Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental contaminants known for their photoinduced toxicity. There are two mechanisms through which this may occur: photosensitization and photomodification. Photosensitization generally leads to the production of singlet oxygen, a reactive oxygen species (ROS), which is highly damaging to biological molecules. Photomodification of PAHs, usually via oxygenation, results in the formation of new compounds (oxyPAHs), and can occur under environmentally relevant levels of actinic radiation. <br /><br /> PAHs and oxyPAHs readily adsorb to the organic phase of particulate matter in the environment such as sediments. It is logical to conclude that sediment transport will also facilitate the transport of these contaminants, and it has been shown that in the course of transport, degradative processes evoke a change in the profile of the PAHs present. Sediment samples taken along a transect from Hamilton Harbour were fractionated, and analyzed using a 2D HPLC method. All sediments contained intact and modified PAHs, although a marked change was noted in the profile of compounds present in the samples, which differ in distance from shore. Fractions of sediment extract were tested for toxicity using a bacterial respiration assay. Toxicity was observed in fractions containing modified PAHs, and was similar to that of intact PAH-containing fractions. <br /><br /> Subsequently, the toxicities of 16 intact PAHs were assessed to <i>Daphnia magna</i> under two ultraviolet radiation (UV) conditions. The toxicity of intact PAHs generally increased in the presence of full spectrum simulated solar radiation (SSR), relative to visible light plus UVA only. To expand the existing data on the effects of PAH photoproducts to animals, fourteen oxyPAHs were also assayed with <i>D. magna</i>, most of which were highly toxic without further photomodification. The data presented highlight the effects of UV radiation on mediating PAH toxicity. The importance of the role of photomodification is also stressed, as several oxyPAHs were highly toxic to <i>D. magna</i>, a key bioindicator species in aquatic ecosystems. <br /><br /> A QSAR model previously developed for <i>Lemna gibba</i> showed that a photosensitization factor (PSF) and a photomodification factor (PMF) could be combined to describe toxicity. To determine whether it was predictive for <i>D. magna</i>, toxicity was assessed as both EC50 and ET50. As with <i>L. gibba</i> and <i>Vibrio fischeri</i>, neither the PSF nor the PMF alone correlated to D. magna toxicity. However, a PSF modified for <i>D. magna</i> did in fact exhibit correlation with toxicity, which was further improved when summed with a modified PMF. The greatest correlation was observed with EC50 toxicity data. This research provides further evidence that models that include factors for photosensitization and photomodification will likely be applicable across a broad range of species. To gain further knowledge of the roles that the variables contributing to the photosensitization and photomodification, a structural equation model was constructed based on the <i>D. magna</i> QSAR. This model accounted for a high amount of variance in six sets of toxicity data, as well as insight into the mechanisms of phototoxicity affecting different aquatic organisms.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental contaminants known for their photoinduced toxicity. There are two mechanisms through which this may occur: photosensitization and photomodification. Photosensitization generally leads to the production of singlet oxygen, a reactive oxygen species (ROS), which is highly damaging to biological molecules. Photomodification of PAHs, usually via oxygenation, results in the formation of new compounds (oxyPAHs), and can occur under environmentally relevant levels of actinic radiation. <br /><br /> PAHs and oxyPAHs readily adsorb to the organic phase of particulate matter in the environment such as sediments. It is logical to conclude that sediment transport will also facilitate the transport of these contaminants, and it has been shown that in the course of transport, degradative processes evoke a change in the profile of the PAHs present. Sediment samples taken along a transect from Hamilton Harbour were fractionated, and analyzed using a 2D HPLC method. All sediments contained intact and modified PAHs, although a marked change was noted in the profile of compounds present in the samples, which differ in distance from shore. Fractions of sediment extract were tested for toxicity using a bacterial respiration assay. Toxicity was observed in fractions containing modified PAHs, and was similar to that of intact PAH-containing fractions. <br /><br /> Subsequently, the toxicities of 16 intact PAHs were assessed to <i>Daphnia magna</i> under two ultraviolet radiation (UV) conditions. The toxicity of intact PAHs generally increased in the presence of full spectrum simulated solar radiation (SSR), relative to visible light plus UVA only. To expand the existing data on the effects of PAH photoproducts to animals, fourteen oxyPAHs were also assayed with <i>D. magna</i>, most of which were highly toxic without further photomodification. The data presented highlight the effects of UV radiation on mediating PAH toxicity. The importance of the role of photomodification is also stressed, as several oxyPAHs were highly toxic to <i>D. magna</i>, a key bioindicator species in aquatic ecosystems. <br /><br /> A QSAR model previously developed for <i>Lemna gibba</i> showed that a photosensitization factor (PSF) and a photomodification factor (PMF) could be combined to describe toxicity. To determine whether it was predictive for <i>D. magna</i>, toxicity was assessed as both EC50 and ET50. As with <i>L. gibba</i> and <i>Vibrio fischeri</i>, neither the PSF nor the PMF alone correlated to D. magna toxicity. However, a PSF modified for <i>D. magna</i> did in fact exhibit correlation with toxicity, which was further improved when summed with a modified PMF. The greatest correlation was observed with EC50 toxicity data. This research provides further evidence that models that include factors for photosensitization and photomodification will likely be applicable across a broad range of species. To gain further knowledge of the roles that the variables contributing to the photosensitization and photomodification, a structural equation model was constructed based on the <i>D. magna</i> QSAR. This model accounted for a high amount of variance in six sets of toxicity data, as well as insight into the mechanisms of phototoxicity affecting different aquatic organisms.

The objective of this study is to examine core-shell type plasmonic metamaterials aimed at the development of materials with unique electromagnetic properties. The building blocks of metamaterials under study consist of gold as a metal component, and silica and precipitated calcium carbonate (PCC) as the dielectric media. The results of this study demonstrate important applications of the core-shells including scattering suppression, airborne obscurants made of fractal gold shells, photomodification of the fractal structure providing windows of transparency, and plasmonics core-shell with a gain shell as an active device. Plasmonic resonances of the metallic shells depend on their nanostructure and geometry of the core, which can be optimized for the broadband extinction. Significant extinction from the visible to mid-infrared makes fractal shells very attractive as bandpass filters and aerosolized obscurants. In contrast to the planar fractal films, where the absorption and reflection equally contribute to the extinction, the shells' extinction is caused mainly by the absorption. This work shows that the Mie scattering resonance of a silica core with 780 nm diameter at 560 nm is suppressed by 75% and only partially substituted by the absorption in the shell so that the total transmission is noticeably increased. Effective medium theory supports our experiments and indicates that light goes mostly through the epsilon-near-zero shell with approximately wavelength independent absorption rate. Broadband extinction in fractal shells allows as well for a laser photoburning of holes in the extinction spectra and consequently windows of transparency in a controlled manner. Au fractal nanostructures grown on PCC flakes provide the highest mass normalized extinction, up to 3 m^2/g, which has been demonstrated in the broad spectral range. In the nanoplasmonic field active devices consist of a Au nanoparticle that acts as a cavity and the dye molecules attached to it via thin silica shell as the active medium. Such kind of devices is considered as a nano-laser or nano-amplifier. The fabricated nanolasers were studied for their photoluminescence kinetic properties. It is shown that the cooperative effects due to the coupling of dye molecules via Au nanoparticle plasmons result in bi-exponential emission decay characteristics in accord with theory predictions. These bi-exponential decays involve a fast superradiant decay, which is followed by a slow subradiant decay. To summarize, this work shows new attractive properties of core-shell nanoparticles. Fractal Au shells on silica cores prove to be a good scattering suppressor and a band pass filter in a broadband spectral range. They can also be used as an obscurant when PCC is used as the core material. Finally, gold nanoparticles coated with silica with dye results in bi-exponential decays.