The distribution of butyltin compounds (BTs) in the sediments and seawater, at the river outfalls, fishing ports, shipyards, and industrial zone docks of Kaohsiung Harbor, Taiwan were investigated. Twenty sediment and seawater samples were collected from various locations in the Harbor in 2006, and analyzed for monobutyltin (MBT), dibutyltin (DBT), and tributyltin (TBT). Results showed that the concentration of total BTs varied from 1.5 to 151 ng/g in sediment samples, with TBT being the major component of the sediment samples. This suggests that sediments could be the most possible sink of TBT brought by the sorption mechanism. The concentrations of BTs ranged from 9.7 to 270 ng/L in seawater samples, whereas DBT and MBT, the degradation byproducts of TBT, were mainly the most abundant BT compounds of the seawater samples. This indicates that the abiotic or biotic degradation potential of TBT was significant. Spatially, the highest concentrations of BTs were observed in both water and sediment samples collected from the shipyard and fishing port areas. This indicates that the shipping related activities (e.g., navigation, ship repair, and ship building), would contribute most of BTs in the environment. Results show that the concentrations of degradation products (DBT and MBT) were related closely to temperature, salinity, dissolved oxygen (DO), and chlorophyll-a of the seawater. This implies that seasonal changes of the water parameters controlled the degradation of TBT in seawater. The observed levels of BT compounds in both seawater and sediments were much higher than those required to induce toxic effects on marine organisms suggesting that appropriate TBT control strategies should be taken in Kaohsiung Harbor. Sediment samples were collected from the river outfalls, fishing ports, shipyards, and industrial zone docks of Kaohsiung Harbor, Taiwan to evaluate the distribution of polycyclic aromatic hydrocarbons (PAHs) in sediments. Collected sediment samples from 12 locations were analyzed for 17 different PAHs, organic content, and grain size. The results show that the total PAH concentrations varied from 472 to 16,201 ng/g dry wt, with a mean concentration of 5,764 ng/g dry wt The highest PAH concentrations were from the industrial zone docks situated in south Kaohsiung Harbor, ranging from 8,788 to 16,201 ng/g dry wt Among those sediment samples, the 5-, 6-ring PAHs were predominant PAH congeners in sediments, ranging from 42 to 71%. However, the dominant PAH congeners were 2-, 3-ring PAHs (37 to 42%) collected from steel industrial zone docks. This indicates that the sources for the PAH contamination at steel industrial zone docks were different from the other zones in Kaohsiung Harbor. According to the diagnostic ratios, the possible source of PAHs in the industrial zone dock could be coal combustion while in the other zones it could be petroleum combustion. The total PAH levels were expressed as the total toxic equivalent (TEQcarc). The total TEQcarc varied from 55 to 1,964 ng TEQ/g dry wt. Higher total TEQcarc values were found at industrial zone docks (from 1,404 to 1,964 ng TEQ/g dry wt). As compared with the US Sediment Quality Guidelines (SQGs), the observed levels of PAHs at industrial zone docks exceeded the effects range low (ERL), and could thus cause acute biological damage. However, the lower levels of PAHs at the other zones would not exert adverse biological effects. Results would be helpful in developing strategies for sediment remediation in Kaohsiung Harbor.

In this study our purposes were to investigate the spatial distribution and seasonal variation of polycyclic aromatic hydrocarbons (PAHs) in the dissolved and particulate phase of PAHs in Er-Jen River. In addition, the potential sources of PAHs in Er-Jen River were investigated not only by finger printing, but also principal component analysis (PCA) and hierarchical cluster analysis (HCA). ¡@¡@Concentrations of dissolved and particulate PAHs ranged from 13.8 to 516 ng/L and from 4.05 to 55.9 ng/L, respectively. In March (dry season), concentrations of dissolved and particulate PAHs ranged from 38.3 to 186 ng/L and from 4.05 to 25.9 ng/L, respectively. In addition, concentrations of dissolved and particulate PAHs ranged from 32.3 to 82.8 ng/L and from 14.8 to 85.3 ng/L, respectively in September (wet season). The highest total PAH concentration in this area was found in Station Er-3 which is located on a tributary of Er-Jen River. Total PAH concentrations in wet season were higher than those found in dry season for all stations in Er-Jen River, except for station Er-3, which suggesting that different geography might be the reason. ¡@¡@Results from correlation analysis indicated that distributions of PAH concentrations for particulate phase in Er-Jen River correlated well with flow rate, suspended solid concentrations and salinity. Total PAH concentration of station Er-2, which was located at the downstream Er-Jen River, was highly correlated with salinity; while total PAH concentrations in other stations were mainly affected by flow rate, suspended solid concentrations and some potential sources of pollution. Results from PCA, HCA and finger printing all indicated the origins of PAHs were complex sources in the study area, including pyrogenic, petrogenic and diagenetic/biogenic origins. The origins of PAHs in dissolved phase were mainly from both pyrogenic and petrogenic sources; while those in particulate phase were mainly from pyrogenic sources. In addition, the pyrogenic origins in both dissolved and particulate phase were mostly from liquid fuel combustion. In wet season, howerer, diagenetic/biogenic origins were also found in particulate phase at the sampling sites of Er-Jen River. ¡@¡@The annual total PAH fluxes of Er-Jen River were estimated to be 23.1 kg For dissolved phase, the average daily fluxes in dry and wet season were 5.9 g/day and 65.8 g/day, respectively, with an annual mean fluxe of 11.3 kg/year. For particulate phase, the mean daily fluxes in dry and wet season were 0.8 g/day and 76.2 g/day, respectively, with an annual mean flux of 11.8 kg/year. In general, the total PAH fluxes in wet season were higher than dry season. The total annual PAH fluxes in Er-Jen River were generally less than those reported worldwide, and comparable to those in San Francisco River in USA, but higher than those in Le Havre River in France.

Water, suspended particle and sediment samples from Kao-ping estuary were collected and measured for concentrations of polycyclic aromatic hydrocarbons (PAHs) during March 2004 and April 2005. In addition, sediments from neighboring coastal area were also analyzed to estimate distribution, transportation and possible sources of PAHs. Total PAH concentrations varied from 33.0 to 910 ng/g dry weight (dw) in coastal sediments, and diagnostic ratios reflect a mixed sources of petrogenic and pyrolytic inputs. Due to the contribution of Kao-ping River, spatial distribution of PAH concentrations at coastal sediments near river mouth varied dramatically. Results of hierachical cluster analysis showed that PAH concentration distribution was influenced by Kao-ping canyon, and biogenic source might be the major PAH source for offshore sediments. Total PAH concentrations in river sediment varied from 63.0 to 720 ng/g dw. Higher concentration was measured between the Water Main pipe and Shuang-yuan Bridge, and possible sources were from both petrogenic and pyrolytic sources. Sediment of Dung-gang harbour had highest concentration, 28,000ng/g dw, in this study, which was contributed from petrogenic sources due to its intensive boating activities. Except fluorene and phenanthrene in harbour sediments, individual PAH concentrations of other sediments are lower or near the Effect Range Low value, concentrations might lead to possible adverse effects upon organism. Total PAH concentrations varied from 5.0 to 82.0 ng/L in suspended particulate phase and from 5.5ng/L to 46.0ng/L in dissolved phase, respectively. Most of high molecular weight PAH concentrations (>5-ring PAHs) in dissolved phase were below method detection limits. The partition coefficients¡]Koc¡^values of PAHs were 1 to 2 orders higher than predicted values. It might be attributed to soot particles which have extremely high sorption capacities. Correlation coefficients between total PAH concentrations in sediments versus total organic carbon¡]TOC¡^ and fine particle content¡]<63£gm%¡^were significant ¡]R=0.575, 0.800, 0.851 and 0.657, P<0.01¡^. In addition, PAHs in suspended particulate phase and dissolved phase were also significantly correlated to particulate organic carbon¡]POC¡^ and dissolved organic carbon¡]DOC¡^, respectively. The distribution of calculated PAH concentrations from organic carbon was higher in surface water than bottom water. Unlike salinity, there was no decreasing or increasing trend of these concentrations among river samples. It is possible that contamination was not come from upstream, but from estuary area where plume was lifted and diffused upstream by neat seawater. The flux in Wan-da Bridge was higher than downstream estuary area that might be due to PAH concentrations reduction by sedimentation or degradation.

Refinery operations have been associated with a wide variety of atmospheric emissions consisting of criteria air pollutants, volatile organic components, hazardous air pollutants as well as other pollutants. With approximately 100 oil refineries in the Wider Caribbean region (WCR), hydrocarbons in this region pose significant environmental and human health risks. One of the oldest and largest refineries in the WCR is the Isla Refineriá, which is located on the island of Curaçao, and has been the basis of historical debates and conflict between the public and the local government over the environmental and human health risks. This research aims to establish baseline levels of ambient petrochemical emissions in Curaçao, specifically polycyclic aromatic hydrocarbons (PAHs), inhalable particulate matter (PM10) and sulfur dioxide (SO2), and to evaluate through comparative literature analysis and recommended public health guidelines the potential health risks in Curaçao. In addition, source elucidation of PAHs was conducted using concentration profiles, distribution profiles, binary diagnostic ratios and factor analysis. Passive air samplers with polyurethane foam collection disks (PAS-PUFs) were deployed in 2011 (n=43) and in 2014 (n=30) to measure ambient PAH concentrations. Ambient PAH concentrations ranged from 1.2 ng/m3 in 2011 and 27.3 to 660.1 ng/m3 in 2014, demonstrating no temporal differences. However, there were highly significant spatial differences, with the samples downwind of the refinery having significantly higher ambient PAH concentrations than those upwind in 2014. Source elucidation revealed the ambient PAHs were dominated by petrogenic emission sources (i.e., refinery) in the 2011 and the 2014 downwind samples, whereas the 2014 upwind locations were equally influenced by both petrogenic (i.e., refinery) and pyrogenic (i.e., vehicle emissions) sources. Available hourly, daily and monthly PM10 and SO2 measurements were downloaded from June 2010 through December 2014 from two local air monitoring stations. Concentrations of both PM10 and SO2 in Curaçao are among the highest reported globally, demonstrating an increasing trend over time and exceed current public health guidelines recommended by local and international agencies. It is plausible that the residents of Curaçao may experience health effects often associated with PM10 and SO2, however the epidemiological evidence is inadequate to infer causality between health effects and long-term exposures. Using the USEPA’s risk analysis methodology the resulting cumulative lifetime cancer risk estimates from PAH inhalation were below the level of concern (1.0 x 10-4). In contrast, by evaluating the potency adjusted concentrations relative to the most toxic compound (benzo[a]pyrene), age class (children and adults) extrapolated and site specific risks indicated levels exceeding the upper bound acceptable risk (1.0 x 10-4) by almost two orders of magnitude suggesting the need for remediation.

The overall objective of the present study was to evaluate the effectiveness of using a variety of hydrophobic biopolymers and hydrophobic biopolymer-coated sands as technically and economically feasible in-situ sediment amendments or alternative capping materials on a laboratory scale. Cutin from tomato peels, cellulolytic enzyme lignin from sitka spruce chips, and keratin azure from commercially dyed sheeps wool were isolated, prepared, tested, and evaluated as feasible hydrophobic biopolymers for the removal of selected Polycyclic Aromatic Hydrocarbons (PAHs). Testing included chemical and physical characterization, as well as the measurement of kinetics and equilibrium sorption parameters for the sorbates naphthalene, phenanthrene, and pyrene as model hydrophobic organic contaminants. Tomato peel cutin exhibited the largest overall affinity for PAHs, however, keratin azure was selected for further evaluation as the most feasible material due to its low preparation cost. Amendment of industrial sand with a stable, uniform, cross-linked keratin azure derivative was achieved to produce hydrophobic biopolymer-coated sand products containing zero, moderate, and high mass fractions of sand. Chemical and physical material parameters, as well as kinetics and equilibrium sorption parameters for the sorbates naphthalene, phenanthrene, and pyrene, were then obtained for the coated sand products. This allowed simple finite difference modeling of PAH fate and transport through a thin cap comprised of the same, insight into the specific sorption mechanisms involved, and information which could prove useful in predicting potential of keratin products to provide a suitable capping material. Conclusions and recommendations for future research focus on the technical and economical feasibility of the prepared hydrophobic biopolymers and hydrophobic biopolymer-coated sand products as capping or in-situ sediment amendments. / text

The accumulation of persistent contaminants is a significant issue for the health of aquatic environments. This study aims to determine the effects of polycyclic aromatic hydrocarbons (PAH) on the stress response of fish by monitoring plasma cortisol levels and the expression of key hypothalamic-pituitary-interrenal (HPI) stress axis regulators. Injection of benzo(a)pyrene (BaP), a ubiquitous PAH, induced a differential dose- and time-dependentcortisol response in rainbow trout and brown bullhead. BaP exposure also elicited a species-specific transcriptional response at all levelsof the HPI axis.Similarly, the HPI axis response to a standardized emersionstressor revealed species-specific differences. In the field, exposure of different brown bullhead populations to sediment with complex PAH mixtures did not consistently affect cortisol levels and providedno evidence of genetic adaptation of the stress response. Thus, future studies are needed to bridge the gap in our understanding between the laboratory and field effects of PAHs on the stress response of fish.

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.

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 (&sim;5% v/v). The hydrocarbon compounds were efficiently reduced to their corresponding fully saturated polycyclic hydrocarbon homologs with mild conditions of temperature (90&deg;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.