ stages of hydration from the remaining anhydrous mass. Materials which showed high energy storage density and improved cycle stability during this first evaluation were cleared for multi-cycle measurements of 10 to 25 dehydration and hydration cycles at Tmax = 100 to 120°C and the evaluations at m = 20 to 100g scale. An estimate for the specific heat capacities at different temperatures of the materials which passed the initial stage was calculated from the TGA/DSC results as well. The laboratory scale measurement setup went through five stages of refining, which led to reducing the intended maximum sample mass from m = 100g to m = 20g. A switch from supplied liquid water to water vapor as the used reactant was also implemented in exchange for improved dehydration conditions. Introducing a vacuum pump for evaporating the water limited the influence of outside heat sources during hydration and in-situ dehydration was enabled as to not disturb the state the samples were settling in between measurements. Baseline calculation from blanc measurements with glass powder and attempts to calculate the specific heat capacity cp of the tested materials by 6 applying the Joule-Lenz-law to the measurement apparatus was another step of method development. The evaluation process of the laboratory scale tests at the final setting consisted of 1 to 5 cycle measurements of in-situ dehydration and hydrations with applied vacuum for t = 30 minutes at p ~ 30mbar. Upscaling the sample mass to m = 20g allowed for a close observation of different material behaviors. Agglomeration, melting and dissolving of the m = 10mg samples during the TGA/DSC analysis can be deducted from the recorded measurement curves and the state of the sample after measurement. However, at laboratory scale the visible volume changes, observed sample consistency after agglomeration and an automatic removal of molten and dissolved sample mass during the measurement allowed for a better characterization and understanding of the magnitude of the actual changes. This was done for the first time, particularly for mixed salts. Of the original number of 62 samples, 4 mixtures which passed the initial TGA/DSC screening namely {2MgCl2+ KCl}, {2MgCl2+CaCl2}, {5SrBr2+8CaCl2} and {2ZnCl2 + CaCl2} were chosen for further evaluation. The multi-cycle TGA/DSC measurements of {2MgCl2+ KCl}, {2MgCl2+CaCl2} and {5SrBr2+8CaCl2} showed an improved cycle stability for all three materials over the untreated educts. Of the four materials {2ZnCl2 + CaCl2} displayed the strongest deliquescence during hydration in the upscaled experimental setup. {2MgCl2+CaCl2} proved to be the most stable material regarding the heat storage density. The {MgCl2} content of the mixture is likely to partially or completely react to {Mg(OH)Cl} at temperatures of T > 110°C, which however does not impede the heat storage density. {5SrBr2+8CaCl2} displayed a low melting point in hydrated state, causing a fast material loss. This makes it an undesirable storage material. A lower heating rate may still help to avoid an early melting. The {2MgCl2+KCl} mixture was the most temperature stable of the mixtures showing no melting or dissolving behavior. A reaction of the {MgCl2} component of the mixture to {Mg(OH)Cl} was not observed within the applied temperature range of T = 25 to 200°C.
Herbizide, die durch Spray-Drift, Volatilisation oder Winderosion aus landwirtschaftlichen Flächen ausgetragen werden können wiederum auf Nichtzielpflanzen gelangen. Es wird angenommen, dass Wälder eine Senke für luftgetragene Pestizide darstellen. Wirkungen von luftgetragenen Herbiziden auf Nichtzielpflanzen können nicht ausgeschlossen werden. An Blättern von Nichtzielpflanzen haftende Herbizide können wiederum durch Regenereignisse aus der Laubschicht ausgewaschen werden und in den Boden gelangen. Welche Stoffe nach deren Deposition ausgewaschen werden oder aber in der Laubschicht verbleiben hängt vom Verteilungsverhalten an der Blattoberfläche ab. In der vorliegenden Dissertation wurde das Verteilungsverhalten von current-use Herbiziden und einiger ihrer Abbauprodukte an der Oberfläche von Nichtzielpflanzen bestimmt. Als Modellorganismus diente die Waldkiefer Pinus Sylvestris L. mit deren Nadeln Versuche zur Charakterisierung des Adsorptions- und Desorptionsverhaltens von 55 Herbiziden aus wässrigen Lösungen durchgeführt wurden. Es wurden Verteilungsversuche sowohl mit rekonstituiertem epikutikulärem Wachs als auch mit intakten Kiefernnadeln durchgeführt. Für den Stoff Terbuthylazin konnte bei Versuchen mit rekonstituierten epikutikulären Wachsen eine Aufnahme aus der wässrigen Lösung in das Wachs festgestellt werden. Der Verteilungskoeffizient zwischen Wachs und Wasser betrug für die Adsorption log KWachsW = 3, 0. Für die Desorption wurde ein höherer Verteilungskoeffizient von log KWachsW = 3, 3 ermittelt und auf Grund der Differenz eine teilweise irreversible Bindung des Terbuthylazins an das epikutikuläre Wachs angenommen. Sorptionsversuche mit wässrigen Lösungen und intakten Kiefernnadeln zeigten für 19 weitere Herbizide mit einem log KOW > 3,8 eine schnelle Adsorption aus der wässrigen Phase an die Nadeloberfläche mit einer mittleren Lebensdauer für die Adsorption von 12 Minuten (Aclonifen, Bifenox, Bromoxynil-octanoat, Diflufenican, Fenoxaprop-p-ethyl, Fluazifop-p-butyl, Fluroxypyrmeptyl, Haloxyfop-ethoxyethyl, Haloxyfop-methyl, Mefenpyr-diethyl, PCP, Pendimethalin, Picolinafen, Propaquizafop, Prosulfocarb, Pyridate, Quizalofop-ethyl, Triallate und Trifluralin). Die für diese Stoffe ermittelten Kutikula/Wasser-Verteilungskoeffizienten liegen im Bereich log KCW = 3,3 bis 4,8. Für 7 Stoffe war nach einer schnellen Verringerung der Konzentration in der wässrigen Phase eine weitere stetige Abnahme der Herbizidkonzentration mit einer Lebensdauer unter 2000 Minuten zu beobachten (Fluroxypyr-meptyl, Fenoxaprop-p-ethyl, Propaquizafop, Quizalofop-ethyl, Trifluralin, Fluazifop-p-butyl und Haloxyfop-methyl), was durch eine Aufnahme der Stoffe über die epikutikuläre Wachsschicht in das innere Gewebe der Kiefernnadeln erklärt werden kann. Die Stoffe Bromoxynil-octanoat, Fluroxypyr-meptyl, Propaquizafop, Quizalofop-ethyl und Trifluralin zeigten eine irreversible Aufnahme aus wässrigen Lösungen in Kiefernnadeln. In einem Laborversuch wurde die Deposition von Herbiziden auf intakten Kiefernnadeln simuliert. Die Verteilung zwischen der epikutikulären Wachsschicht, Niederschlagswasser und den nach Extraktion mit Dichlormethan verbleibenden Nadeln wurde für das Herbizid Isoproturon und seine Abbauprodukte ermittelt. Das hierfür entwickelte Versuchsdesign erlaubte die Messung der Verteilungsvorgänge an intakten, noch am Zweig befindlichen Kiefernnadeln. Die Translokation, Volatilisation und die Bildung von Abbauprodukten konnten quantifiziert werden. Die Laborversuche ergaben, dass Isoproturon bei Kontakt mit wässrigen Lösungen sofort (Lebensdauer unter 1 Minute) von der Oberfläche der Kiefernnadeln desorbiert und nicht in das innere Gewebe der Kiefernnadel aufgenommen wird. Darüber hinaus treten bei Driftrückständen kleiner Stoffmenge und Schichtdicke (1 ng/mm²) für Isoproturon hohe Verluste (zwischen 47 und 88 % der ursprünglich applizierten Menge) durch Volatilisation und abiotischen Abbau auf. Aus den Ergebnissen der Laborversuche können Rückschlüsse zum Verbleib des Herbizids Isoproturon im Waldökosystem getroffen werden. Sie zeigen, dass Driftrückstände von polaren Herbiziden durch Regenereignisse aus der Vegetationsoberfläche von Nichtzielpflanzen ausgetragen werden und in andere Umweltkompartimente gelangen können.
Subaquatic ammunition dumpsites of both, conventional as well as chemical ammunition do practically exist in every single ocean and even in a significant number of inland waters. Most of these dumpsites are based on related post world war dumping actions, when victorious and defeated states had to get rid of their enormous surplus stocks of ammunition and especially the not easy to be handled chemical warfare agents like mustard, phosgene and even nerve agents. After first attempts of conventional destruction like burning, explosion or even simple emptying of chemical agents into pits or holes in the ground, those attempts soon emerged to be very time-consuming and dangerous. Adequate destruction technologies of today’s standards like detonation chambers or plasma kiln did just not exist at that time. The persons in charge soon focused on a much more promising solution attempt: the dumping of this ammunition into surrounding water bodies. In the case of the post World War II dumping actions, the focusing on the former deep water sites soon turned out to be not practicable, based on related enormous costs and logistical problems. The Baltic Sea – with maximum water depths of about 150 m – seemed then to represent the easiest way to get rid of the problematic ammunition. By these activities 65,000 to up to 300.000 tons of chemical ammunition ended up in the Baltic Sea. Concerning conventional ammunition like water mines, torpedo warheads, high explosive devices etc., there is practically no information available but experts assume at least another 100.000 tons of conventional material in the Baltic Sea. Environmental aspects and the issue of protection of the sea were – like in other cases of subaquatic dumping actions worldwide – completely ignored at that time. Nevertheless, subaquatic dumping actions took place until the late 1980ies. Today these dumping sites – whether based on conventional or on chemical ammunition – do represent a very problematic and highly dangerous heritage to present and future generations: Corrosion of the containers and shells results in a not to be forecasted diffuse emission or rather leaking of the ammunition contents into the water body. Substances that are in most cases highly or even extremely toxic for humans, flora as well as fauna contaminate the marine environment with mostly unknown toxicological and ecotoxicological effects. The majority of these substances are known to have carcinogenic, teratogenic and/or mutagenic effects and practically nothing is known about the potential of these substances to end up in the food chains. Especially in recent years there are more and more findings of significantly increased arsenic values in fish that cannot be explained but there are strong signs that these values are based on ammunition dumpsites. Besides the mentioned toxicological and ecotoxicological effects, there are further significant risks as e.g. the possible access to the ammunition also in the context of terrorist and right-wing extremist activities, the continuous catching of and resulting injuring of fishermen by ammunition, the constant endangering of the civil and commercial shipping by direct contact or rather too close convergence to dumped ammunition especially in the context of self detonation or a sudden release of significant amounts of these substances e.g. in the context of an accident and last but not least the uncontrollable landing of containers and ammunition as well as already flushed out contents on coasts and beaches. Basically can be stated that there is still a significant need of action and scientific investigation in the general topic of subaquatic ammunition dumpsites and that related measures have to be taken immediately – especially concerning our sense of responsibility for future generations.
