ABSTRACT Hydrophobic organic pollutants (HOPs) are in general characterized by high toxicity, long environmental half-life and high bio-accumulation factors. Due to their hydrophobicity, HOPs tend to sorb onto particles in environment. The influence of the dissolved organic matters (DOMs) on the sorption partition coefficient is observed because of their interactions with HOPs. This binding between DOM and HOPs increases apparent solubility and mobility of the HOPs in natural aquatic system. On the purpose of obtaining data closer to the real world, many aquatic factors, such as the concentration and types of DOM, pH value and ionic strength, are studied intensively recently. There are many studies about the mechanisms in the association of DOM and HOPs. Most of them assume achievement of equilibrium in their measurement. Recently, it was reported (Engebretson and von Wandruszka, 1998) that slow, revering, and even oscillating kinetics are observed. It is great concern and interest to those related studies in literatures. Complicated kinetic may in fact be a cause of the reproducibility problems for measurements of HOPs associated with both humic acid and metals. As such, by monitoring fluorescence intensity, we investigate the equilibrium kinetic of pyrene in HA solutions. In this study, results show that there are two stages of the fluorescence intensity after pyrene spiked into HA solutions: First, the fluorescence intensity decreases steeply due to the first dispersion of pyrene and the reaction of pyrene and HA (the front is dominance). Secound, fluorescence intensity decreases gently because of wall-effect. The dispersion rate of pyrene in HA solutions is difference with HA molecular size and quantity. As the ionic strength rising, cations reacting with specific binding sites on HA, the molecules¡¦ configuration of HA is changed, and less obstruct for dispersing of pyrene. It works as well as little molecular quantity. For second stage when ionic strength rising, wall- associations is less because of the hydrophobic-binding of pyrene and LHA is more stronger. Furthermore, it is not observed the ¡§migration¡¨ of Mg2+ within the LHA molecular structure as described by Engebretson and von Wandruszka .The reasons that make different results may depend on the species of humic acid. Therefore, the observations of Engebretson and von Wandruszka could not be used directly questioning those results in literatures. In addition, the effects of various cations (Mg2+, Ca2+and Sr2+) on Kdom are studied. It is believed different cation reacts with different specific binding sites on HA. As such, both charge density and affinity of cation with specific binding sites on HA should be considered in discussing the effects of metal ionic on the binding constants between PAHs and DOM.

The biodegradability and physicochemical properties of unsubstituted and methylated polycyclic aromatic hydrocarbons (PAHs) were investigated. The focus was on the development of models expressing the influence of molecular structure and properties on observed behavior. Linear free energy relationships (LFERs) were developed for the estimation of aqueous solubilities, octanol/water partition coefficients, and vapor pressures as functions of chromatographic retention time. LFERs were tested in the estimation of physicochemical properties for twenty methylated naphthalenes containing up to four methyl substituents. It was determined that LFERs can accurately estimate physicochemical properties for methylated naphthalenes. Twenty unsubstituted and methylated PAHs containing up to four aromatic rings were biodegraded individually by Sphingomonas paucimobilis strain EPA505, and Monod-type kinetic coefficients were estimated for each PAH using the integral method. Estimated extant kinetic parameters included the maximal specific biodegradation rate, the affinity coefficient, and the inhibition coefficient. The generic Andrews model adequately simulated kinetic data. The ability of PAHs to serve as sole energy and carbon sources was also evaluated. Quantitative structure-biodegradability relationships (QSBRs) were developed based on the estimates of the kinetic and growth parameters. A genetic algorithm was used for QSBR development. Statistical analysis and validation demonstrated the predictive value of the QSBRs. Spatial and topological molecular descriptors were essential in explaining biodegradability. Mechanistic interpretation of the kinetic data and the QSBRs provided evidence that simple or facilitated diffusion through the cell membranes is the rate-determining step in PAH biodegradation by strain EPA505. A kinetic experiment was conducted to investigate biodegradation of PAH mixtures by strain EPA505. The investigation focused on 2-methylphenanthrene, fluoranthene, and pyrene, and their mixtures. Integrated material balance equations describing different interaction types were fitted to the depletion data and evaluated on a statistical and probabilistic basis. Mixture degradation was most adequately described by a pure competitive interaction model with mutual substrate exclusivity, a fully predictive model utilizing parameters estimated in the sole-PAH experiments only. The models developed in this research provide insight into how molecular structure and properties influence physicochemical properties and biodegradability of PAHs. The models have considerable predictive value and could reduce the need for laboratory testing.

No description available.

Accurate characterization of risk of adverse ecological effects related to contaminated sediment presents a particularly difficult challenge. A series of studies has been conducted to investigate the utility of various tools for assessment of sediment toxicity. The goal of this research was to provide information which could help increase the accuracy with which predictions of toxicity could be made at hazardous sites. A calibration study was conducted using model PAHs, PCBs, a binary PAH mixture and a coal-tar mixture. This study was a collaborative effort among five university-based Superfund Research Programs (SRPs). Each program, with the help of funding through the NIEHS Superfund Research Program, has developed a chemical-class specific assay to estimate toxicity of contaminants in sediment. This suite of bioassays expands the range of data typically obtained through the use of standard aquatic toxicity assays. A series of caged in situ exposure studies has been conducted using juvenile Chinook salmon and Pacific staghorn sculpin in the Lower Duwamish Waterway. The study aimed to investigate the utility of selected biomarkers in evaluating the relationship between contaminants present in environmental samples and response in receptors following an in situ caged exposure. Results found that DNA adducts detected in exposed fish were significantly higher than controls in 2004 and 2006, and DNA adducts appear to be a reliable indicator of exposure, although no dose-response relationship was present. Western blot analysis of CYP1A1 was not indicative of exposure levels. The final study conducted was concerned with evaluating the utility of using solid phase microextraction (SPME) fibers in situ to evaluate contaminated sediment. Levels of PAHs and PCBs in sediment often exceeded sediment quality guidelines; however, results from aquatic toxicity bioassays using Hyalella azteca were mostly negative, thus levels of contaminants detected on SPME fibers could not be associated with adverse effects in Hyalella. However, regression analysis of total PAHs present in sediment and levels of PAHs detected in porewater SPME fiber samplers, which were placed 5 cm into the sediment for 30 days, revealed a strongly correlated linear relationship (R2 = .779). Normalization of the sediment data to total organic carbon was performed to determine if the trend would remain present, and the linear relationship was again confirmed (R2 =.709).

No description available.

Cachaça é a terceira das bebidas alcoólicas fermento-destilado mais consumida no mundo, com uma produção de aproximadamente 2,5 litros de bilhões por ano. Tradicionalmente, a cachaça é produzida a partir da destilação do mosto fermentado da cana-de-açúcar. Porém, ela pode sofrer a contaminação por HPAs (Hidrocarbonetos Policíclicos Aromáticos) quando a cana-de-açúcar utilizada na sua produção é queimada antes da sua colheita. Objetivando a distinção entre as amostras de cachaça produzidas a partir da cana-de-açúcar colhida após a queima ou não dos canaviais, foram analisados 15 HPAs em 26 amostras de cachaça produzidas com cana-de-açúcar queimada e 105 amostras de cachaça produzidas com cana-de-açúcar não queimada. As amostras de cachaça foram previamente concentradas por extração em fase sólida (SPE) e analisadas por cromatografia liquida de alta eficiência (HPLC), acoplada a um detector de fluorescência. Este método apresentou uma boa separação cromatográfica para a análise dos seguintes HPAs estudados: naftaleno, acenafteno, fluoreno, fenantreno, antraceno, fluoranteno, pireno, benzo(a)antraceno, criseno, benzo(b)fluoranteno, benzo(k)fluoranteno, benzo(a)pireno, dibenzo(a,h)antraceno, benzo(g,h,i)perileno e indeno(1,2,3-c,d)pireno. O método cromatográfico apresentou bons limites de detecção (5,68E-04 a 45,4 µg L-1), boa porcentagem de extração e recuperação (81,5 ± 9 % a 113 ± 5 %) e uma boa reprodutibilidade (> 90,0 %). As amostras produzidas a partir de cana-de-açúcar queimada apresentaram teores médios totais dos HPAs de 21,1 µg L-1, enquanto que as amostras produzidas com cana-de-açúcar não queimada apresentaram teores médios totais dos HPAs de 1,91 µg L-1. Os dados analíticos foram tratados por meio de análise multivariada (PCA, FA, PLS, DA, LDA, QDA e CDA), possibilitando uma boa distinção entre as amostras produzidas com cana queimada e não queimada. Os resultados dos modelos estatísticos revelaram uma elevada probabilidade (85,0 %) na diferenciação entre estes dois grupos de cachaça / Cachaça is the third most consumed fermented alcoholic beverage in the world, with a production of nearly 2.5 billion liters a year. Traditionally, cachaça is made from the distillation of the fermented sugar cane juice. However, it may be contaminated by PAHs (Polycyclic Aromatic Hydrocarbons) when the sugar cane used for its production is burned before harvesting. Aiming at distinguishing spirits made from burned and non-burned sugar cane, 15 PAHs in 26 cachaças samples obtained from non-burned and 105 cachaça samples obtained from burned sugar cane have been analyzed. The cachaça samples were previously concentrated by solid phase extraction (SPE) and analyzed by high performance liquid chromatography (HPLC), coupled with a fluorescence detector. This method presented good chromatographic separation for the analysis of the following PAHs: naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz(a)anthracene, chrysene, benz(b)fluoranthene, benz(k)fluoranthene, benz(a)pyrene, dibenz(a,h)anthracene, benz(g,h,i)perylene, and indeno(1,2,3- c,d)pyrene. The chromatographic method showed good detection limits (5.68E-04 to 45.4 ? g L-1), good index for the clean up percentage and recovery (from 81.5 ± 9% to 113 ± 5%) and a good reproducibility (> 90.0%). The samples obtained from burned sugar cane presented 21.1 ? g L-1 total PAHs average contents while the ones obtained from non-burned sugar cane showed PAHs average contents of 1.91 ?g L-1. Such analytical data were treated by means of the multivariate statistical methods (PCA, FA, PLS, LDA, QDA and CDA), thus allowing good distinction among the samples obtained from burned and non-burned sugar cane. Results of the Abstract IQSC-USP statistical models presented high probability (85.0%) for the distinction between these two groups of spirits.

Os hidrocarbonetos policíclicos aromáticos (HPAs) por serem considerados contaminantes persistentes, pela sua ubiqüidade no meio ambiente e pelo reconhecimento de sua genotoxicidade, têm estimulado atividades de pesquisa com o objetivo de determinar e avaliar as origens, transporte, transformação, efeitos biológicos e a acumulação em compartimentos de ecossistemas aquático e terrestre. Nesta dissertação, a matriz estudada foi o sedimento coletado na represa do Parque Pedroso em Santo André, SP. A técnica analítica empregada foi a cromatografia líquida em fase reversa com detector UV/Vis. O tratamento dos dados foi estabelecido durante o processo de desenvolvimento da metodologia para que houvesse confiabilidade nos resultados. As etapas envolvidas foram avaliadas usando o conceito da Validação de Ensaios Químicos. Os parâmetros selecionados para a validação analítica foram Seletividade, Linearidade, Intervalo de Trabalho, Sensibilidade, Exatidão, Precisão, Limite de Detecção, Limite de Quantificação e Robustez. Esses parâmetros apresentaram resultados satisfatórios, o que permite a aplicação da metodologia desenvolvida, sendo ainda um método simples que permite a minimização da contaminação e da perda de compostos por excesso de manipulação. Para os HPAs estudados não foram encontrados resultados positivos, acima do limite de detecção, em nenhuma das amostras coletadas na primeira fase. Já na segunda coleta foram encontradas pequenas alterações principalmente em acenaftileno, fluoreno e benzo[a]antraceno. Embora a área se encontre preservada, já se notam pequenos sinais de contaminação. / The polycyclic aromatic hydrocarbons (PAHs), by being considered persistent contaminants, by their ubiquity in the environment and by the recognition of their genotoxicity, have stimulated research activities in order to determine and evaluate their sources, transport, processing, biological effects and accumulation in compartments of aquatic and terrestrial ecosystems. In this work, the matrix studied was sediment collected at Pedroso Park\'s dam at Santo André, SP. The analytical technique employed was liquid chromatography in reverse phase with a UV/Vis detector. Statistics treatment of the data was established during the process of developing the methodology for which there was reliable results. The steps involved were evaluated using the concept of Validation of Chemical Testing. The parameters selected for the analytical validation were selectivity, linearity, Working Range, Sensitivity, Accuracy, Precision, Limit of Detection, Limit of quantification and robustness. These parameters showed satisfactory results, allowing the application of the methodology, and is a simple method that allows the minimization of contamination and loss of compounds by over-handling. For the PAHs tested were no found positive results, above the limit of detection, in any of the samples collected in the first phase. But, at the second collection, were found small changes mainly acenaphthylene, fluorene and benzo[a]anthracene. Although the area is preserved, it is possible to realize little signs of contamination.

While investigating strategies to prepare precursors to highly strained buckybowls, we focused our attention on the Lewis acid aldol cyclization of 1-acenaphthenone derivatives which has been shown to produce a cyclic tetramer as a byproduct. Surprisingly, despite the interesting structural and electronic properties that have recently been observed as a result of the incorporation of eight-membered rings into polycyclic aromatic hydrocarbons, this cyclic tetramer has largely been ignored. As a result of this, we set our sights on the isolation and characterization of this cyclic tetramer. The initial approach employed subjecting 1-acenaphthenone to the most common conditions used in trimerization—TiCl4 in boiling o-dichlorobenzene. Surprisingly, this resulted in exclusive formation of the cyclic tetramer, which we have named tridecacyclene. The results of these studies were promising, establishing structural characterization and supramolecular assemblies with C60 in the solid-state. The optoelectronic properties revealed a significantly lower reduction potential (~0.4 eV) than the trimeric species of 1-acenaphthenone. This is attributed to the central eight-membered ring of tridecacyclene. Reduction proceeded through two single-electron processes. Further examining the electrochemical properties, we were able to gain new insight into the relation of structure and aromaticity. Reduction of tridecacyclene with potassium metal allowed us to characterize the radical anion and dianion through NMR and UV-Vis spectroscopy. Solid-state analysis of the dipotassium adduct revealed that despite the propensity of the reduced form of cyclooctatetraene derivatives to flatten as the molecule adopts a Hückel aromatic core, tridecacyclene maintains its tub shape. Significant bond equalization was observed in the center eight-membered ring—a strong indication of a delocalized π-system. This was supported by harmonic oscillator model of aromaticity calculations of the central ring with the value increasing from 0.09 to 0.48 where a value of 1 indicates a fully aromatic ring. Tridecacyclene represents the precursor to a fragment of the fullerene C240. A broad variety of reactions to facilitate the necessary strain inducing C–C bonds to formthe fragment have been attempted. To date, we have not been able to synthesize the fragment. However, the parent molecule tridecacyclene shows great promise in the development of non-aqueous redox flow batteries and is currently being explored for this purpose in our laboratory.

This work detailed the physical and chemical characterization of oil water mixtures prepared using fresh and weathered Macondo related oils under different conditions of mixing energy/time and in the presence/absence of chemical dispersants. The results indicated that WAFs produced consistent, droplet free solutions for both source and weathered oils with concentration ranges that represented the soluble components of the oil used. Chemically enhanced WAFs prepared with the source oil generated a large amount of micron-size droplets; however the viscosity of the weathered oils were a limiting factor for the preparation of CEWAFs with weathered oils. Droplet size distributions were influenced by the amount of energy in the system and the oil weathering stage, when high energy WAFs were made the increase in weathering of the oil resulted in the formation of smaller droplets that were more stable over time.

As a potential bioremediation system for contaminated soils, I evaluated the use of an arbuscular mycorrhizal (AM) fungus, Glomus intraradices on roots and shoots uptake of polycyclic aromatic hydrocarbons (PAHs), alkyl PAHs, and toxic metals in Echinacea purpurea, in using a controlled 20-week greenhouse study and a complimentary 2-year field study. E. purpurea seeds were either inoculated with the mycorrhizal fungus (AM) or not inoculated (non-AM) and grown in soil provided by the National Capital Commission (NCC) that have known contamination. In the greenhouse study, AM inoculation increased the uptake of alkyl PAHs in the roots of E. purpurea. The AM inoculation showed no effect on root uptake of PAHs and toxic metals over the 20-week study period. However, when I calculated the uptake rates (k1) for PAHs between both treatments, the AM treated roots ha 10-fold higher k1 values than non-AM treated roots. The soil concentrations of PAHs were found to increase over time with AM inoculation, suggesting, that AM fungi are causing a solvent depletion through root uptake of minerals and carbon, which concentrates the more hydrophobic PAHs in soils. Alkyl PAHs and metals showed no change over time amongst any of the treatments. Assessing the performance of AM fungi on the uptake of contaminants under field conditions, only PAHs showed increased bioaccumulation in the shoots of E. purpurea with AM inoculation. Alkyl PAHs and metals in plant material were unaffected by the AM inoculation, but increased significantly from year 1 to year 2. The uptake rates among treatments were similar, with non-AM roots having slightly greater uptake. Soil concentrations of PAHs and alkyl PAHs were unaffected over the course of the experiment. Our control soil, however, showed significant increases in concentration from year 1 to year 2 with alkyl PAHs. These results quantified the influence of AM hyphae-mediated uptake of organic and inorganic contaminant transfer from soil to plants and the bioaccumulation kinetics for contaminants by E. purpurea that will be useful for environmental models and phytoremediation strategies.