Photochemical degradation of triclosan: a comparison between different light sources

New emerging contaminants could represent a danger to the environment and Humanity with repercussions not yet known. One of the major worldwide pharmaceutical and personal care productions are antimicrobials products, triclosan, is an antimicrobial agent present in most products. Despite the high removal rate of triclosan present in wastewater treatments, triclosan levels are on the rise in the environment through disposal of wastewater effluent and use of sewage sludge in land application. Regulated in the EC/1272/2008 (annex VI, table 3.1), this compound is considered very toxic to aquatic life and it has been reported that photochemical transformation of triclosan produces dioxins. In the current work it was defined three objectives; determination of the most efficient process in triclosan degradation, recurring to photochemical degradation methods comparing different sources of light; identification of the main by-products formed during the degradation and the study of the influence of the Fenton and photo-Fenton reaction. Photochemical degradation methods such as: photocatalysis under florescent light (UV), photocatalysis under visible light (sunlight), photocatalysis under LEDs, photo-Fenton and Fenton reaction have been compared in this work. The degradation of triclosan was visualized through gas chromatography/mass spectrometry (GC/MS). In this study photo-Fenton reaction has successfully oxidized triclosan to H2O and CO2 without any by-products within 2 hours. Photocatalysis by titanium dioxide (TiO2) under LEDs was possible, having a degradation rate of 53% in an 8 hours essay. The degradation rate of the Fenton reaction, UV light and sunlight showed degradation between 90% and 95%. The results are reported to the data observed without statistic support, since this was not possible during the work period. Hydroquinone specie and 2,4-dichlorophenol by-products were identified in the first hour of photocatalysis by UV. A common compound, possibly identified has C7O4H , was present at the degradation by UV, sunlight and LEDs and was concluded to be a contaminant. In the future more studies in the use of LEDs should be undertaken given the advantages of long durability and low consumption of energy of these lamps and that due to their negative impact on the environment fluorescent lamps are being progressively made unavailable by governments, requiring new solutions to be found. Fenton and photo-Fenton reactions can also be costly processes given the expensive reagents used.

Characterization of an OPCPA laser amplifier based on the nonlinear crystal YCOB

The work described in this thesis was performed at the Laboratory for Intense Lasers (L2I) of Instituto Superior Técnico, University of Lisbon (IST-UL). Its main contribution consists in the feasibility study of the broadband dispersive stages for an optical parametric chirped pulse amplifier based on the nonlinear crystal yttrium calcium oxi-borate (YCOB). In particular, the main goal of this work consisted in the characterization and implementation of the several optical devices involved in pulse expansion and compression of the amplified pulses to durations of the order of a few optical cycles (20 fs). This type of laser systems find application in fields such as medicine, telecommunications and machining, which require high energy, ultrashort (sub-100 fs) pulses. The main challenges consisted in the preliminary study of the performance of the broadband amplifier, which is essential for successfully handling pulses with bandwidths exceeding 100 nm when amplified from the μJ to 20 mJ per pulse. In general, the control, manipulation and characterization of optical phenomena on the scale of a few tens of fs and powers that can reach the PW level are extremely difficult and challenging due to the complexity of the phenomena of radiation-matter interaction and their nonlinearities, observed at this time scale and power level. For this purpose the main dispersive components were characterized in detail, specifically addressing the demonstration of pulse expansion and compression. The tested bandwidths are narrower than the final ones, in order to confirm the parameters of these elements and predict the performance for the broadband pulses. The work performed led to additional tasks such as a detailed characterization of laser oscillator seeding the laser chain and the detection and cancelling of additional sources of dispersion.

Radiation damage in flexible TFTs and organic detectors

In this thesis was investigated the radiation hardness of the building blocks of a future flexible X-ray sensor system. The characterized building blocks for the pixel addressing and signal amplification electronics are high mobility semiconducting oxide transistors (HMSO-TFTs) and organic transistors (OTFTs), whereas the photonic detection system is based on organic semiconducting single crystals (OSSCs). TFT parameters such as mobility, threshold voltage and subthreshold slope were measured as function of cumulative X-ray dose. Instead for OSSCs conductivity and X-ray sensitivity were analysed after various radiation steps. The results show that ionizing radiation does not lead to degradation in HMSO-TFTs. Instead OTFTs show instability in mobility which is reduced up to 73% for doses of 1 kGy. OSSC demonstrate stable detector properties for the tested total dose range. As conclusion, HMSO-TFTs and OSSCs can be readily employed in the X-ray detector system allowing operation for total doses exceeding 1 kGy of ionizing radiation.

Ion-beam sources based on superionic solid electrolytes

An ion emitter consisting of a sharp silver tip covered in RbAg4I5 solid electrolyte film has been developed and studied. An accelerating potential is applied and Ag+ ions are emitted from the tip’s apex by field evaporation. The emitted ions are collected by a Faraday cup, producing a current on the pico/nanoampere level which is read by an electrometer. The tips were produced mechanically by sandpaper polishing. The sharpest tip produced had a 2:4 m apex radius. Two deposition methods were studied: thermal vacuum and pulsed laser deposition. The best tip produced a peak current value of 96nA at 180oC, and a quasi-stable 4nA emission current at 160oC, both using an extraction potential of 10kV . The emission dependence on time, temperature and accelerating potential has been studied. Deposited films were characterized by X-ray diffraction (XRD), profilometry, optical and Scanning Electron Microscope (SEM) and Secondary Ion Mass Spectroscopy (SIMS) measurements. Several ion emitters were developed, the latter ones were all able to maintain stable high ion emissions for long periods of time. This investigation was a continuation of an ongoing project backed by the European Space Agency, with the objective of making a proof of concept of this kind of ion emitter with potential application on ion thrusters for orbiting satellites. Going forward, it would be interesting to make a finer analysis of the electrolyte’s conductivity at high temperatures, explore Wien Effect-based emission and to further develop a multi-tip ion emitter prototype.

Sources to study Antiquity: Between texts and material culture. Abstract Book

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