HCl ist ein Nebenprodukt bei vielen organischen Chlorierungsprozessen. Die Aufarbeitung von HCl wäre wirtschaftlich sinnvoll. Eine der möglichen Optionen ist die Rückgewinnung des Chlors durch die katalytische HCl-Oxidation mit O2 (Deacon-Prozess). Das Hauptziel dieser Arbeit war es, die katalytische Aktivität von kupferchlorid-haltigen Schmelzen in Abhängigkeit von der Temperatur und dem Verhältnis der Reaktionsgase zu untersuchen. Dazu wurden Versuche unter stationären und instationären Reaktionsbedingungen im Temperaturintervall zwischen 400 und 500 °C durchgeführt. Für das bessere Verständnis des Katalysator-Systems wurde ein thermodynamisches Modell für das Stoffsystem MeCl-CuCl-CuCl2-CuO-HCl-H2O-Cl2-O2 (Me = Li, Na, K) erstellt. Weiterhin wurden mithilfe von kinetischen Untersuchungen Hinweise auf die Rolle der gelösten oxidischen Zwischenverbindungen im stufenweisen Reaktionsmechanismus gefunden. Mit den Versuchsergebnissen wurde gezeigt, dass die MeCl-CuCl-CuCl2-Schmelzen eine genügende katalytische Aktivität besitzen und damit eine Alternative zu den mit Feststoffträgern arbeitenden Katalysatoren darstellen. Zur Minderung von Korrosionsproblemen wurden mehrstufige Prozessführungen kritisch diskutiert.:1 Einleitung. . . . . . . . . . .7 2 Theoretische Grundlagen zum Deacon-Prozess in Salzschmelzen. . . . . . . . . . .9 2.1 Thermochemie des Deacon-Prozesses. . . . . . . . . . .9 2.1.1 Oxidation von HCl mit O2 ohne Katalysator. . . . . . . . . . .9 2.1.2 Oxidation von HCl mit O2 in Gegenwart von CuCl2-haltigen Katalysatoren. . . . . . . . . . .10 2.2 Kinetik der Teilreaktionen in kupferchlorid-haltigen Salzschmelzen. . . . . . . . . . .13 2.2.1 Zersetzung des CuCl2. . . . . . . . . . .14 2.2.2 Oxidation von CuCl. . . . . . . . . . .15 2.2.3 Reaktion zwischen CuO-haltiger Schmelze und Chlorwasserstoff. . . . . . . . . . .17 3 Thermodynamische Modellierung der Mischungen aus LiCl, NaCl, KCl, CuCl und CuCl2. . . . . . . . . . .19 3.1 Thermodynamische Daten der reinen Stoffe. . . . . . . . . . .20 3.2 Mischungsmodelle. . . . . . . . . . .22 3.3 Vorgehensweise bei der Optimierung. . . . . . . . . . .25 3.4 System LiCl-NaCl-KCl. . . . . . . . . . . 25 3.5 System LiCl-CuCl. . . . . . . . . . .26 3.6 System NaCl-CuCl. . . . . . . . . . .28 3.7 System KCl-CuCl. . . . . . . . . . .29 3.8 System LiCl-CuCl2. . . . . . . . . . .30 3.9 System NaCl-CuCl2. . . . . . . . . . .33 3.10 System KCl-CuCl2 . . . . . . . . . . .34 3.11 System CuCl-CuCl2. . . . . . . . . . . 35 3.12 Ternäre Systeme. . . . . . . . . . .39 4 Untersuchungen zur CuO-Löslichkeit und der Stabilität von Oxidchloriden des Kupfers. . . . . . . . . . .46 4.1 Präparation von Cu2OCl2 und K4Cu4OCl10. . . . . . . . . . .46 4.2 Untersuchungen zur CuO-Löslichkeit. . . . . . . . . . .47 4.2.1 Thermodynamische Reaktionsdaten. . . . . . . . . . .47 4.2.2 Auswertung der Literatur. . . . . . . . . . .48 4.2.3 O2-Titration kupferchlorid-haltiger Schmelze. . . . . . . . . . .49 4.2.4 Hochtemperatur-Filtration und CuO-Analyse. . . . . . . . . . .53 4.2.5 Thermischer Zerfall von Cu2OCl2. . . . . . . . . . .55 4.2.6 Thermischer Zerfall von K4Cu4OCl10. . . . . . . . . . .57 4.3 Thermodynamische Modellierung CuO-haltiger Systeme. . . . . . . . . . .59 4.3.1 Cu2OCl2. . . . . . . . . . .59 4.3.2 K4Cu4OCl10. . . . . . . . . . .60 4.3.3 CuO-Löslichkeit. . . . . . . . . . .62 4.3.4 Salzschmelzenmodell mit oxidhaltigen Systemen. . . . . . . . . . .63 4.4 Thermochemie des Deacon-Prozesses mit Modell-Daten. . . . . . . . . . .69 5 Experimentelle Untersuchungen zur katalytischen Oxidation von HCl in Salzschmelzen. . . . . . . . . . .72 5.1 Versuchsprogramm. . . . . . . . . . .72 5.2 Allgemeine Vorgehensweise. . . . . . . . . . .72 5.2.1 Versuchsapparatur. . . . . . . . . . .72 5.2.2 Vorbereitung der Salzmischungen. . . . . . . . . . .74 5.2.3 Bestimmung der Gaszusammensetzung und Umsatzberechnungen. . . . . . . . . . .75 5.2.4 Bestimmung der Schmelzenzusammensetzung. . . . . . . . . . .77 5.2.5 Charakteristik der Reaktoreinsätze Spirale und Fritte. . . . . . . . . . .77 5.3 Versuche mit Salzmischungen auf der Basis von Kupferchlorid. . . . . . . . . . .81 5.3.1 Stationäre Strömungsverhältnisse. . . . . . . . . . .81 5.3.2 Instationäre Bedingungen. . . . . . . . . . .95 6 Vorschläge zur Technologie. . . . . . . . . . .106 7 Zusammenfassung. . . . . . . . . . .112 Literaturverzeichnis. . . . . . . . . . .115 Anhang. . . . . . . . . . .124 A.1 Thermodynamische Standard-Daten. . . . . . . . . . .124 A.2 Thermodynamische Daten für das Modell LiCl-NaCl-KCl-CuCl-CuCl2-CuO-H2O-HCl-O2-Cl2. . . . . . . . . . .126 A.3 Charakteristika der kupferoxidhaltigen Verbindungen. . . . . . . . . . .133 A.3.1 P-XRD- und Raman-Aufnahmen der synthetischen Oxidchloriden. . . . . . . . . . .133 A.3.2 O2 -Titration kupferchlorid-haltiger Schmelze. . . . . . . . . . .134 A.3.3 Thermischer Zerfall von Cu2OCl2 und K4Cu4OCl10. . . . . . . . . . .137 A.3.4 Phasendiagramm KCl-CuCl2-CuO. . . . . . . . . . .138 A.4 Katalytische Oxidation von HCl in Salzschmelzen. . . . . . . . . . .138 A.5 Physikalische Eigenschaften von (Alk-Cl)-CuCl-CuCl Salzschmelzen. . . . . . . . . . .156 A.6 Chemikalien. . . . . . . . . . .161 A.7 Geräte, Anlagen. . . . . . . . . . .162 A.8 Methode zur titrimetrischen Bestimmung von Cu+, Cu+2 und CuO. . . . . . . . . . .164 A.9 Berechnete Chlor- und Sauerstoffpartialdrücke für (Alk-Cl)-CuCl-CuCl2-Schmelzen. . . . . . . . . . .164 A.10 Berechnete Aktivitäten der geschmolzenen Kupferchloride in (Alk-Cl)-CuCl-CuCl2-Schmelzen. . . . . . . . . . .171

Dischargers to the Trinity River in North Texas were required to dechlorinate their effluents in 1990-91. Field surveys were conducted above and below an outfall to determine the response of resident immature insects and caged in situ juvenile Asiatic clams to chlorinated and dechlorinated effluent. Within six months after dechlorination began, insect community composition and C. fluminea survival significantly improved at stations below the outfall. Significantly lower clam growth within one mile below the dechlorinated effluent indicated the presence of non-chlorine toxicants. Effects from chlorinated and dechlorinated effluent exposure were comparable between Ceriodaphnia dubia lab tests and in situ C. fluminea.

Federal regulations such as the Clean Water Act (P.L. 92-500), and its amendments, direct the Environment Protection Agency (EPA) to implement programs to control the releases of conventional pollutants and toxics into the waterways of the United States. The EPA began requiring treatment plants to conduct toxicity tests (biomonitoring) of their effluent discharges. To control toxicity caused by chlorination of wastewater discharges, the EPA also began requiring some treatment facilities to dechlorinate their wastewater before discharging. This research was funded by the EPA to document the changes that occurred in the Trinity River from the dechlorination of the effluent from Ft. Worth's Village Creek municipal wastewater treatment plant. The study occurred over a two year period beginning in August 1990. A wide variety of biological field assessments and toxicological assays were used to measure various responses. Seven river stations, covering approximately twenty river miles, and the treatment plant effluent were assessed. Two of the river stations were upstream from the treatment plant and used as reference sites. The remaining five river stations were downstream from the treatment plant, spread out over seventeen river miles. The study evaluated the impact of chlorination prior to dechlorination, which served as a baseline. Responses determined during dechlorination were compared to the baseline data. An overall improvement in species richness and diversity was seen at those river stations which had previously been adversely impacted by chlorine. Aquatic toxicity tests, such as those required to be used by dischargers, were conducted during this study. Periodic toxicity was observed with these tests in the effluent and river samples after dechlorination was initiated. Those tests, along with in situ toxicity assays, proved to be good predictors of biological community responses.

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The monitoring of pharmaceuticals, heavy metal, pH and free chlorine concentration in drinking water is important for public health and the environment. However, conventional laboratory-based analytical methods are labor-intensive, expensive, and time consuming. This thesis focuses on developing an integrated, highly sensitive, easy-to-use, and low-cost pharmaceuticals, heavy metal, pH and free chlorine sensing system for drinking water quality monitoring. A low-temperature, solution-processed modification of multi-walled carbon nanotubes (MWCNT) with β-cyclodextrin (βCD) on glassy carbon electrode is developed for detecting low levels of acetaminophen. The adsorption properties of βCD are combined with the high surface area of carbon nanotubes towards enhanced electrochemical sensing of acetaminophen with a limit of detection of 11 nM and linear range from 0.05-300 μM. Also, a systematic investigation is carried out using four types of modified MWCNT-βCD. A novel, one-step approach called Steglich esterification modified MWCNT-βCD results in large effective surface area, and fast electron transfer towards sensitive detection of acetaminophen and 17β-estradiol (E2, primary female sex hormone) in the range of 0.005–20 and 0.01–15 μM, with low detection limits of 3.3 and 2.5 nM, respectively. The similar MWCNT-βCD modified electrodes can also detect heavy metal ion (lead, Pb2+) with a limit of detection of <10 ppb. Low frequency noise behavior of these sensors are studied. A spin-coated Pd/PdO based pH sensor, and amine-modified carbon electrode-based free chlorine sensor are fabricated on a common substrate together with the pharmaceuticals and heavy metal sensors. A Wheatstone-bridge temperature sensor is fabricated based on silicon and PEDOT:PSS on another substrate. All the sensors are connected to an Arduino microcontroller based data acquisition system with a smartphone application interface. The integrated sensing system is easy-to-use, low-cost, and can provide accurate monitoring data with real drinking water samples. / Dissertation / Doctor of Philosophy (PhD) / Low-cost, easy-to-use, and sensitive monitoring system for pharmaceuticals, heavy metal, pH and free chlorine in drinking water is crucial for public health safety. In this thesis, we develop solution-based synthesis of multi-walled carbon nanotubes modified by β-cyclodextrin for electrochemical sensing of pharmaceuticals and heavy metal. The modification approaches are compared and characterized to analyze their electrochemical behavior and sensing performances. The developed sensors are highly sensitive toward the detection of acetaminophen (a widely used pain-killer) and estrogen hormone in drinking water. We also develop a modified spin-coating technique to deposit palladium/palladium oxide films for potentiometric pH sensor, a calibration-free free chlorine sensor based on modified carbon electrode, and a resistive temperature sensor. The developed pH, free chlorine and temperature sensors are highly sensitive, and stable with fast response time. All the sensors are integrated and interfaced with a custom-made and smartphone-controlled electronic readout system for accurate and on-site drinking water quality monitoring at low cost.

No / Novel 1- and 1,4-substituted chloroethylaminoanthraquinones with DNA binding and alkylating properties along with their respective hydroxyethylaminoanthraquinone intermediates were synthesized. Selected chloroethylaminoanthraquinones were shown to cross-link DNA and alkylate guanines (at low nM concentration) with a preference for reaction sites containing 5'-PyG. A compound (Alchemix) with the bis-chloroethyl functionality confined to one side chain alkylated but did not cross-link DNA. All the 1,4-disubstituted chloroethylaminoanthraquinones were potently cytotoxic (nM IC50s) against cisplatin-resistant ovarian cancer cell lines.

L'exploitation des réserves d'eau douce, principalement contenues dans les aquifères est une préoccupation croissante dans les zones où elle se traduit par une baisse des niveaux piézométriques.Ce travail de thèse propose de caractériser l'évolution du Système Aquifère du Saharan Septentrional (SASS), et plus particulièrement le Continental Intercalaire (CI) à l'aide d'un couplage entre des outils de modélisation hydrogéologique et de traceurs géochimiques (36Cl, 234U/238U). Situé dans une région semi-aride à aride et s'étendant sur plus d'un million de km2, le CI présente un potentiel d'enregistrement d'une variabilité climatique à grande échelle en plus des baisses piézométriques anthropiques.Nous avons amélioré la définition de la recharge moderne du SASS à l'aide d'une méthode basée sur des données de télédection (entre 0 et 6.75 mm an−1 sur la période 2003-2010) ainsi que de la localisation zones de recharge du Sud Tunisien à l'aide de traceurs isotopiques (14C, 36Cl, 234U). Ces traceurs fournissant un lien évident mais complexe entre les conditions hydrodynamiques présentes et passées, nous nous sommes efforcés d'interpréter les informations paléoenvironnementales apportées par le 36Cl et le 4He sur l'ensemble de la zone tunisienne du CI. Introduites dans un modèle hydrogéologique du CI, les données de 36Cl nous ont permis d'améliorer des hypothèses sur des scénarios de recharge (variant entre 0.5 et 60 mm an−1) pendant les huit derniers cycles interglaciaires-glaciaires (0-775 ka).A partir d'informations complémentaires (échantillons d'eau, affleurements, zone climatique) nous avons finalement construit une représentation "hydro-climato-geochimique" du CI. / Concerns about freshwater availability increase with the rise of populations demands and decrease of piezometric levels in some aquifers. However, this "instantaneous" variability is complicated by a long-term climatic variability that impacts hydrodynamics on timescales of thousands to hundred of thousands of years.This study characterizes the evolution of a large aquifer (extending over more than a million of km2), the Continental Intercalaire (CI), from hydrogeological and geochemical viewpoints, over several hundreds thousand years. For this purpose, we combined hydrogeologic modeling and geochemical tracing methods (36Cl, 234U/238U. . .).The CI is the main aquifer of the North Western Saharan Aquifer System (NWSAS). Located in a semi-arid to arid region, its presence suggests potential records of climatic variability on large temporal and spatial scales. Our results corroborate previous assessment of the modern recharge, which fluctuates between 0 and 6.75 mm yr−1, over the entire NWSAS. We also improve the understanding of previously poorly characterized recharge areas in the South of Tunisia. Isotopic tracers can provide a strong but complex link between past and present hydrodynamic conditions, so we struggled to investigate chlorine-36 and helium-4 paleorecords. In our hydrogeologic model of the CI, chlorine-36 data allowed us to propose some hypotheses about recharge scenarios (varying between 0.5 and 60 mm yr−1) during height of the last interglacial-glacial cycles (0-775 ky). By using multi-scale information (groundwater samples, outcrops and climatic areas), we developed a "hydro-climatic-geochemical" representation of the CI.

<div> <p>Despite its location in the rain shadow of the southern Sierra Nevada, the Panamint Range within Death Valley National Park, CA hosts a complex aquifer system that supports numerous springs. These springs, in turn, support unique groundwater-dependent ecological communities. Spring emergences range in elevation from 2434 m above sea level (within the mountain block) to 77 m below sea level (in the adjacent basins). Waters were collected from representative Panamint Range springs and analyzed for environmental isotopes and geochemical tracers to address the following questions: 1) What is the primary source of recharge for the springs? How much recharge occurs on the Panamint Range? 2) What groundwater flowpaths and geologic units support springflow generation? and 3) What are the residence times of the springs? The stable isotopic composition (δ¹⁸O and δ²H) of spring water and precipitation indicate that localized high-elevation snowmelt is the dominant source of recharge to these perennial springs, though recharge from rainfall is not wholly insignificant. Geochemical evolution was evaluated using principle component analysis to compare the concentrations of all major spring cations and anions in a multidimensional space and group them according to dominant geochemical signatures. These resulting geochemical groups are controlled primarily by topography. The Noonday Dolomite and other carbonate units in the range are identified as the water-bearing units in the mountain block based on the ⁸⁷Sr/⁸⁶Sr of spring waters and rock samples. These units also offer higher hydraulic conductivities than other formations and are chemically similar. Radiocarbon- and ³H derived residence times of these spring waters range from modern to approximately 1840 years, with the shortest residence times at higher altitudes and Hanaupah Canyon and increasing residence times with decreasing altitude. This residence time-altitude relationship is likewise likely topography-driven though there are significant disparities in mountain block storage between the various canyons of the range resulting in variable residence times between drainages. Lower Warm Springs A and B, however, are the exceptions to this trend as they emerge at lower altitudes (750m above sea level) and are likely driven by the transport of groundwater to the surface along faults which increases both the temperature and groundwater residence times of waters from these springs. Benthic macroinvertebrates and benthic and planktonic microbes were also sampled for each spring studied. BMI and microbial community structure in the Panamint Range is likewise topography-controlled with more tolerant communities at lower elevations (within more chemically evolved waters) and less tolerant species in the unevolved waters at higher elevations.</p></div>