The long-term fate of hydrocarbons in the Gulf of Mexico (GOMx) following the 2010 Deepwater Horizon oil spill has yet to be fully characterized. Elemental (% C and % N), stable isotopes (δ13Corganic), and polycyclic aromatic hydrocarbon (PAH) molecular signatures were investigated in shelf and slope sediments collected in October 2010 and 2011 to gain insight into processes affecting the distribution and fate of spilled Macondo oil. Particulate organic carbon (POC) ranged between 1.55 and 2.22 wt. % in 2010 and 0.55 and 2.06 % in 2011 while the corresponding δ13Corganic ranges were from -23.37 to -20.77 ‰ (vs. PDB) in 2010, and -22.68 to -20.75 ‰ (vs. PDB) in 2011. Ranges of total polycyclic aromatic hydrocarbon (TPAH) concentrations were from 72.57 to 7,543.53 ng/g in 2010 and 25.55 to 16,582.77 ng/g in 2011. The range of measured values represented significant deviations from previous background measurements. This provided the basis for concluding that the Macondo spill altered the “background” organic carbon and hydrocarbon signature, that Macondo oil has weathered and/or biodegraded in the year following the spill, and that a significant spatial trend of hydrocarbons extended from the Macondo well across the northern GOMx in October 2010 and 2011.

Graphene is a two-dimensional sp2 hybridized carbon lattice that is also the fundamental building block of graphite. Graphene has attracted significant interest recently due to its distinctive electrical, optical and mechanical properties. These properties have spurred research directed at modifying graphene for use in a variety of electronic, optoelectronic, and sensor technologies. However, before graphene can be used in products, it is necessary to find methods to tune, modify, grow and integrate graphene features while substantially boosting device performance and maintaining current processing compatibility and ease of integration with existing manufacturing infrastructure. This dissertation focuses on developing techniques for controllably doping the graphene layer through scalable, industry friendly and simple chemical doping; using self-assembled monolayer compounds, photo-acid and photo-base generators, polymers and metal-organic species. We have, in fact, demonstrated simple p-n junctions fabricated in this manner. Characteristic I-V curves indicate the superposition of two separate Dirac points from the p and n regions, confirming an energy separation of neutrality points within the complementary regions; Raman studies of these methods have shown that these processes result in extremely low defect levels in the graphene. Our simple methods for producing patterned doping profiles in graphene films and devices open up a variety of new possibilities for forming complex doping profiles in a simple manner in graphene. This work can enable rapid testing, such as controlled work function tuning, complex doping profiles and simple post-fabrication tuning, of concepts for graphene that may be useful in both interconnect and transparent conductor applications. In addition to graphene doping, we also investigated approaches to the synthesis of few-layer graphene flakes, since current techniques still produce inferior materials. Exfoliation of Graphene Sheets by an Electron Donor Surfactant was demonstrated to generate few-layers graphene flakes that rival the electrical quality of reduce graphene-oxide (rGO) flakes. Last but not least, Diels-Alder adducts on silica were explored as a controllable carbon precursor for pristine graphene; these allow for a rational direct-growth-of-graphene-on-surface reaction mediated by copper catalyst, without the use of flammable precursors, such as methane, that are used in current methods of chemical vapor deposition synthesis of graphene.

In der vorliegenden Arbeit wurde die elektronische Struktur verschiedener undotierter und mit Alkalimetallen beziehungsweise 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethan (F 4 TCNQ) dotierter, polyzyklischer aromatischer Kohlenwasserstoffe (PAK) untersucht. Diese Untersuchungen waren motiviert durch verschiedene Veröffentlichungen in denen supraleitendes Verhalten an unterschiedlichen alkalimetalldotierten PAK beschrieben wurde. Erste Studien erfolgten an undotiertem 1,2:8,9-Dibenzopentacen (DBP) und Pentacen unter Nutzung von Photoelektronenspektroskopie (PES), Elektronenenergieverlustspektroskopie (EELS) und Dichtefunktionaltheorie (DFT). Die spektroskopischen Methoden zeigten für beide Materialien eine große Ähnlichkeit der elektronischen Zustände, vor allem im niederenergetischen Bereich, welche durch die theoretischen Ergebnisse bestätigt wurde. Die elektronische Ähnlichkeit beider Materialien ist im starken Gegensatz zu dem in der Literatur bei Dotierung beobachteten Verhalten, bei dem Pentacen zum Mott-Isolator wird, während DBP Supraleitung zeigt. Weitere Untersuchungen erfolgten an Picen und Coronen. Bandstrukturrechnungen zeigten, dass Picen vermutlich ein stark korreliertes Elektronensystem besitzt. Neben dem mit PES ermittelten Ionisationspotential und der Austrittsarbeit waren auch die mit EELS gemessenen optischen Bandlücken der beiden Materialien sehr ähnlich. Unterschiede zeigten sich hingegen vor allem in der Dichte der gemessenen Zustände von Picen und Coronen am Ferminiveau. Bei der Untersuchung der elektronischen Eigenschaften von mit Kalium-dotierten Picen und Coronen wurde trotz der erfolgreichen Dotierung in keinem der untersuchten Filme eine Zustandsdichte am Ferminiveau beobachtet somit wurde auch keiner der untersuchten Filme metallisch. Dasselbe Verhalten konnte auch für Natrium-dotierte Filme beobachtet werden. Eine Diskussion dieses Ergebnisses, welches im Gegensatz zu der von anderen Gruppen in dotierten Molekülen beobachteten Supraleitung steht, erfolgte im Hinblick auf die Bildung unterschiedlich dotierter Phasen, Elektron-Phonon-Kopplung, der Formierung von Bi-Polaronen und Korrelationseffekten. Für ein weitergehendes Verständnis der dotierungsinduzierten elektronischen Eigenschaften in den untersuchten Molekülen wurden diese nicht nur mit Alkalimetallen, sondern teilweise auch mit elektronenziehenden Molekülen wie F 4 TCNQ interkaliert. Dabei entstanden Kristalle verschiedener Ladungstransfersalze. Eine ausführliche Charakterisierung erfolgte für Picen/F 4 TCNQ-Kristalle, welche im Rahmen dieser Arbeit zum ersten Mal hergestellt und untersucht wurden. Dabei wurde zunächst deren Kristallstruktur mit Röntgendiffraktometrie (XRD) bestimmt. Eine Abschätzung der Größe des Ladungstransfers innerhalb der Molekülpaare aus Picen/ F 4 TCNQ erfolgte über Infrarot- und Bindungslängendaten, die auf diese Weise gefunden Werte wurden zusätzlich durch DFT-Rechnungen untermauert. Transportmessungen zeigten außerdem, dass die hergestellten Kristalle entlang ihrer Hauptwachstumsrichtung Isolatoren sind. Die Untersuchung der elektronischen Eigenschaften wurde mit EELS und PES an Picen/ F 4 TCNQ -Dünnfilmen durchgeführt, welche durch die Verdampfung der Einkristalle hergestellt wurden. Die Molekülpaare zeigen einen Ladungstransfer, der neue elektronische Anregungen im Niederenergiebereich der mit EELS gemessenen Verlustfunktion hervorruft. Im weiteren Verlauf der Arbeit erfolgte eine Diskussion bezüglich des Charakters und der Lokalisierung dieser neuen Anregungen. Bei den PES-Messungen zeigte sich der Ladungstransfer durch energetische Verschiebungen in den gemessen Rumpfniveauspektren sowie durch im Vergleich zu den reinen Materialien deutlich veränderte Ionisationspotentiale. Trotz des erfolgreichen Ladungstransfers und der damit verbundenen Füllung von unbesetzten Zuständen mit Elektronen in F 4 TCNQ wurde jedoch in den Valenzbandspektren keine Emission am Ferminiveau beobachtet. DFT-Rechnungen ermöglichten schließlich Aussagen über den Charakter des Ladunstransfers und die daraus resultierende, fehlende Zustandsdichte am Ferminiveau.

Non-competitive adsorption of polycyclic aromatic hydrocarbons (PAHs) from water onto activated carbon was studied alongside the performance of CO2-activated petroleum coke as a low-cost adsorbent. PAH adsorption was a two-stage process: a short, fast initial period followed by a long, slow period corresponding to the intra-particle diffusion of PAH molecules in macropores and micropores. The adsorption capacity was determined by total surface area accessible to PAH and the availability of active surface chemical groups. The positive dependence of adsorption capacity on surface oxygen groups and temperature was observed, suggesting a chemical nature of PAH adsorption. The interaction between PAH-activated carbon was however, weak and energetically similar to that of hydrogen bonds. Overall, PAH adsorption was an exothermic process that combined physisorption and chemisorption. CO2-activated petroleum coke had a greater SSA-normalized capacity than coal-derived commercial activated carbon (0.26 vs. 0.19 mg/m2). The capacity was significantly increased by post-oxidation to 0.62 mg/m2.

Non-competitive adsorption of polycyclic aromatic hydrocarbons (PAHs) from water onto activated carbon was studied alongside the performance of CO2-activated petroleum coke as a low-cost adsorbent. PAH adsorption was a two-stage process: a short, fast initial period followed by a long, slow period corresponding to the intra-particle diffusion of PAH molecules in macropores and micropores. The adsorption capacity was determined by total surface area accessible to PAH and the availability of active surface chemical groups. The positive dependence of adsorption capacity on surface oxygen groups and temperature was observed, suggesting a chemical nature of PAH adsorption. The interaction between PAH-activated carbon was however, weak and energetically similar to that of hydrogen bonds. Overall, PAH adsorption was an exothermic process that combined physisorption and chemisorption. CO2-activated petroleum coke had a greater SSA-normalized capacity than coal-derived commercial activated carbon (0.26 vs. 0.19 mg/m2). The capacity was significantly increased by post-oxidation to 0.62 mg/m2.

Sites contaminated with polyaromatic hydrocarbons (PAHs) pose serious health and safety risks to the surrounding environment due to their toxicity, persistence and accumulation in the environment. Because certain members of this class have been demonstrated to be both carcinogenic and mutagenic, PAHs are considered as environmental priority pollutants (US EPA). The studies in this thesis provide an efficient, economical and environmentally benign technique for the remediation of PAH contaminated soil/sediment by means of PAH mobilization with surfactant followed with a catalytic hydrogenation in supercritical carbon dioxide (scCO2). / Catalytic hydrogenation of naphthalene, acenaphthylene, ancenaphthene, anthracene, phenanthrene, chrysene and benzo[a]pyrene over alumina supported palladium (5% Pd0/gammaAl2O3) commercial catalyst were investigated in either a batch reaction mode or a continuous reaction system in H2-scCO2 (∼5% v/v). The hydrocarbon compounds were efficiently reduced to their corresponding fully saturated polycyclic hydrocarbon homologs with mild conditions of temperature (90°C) and pressure (60 psi H2 or 3000 psi H2-scCO2). The bacterial reverse mutation assay demonstrated that both the fully and partially hydrogenated products of chrysene and benzo[a]pyrene were devoid of mutagenic activity. / A laboratory study was conducted on the surfactant-assisted mobilization of PAH compounds combined with reagent regeneration and detoxification steps to generate innocuous products. Five minutes of ultrasonication of field contaminated soil with a 3% (w/v) surfactant suspension mobilized appreciable quantities of all PAH compounds. Formulating the Brij 98 surfactant in 0.1 M phosphate buffer (pH 8.0) mobilized the largest quantities of PAH compounds and the recovery of surfactant (>90%) but soil residues exceeded permissible maxima for five- and six-ring analytes. Five successive washes were required to reduce the residual fraction to permissible levels. The mobilized PAH compounds were then detoxified at line by catalytic hydrogenation in a 5% H2-scCO2 (v/v) atmosphere. / New palladium hydrogenation catalysts were fabricated in the laboratory with specific processes on various supports. The hydrogenation of phenanthrene and benzo[a]pyrene in a fixed bed micro reactor demonstrated that the catalyst that was fabricated from organosoluble precursor loaded on aluminum oxide (2.5% Pd0/gammaAl2O3) was four times more efficient than the commercial catalyst that was used for PAH hydrogenations.

Polycyclic aromatic hydrocarbons (PAHs) are a group of toxic air pollutants formed during incomplete combustion and are ubiquitously distributed in the environment. To determine particle-bound PAHs in archived PM2.5 samples taken with low flow rate in Atlanta, a sensitive and robust method was developed for measuring 28 PAHs and methyl PAHs in PM samples using isotope dilution gas chromatography/high resolution mass spectrometry (GC/HRMS). The method was then used to analyze PM2.5 samples collected at three sites (rural, urban, suburban-highway) from the Assessment of Spatial Aerosol Composition in Atlanta (ASACA) network. Distinct seasonal and spatial variations were observed in PAH concentration. Particle-bound PAH levels were significantly higher in winter than in summer. The suburban-highway site had higher PM2.5-bound PAH concentration than did the urban site, and the rural site had the lowest PAH levels. Retene, a proposed biomass burning tracer, captured both the high leaves-grasses-bushes-branches burning season and the high wood burning months, suggesting that it might be a better marker for all biomass burning, while potassium ion might be a more specific tracer for wood burning. Human exposure to PAHs can be assessed by characterizing their hydroxy PAH (OH-PAH) metabolites in urine samples. A method was developed to measure 24 urinary OH-PAHs, metabolites of 8 parent PAHs, using enzymatic de-conjugation, automatic liquid-liquid extraction, and GC/HRMS. A study was then carried out to evaluating the variability of the urinary biomarker levels in a non-occupationally exposed non-smoking reference group. Levels of urinary PAH metabolites varied widely both within-subject and between-subjects and the within-day variance far exceeded the between-day variance. There were also considerable temporal correlations for these biomarkers. Sample size calculations were conducted and taking 24-hour voids would require the least number of subjects, which should be considered during epidemiological study design. Finally, a study was conducted to evaluate exposure to ambient PAHs in an urban setting among 8 non-occupationally exposed non-smoking volunteers employing both personal air sampling and urine biomonitoring. PAH levels varied largely in air samples taken at home, at work, and while driving or jogging. Monitoring urinary OH-PAH levels can capture both inhalation and dietary exposures. Total inhaled PAH was correlated with total excreted OH-PAHs, suggesting that by combining personal air sampling and biomonitoring, exposure to environmental PAHs can be well characterized even for low-level exposure.

The research described in the thesis details the investigation of build-up and wash-off process kinetics of Polycyclic Aromatic Hydrocarbons (PAHs) and heavy metals in urban areas. It also discusses the design and development of a rainfall simulator as an important research tool to ensure homogeneity and reduce the large number of variables that are usually inherent to urban water quality research. The rainfall simulator was used to collect runoff samples from three study areas, each with different land uses. The study areas consisted of sites with typical residential, industrial and commercial characteristics in the region. Build-up and wash-off samples were collected at each of the three sites. The collected samples were analysed for a number of chemical and physico-chemical parameters. In addition to this, eight heavy metal elements and 16 priority listed PAHs were analysed in five different particle size fractions of the build-up and wash-off samples. The data generated from the testing of the samples were evaluated using multivariate analysis, which reduced the complexity involved in determining the relative importance of a single parameter in urban water quality. Consequently, variables and processes influencing loadings and concentrations of PAHs and heavy metals in urban stormwater runoff from paved surfaces at any given time were identified and quantified using Principal Component Analysis (PCA). Furthermore, the process kinetics found were validated using a multivariate modelling approach and Partial Least Square (PLS) regression, which confirmed the transferability of chemical processes in urban water quality. Fine particles were dominant in both the build-up and wash-off samples from the three sites. This was mirrored in the heavy metal and PAH concentrations at the three sites, which were significantly higher in particles between 0.45-75μm than in any other fraction. Thus, the larger surface area and electrostatic charge of fine particles were favourable in sorbing PAHs and heavy metals. However, factors such as soil composition, total organic carbon (TOC), the presence of Fe and Mn-oxides and pH of the stormwater were all found to be important in partitioning of the metals and PAHs into different fractions. Additionally, PAHs were consistently found in concentrations above their aqueous solubility, which was attributed to colloidal organic particles being able to increase the dissolved fraction of PAHs. Hence, chemical and physico-chemical parameters played a significant role in the distribution of PAHs and heavy metals in urban stormwater. More importantly, the research showed the wide range of factors that distribute metals and PAHs in an urban environment. Furthermore, it indicated the need for monitoring these parameters in urban areas to ensure that urban stormwater management measures are effective in improving water quality. The build-up and wash-off process kinetics identified using PCA at the respective land uses were predicted using PLS and it was found that the transferability of the governing processes were high even though the PAHs and metal concentrations and loads were highly influenced by the source strength at each site. The increased transferability of fundamental concepts in urban water quality could have significant implications in urban stormwater management. This is primarily attributed to common urban water quality mitigation strategies relying on studies based on physical concepts and processes derived from water quantity studies, which are difficult to transfer between catchments. Hence, a more holistic approach incorporating chemical processes compared to the current piecemeal solutions could significantly improve the protection of key environmental values in a region. Furthermore, urban water quantity mitigation measures are generally designed to reduce the impacts of high-flow events. This research suggests that fairly frequent occurring rainfall events, such as 1-year design rainfall events, could carry significant heavy metal and PAH concentrations in both particulate and dissolved fractions. Hence, structural measures, designed to decrease quantity and quality impact on receiving waters during 10 or 20-year Average Recurrence Interval (ARI) events could be inefficient in removing the majority of PAHs and heavy metals being washed off during more frequent events. The understanding of physical and chemical processes in urban stormwater management could potentially lead to significant improvements in pollutant removal techniques which in turn could lead to significant socio-economic advantages. This project can serve as a baseline study for urban water quality investigations in terms of adopting new methodology and data analysis.

Diss. (sammanfattning) Uppsala : Uppsala universitet, 2007. / Härtill 4 uppsatser.

Thesis (Ph.D.)--McMaster University (Canada), 1996. / Source: Dissertation Abstracts International, Volume: 58-06, Section: B, page: 3006. Adviser: B. E. McCarry.