Bioremediation of PAHs - Limitations and soultions

Introduction 1.1 Occurrence of polycyclic aromatic hydrocarbons (PAH) in the environment Worldwide industrial and agricultural developments have released a large number of natural and synthetic hazardous compounds into the environment due to careless waste disposal, illegal waste dumping and accidental spills. As a result, there are numerous sites in the world that require cleanup of soils and groundwater. Polycyclic aromatic hydrocarbons (PAHs) are one of the major groups of these contaminants (Da Silva et al., 2003). PAHs constitute a diverse class of organic compounds consisting of two or more aromatic rings with various structural configurations (Prabhu and Phale, 2003). Being a derivative of benzene, PAHs are thermodynamically stable. In addition, these chemicals tend to adhere to particle surfaces, such as soils, because of their low water solubility and strong hydrophobicity, and this results in greater persistence under natural conditions. This persistence coupled with their potential carcinogenicity makes PAHs problematic environmental contaminants (Cerniglia, 1992; Sutherland, 1992). PAHs are widely found in high concentrations at many industrial sites, particularly those associated with petroleum, gas production and wood preserving industries (Wilson and Jones, 1993). 1.2 Remediation technologies Conventional techniques used for the remediation of soil polluted with organic contaminants include excavation of the contaminated soil and disposal to a landfill or capping - containment - of the contaminated areas of a site. These methods have some drawbacks. The first method simply moves the contamination elsewhere and may create significant risks in the excavation, handling and transport of hazardous material. Additionally, it is very difficult and increasingly expensive to find new landfill sites for the final disposal of the material. The cap and containment method is only an interim solution since the contamination remains on site, requiring monitoring and maintenance of the isolation barriers long into the future, with all the associated costs and potential liability. A better approach than these traditional methods is to completely destroy the pollutants, if possible, or transform them into harmless substances. Some technologies that have been used are high-temperature incineration and various types of chemical decomposition (for example, base-catalyzed dechlorination, UV oxidation). However, these methods have significant disadvantages, principally their technological complexity, high cost , and the lack of public acceptance. Bioremediation, on the contrast, is a promising option for the complete removal and destruction of contaminants. 1.3 Bioremediation of PAH contaminated soil & groundwater Bioremediation is the use of living organisms, primarily microorganisms, to degrade or detoxify hazardous wastes into harmless substances such as carbon dioxide, water and cell biomass Most PAHs are biodegradable unter natural conditions (Da Silva et al., 2003; Meysami and Baheri, 2003) and bioremediation for cleanup of PAH wastes has been extensively studied at both laboratory and commercial levels- It has been implemented at a number of contaminated sites, including the cleanup of the Exxon Valdez oil spill in Prince William Sound, Alaska in 1989, the Mega Borg spill off the Texas coast in 1990 and the Burgan Oil Field, Kuwait in 1994 (Purwaningsih, 2002). Different strategies for PAH bioremediation, such as in situ , ex situ or on site bioremediation were developed in recent years. In situ bioremediation is a technique that is applied to soil and groundwater at the site without removing the contaminated soil or groundwater, based on the provision of optimum conditions for microbiological contaminant breakdown.. Ex situ bioremediation of PAHs, on the other hand, is a technique applied to soil and groundwater which has been removed from the site via excavation (soil) or pumping (water). Hazardous contaminants are converted in controlled bioreactors into harmless compounds in an efficient manner. 1.4 Bioavailability of PAH in the subsurface Frequently, PAH contamination in the environment is occurs as contaminants that are sorbed onto soilparticles rather than in phase (NAPL, non aqueous phase liquids). It is known that the biodegradation rate of most PAHs sorbed onto soil is far lower than rates measured in solution cultures of microorganisms with pure solid pollutants (Alexander and Scow, 1989; Hamaker, 1972). It is generally believed that only that fraction of PAHs dissolved in the solution can be metabolized by microorganisms in soil. The amount of contaminant that can be readily taken up and degraded by microorganisms is defined as bioavailability (Bosma et al., 1997; Maier, 2000). Two phenomena have been suggested to cause the low bioavailability of PAHs in soil (Danielsson, 2000). The first one is strong adsorption of the contaminants to the soil constituents which then leads to very slow release rates of contaminants to the aqueous phase. Sorption is often well correlated with soil organic matter content (Means, 1980) and significantly reduces biodegradation (Manilal and Alexander, 1991). The second phenomenon is slow mass transfer of pollutants, such as pore diffusion in the soil aggregates or diffusion in the organic matter in the soil. The complex set of these physical, chemical and biological processes is schematically illustrated in Figure 1. As shown in Figure 1, biodegradation processes are taking place in the soil solution while diffusion processes occur in the narrow pores in and between soil aggregates (Danielsson, 2000). Seemingly contradictory studies can be found in the literature that indicate the rate and final extent of metabolism may be either lower or higher for sorbed PAHs by soil than those for pure PAHs (Van Loosdrecht et al., 1990). These contrasting results demonstrate that the bioavailability of organic contaminants sorbed onto soil is far from being well understood. Besides bioavailability, there are several other factors influencing the rate and extent of biodegradation of PAHs in soil including microbial population characteristics, physical and chemical properties of PAHs and environmental factors (temperature, moisture, pH, degree of contamination). Figure 1: Schematic diagram showing possible rate-limiting processes during bioremediation of hydrophobic organic contaminants in a contaminated soil-water system (not to scale) (Danielsson, 2000). 1.5 Increasing the bioavailability of PAH in soil Attempts to improve the biodegradation of PAHs in soil by increasing their bioavailability include the use of surfactants , solvents or solubility enhancers.. However, introduction of synthetic surfactant may result in the addition of one more pollutant. (Wang and Brusseau, 1993).A study conducted by Mulder et al. showed that the introduction of hydropropyl-ß-cyclodextrin (HPCD), a well-known PAH solubility enhancer, significantly increased the solubilization of PAHs although it did not improve the biodegradation rate of PAHs (Mulder et al., 1998), indicating that further research is required in order to develop a feasible and efficient remediation method. Enhancing the extent of PAHs mass transfer from the soil phase to the liquid might prove an efficient and environmentally low-risk alternative way of addressing the problem of slow PAH biodegradation in soil.

A multi-objective genetic algorithm optimisation using variable speed pumps in water distribution systems

Due to its practical importance and inherent complexity, the optimisation of distribution networks for supplying drinking water has been the subject of extensive study for the past 30 years. The optimization is governed by sizing the pipes in the water distribution network (WDN) and / or optimises specific parts of the network such as pumps, tanks etc. or try to analyse and optimise the reliability of a WDN. In this thesis, the author has analysed two different WDNs (Anytown City and Cabrera city networks), trying to solve and optimise a multi-objective optimisation problem (MOOP). The main two objectives in both cases were the minimisation of Energy Cost (€) or Energy consumption (kWh), along with the total Number of pump switches (TNps) during a day. For this purpose, a decision support system generator for Multi-objective optimisation used. Its name is GANetXL and has been developed by the Center of Water System in the University of Exeter. GANetXL, works by calling the EPANET hydraulic solver, each time a hydraulic analysis has been fulfilled. The main algorithm used, was a second-generation algorithm for multi-objective optimisation called NSGA_II that gave us the Pareto fronts of each configuration. The first experiment that has been carried out was the network of Anytown city. It is a big network with a pump station of four fixed speed parallel pumps that are boosting the water dynamics. The main intervention was to change these pumps to new Variable speed driven pumps (VSDPs), by installing inverters capable to diverse their velocity during the day. Hence, it’s been achieved great Energy and cost savings along with minimisation in the number of pump switches. The results of the research are thoroughly illustrated in chapter 7, with comments and a variety of graphs and different configurations. The second experiment was about the network of Cabrera city. The smaller WDN had a unique FS pump in the system. The problem was the same as far as the optimisation process was concerned, thus, the minimisation of the energy consumption and in parallel the minimisation of TNps. The same optimisation tool has been used (GANetXL).The main scope was to carry out several and different experiments regarding a vast variety of configurations, using different pump (but this time keeping the FS mode), different tank levels, different pipe diameters and different emitters coefficient. All these different modes came up with a large number of results that were compared in the chapter 8. Concluding, it should be said that the optimisation of WDNs is a very interested field that has a vast space of options to deal with. This includes a large number of algorithms to choose from, different techniques and configurations to be made and different support system generators. The researcher has to be ready to “roam” between these choices, till a satisfactory result will convince him/her that has reached a good optimisation point.

La misura dell'impedenza locale con tecnologia Contact nello studio elettrofisiologico

Questo lavoro di Tesi Magistrale, si focalizza sulla più importante delle aritmie atriali, ovvero la Fibrillazione Atriale, e sul trattamento della stessa attraverso le procedure di ablazione a radio frequenza (RF). Il lavoro di tesi, svolto presso l'Ospedale 'M. Bufalini' di Cesena, affronta in particolare l'uso della tecnologia EnSite NavX (un sistema di mappaggio elettroanatomico delle cavità cardiache) ed EnSite Contact (un sistema basato sulla misura dell'impedenza locale per la valutazione del contatto elettrodo tessuto). L'acquisizione e l'analisi dei dati di ECI (indice di accoppiamento elettrico), forniti dal modulo Contact, hanno permesso di comprendere come questo parametro, derivato dalla misura dell'impedenza locale, possa contribuire a fornire importanti informazioni in real-time all'elettrofisiologo e come lo studio della sua dinamica, con particolare attenzione alle variazioni tra pre e post ablazione, possa risultare utile per verificare l'avvenuta erogazione di energia ai tessuti.

Search for time-integrated cp violation in $d^0 \rightarrow k^+k^-$ and $d^0 \rightarrow \pi^+\pi^-$ decays at lhcb.

The LHCb experiment at the LHC, by exploiting the high production cross section for $c\overline{c}$ quark pairs, offers the possibility to investigate $\mathcal{CP}$ violation in the charm sector with a very high precision.\\ In this thesis a measurement of time-integrated \(\mathcal{CP}\) violation using $D^0\rightarrow~K^+K^-$ and $D^0\rightarrow \pi^+\pi^-$ decays at LHCb is presented. The measured quantity is the difference ($\Delta$) of \(\mathcal{CP}\) asymmetry ($\mathcal{A}_{\mathcal{CP}}$) between the decay rates of $D^0$ and $\overline{D}^0$ mesons into $K^+K^–$ and $\pi^+\pi^-$ pairs.\\ The analysis is performed on 2011 data, collected at \(\sqrt{s}=7\) TeV and corresponding to an integrated luminosity of 1 fb\(^{-1}\), and 2012 data, collected at \(\sqrt{s}=8\) TeV and corresponding to an integrated luminosity of 2 fb\(^{-1}\).\\ A complete study of systematic uncertainties is beyond the aim of this thesis. However the most important systematic of the previous analysis has been studied. We find that this systematic uncertainty was due to a statistical fluctuation and then we demonstrate that it is no longer necessary to take into account.\\ By combining the 2011 and 2012 results, the final statistical precision is 0.08\%. When this analysis will be completed and published, this will be the most precise single measurement in the search for $\mathcal{CP}$ violation in the charm sector.

Dielectrophoresis (dep) and electrowetting (ewod) as an anti-fouling process for antibacterial surfaces

Nowadays the medical field is struggling to decrease bacteria biofilm formation which leads to infection. Biomedical devices sterilization has not changed over a long period of time. This results in high costs for hospitals healthcare managements. The objective of this project is to investigate electric field effects and surface energy manipulation as solutions for preventing bacteria biofilm for future devices. Based on electrokinectic environments 2 different methods were tested: feasibility of electric gradient through mediums (DEP) reinforced by numerical simulations; and EWOD by the fabrication of golden interdigitated electrodes on silicon glass substrates, standard ~480 nm Teflon (PTFE) layer and polymeric gasket to contain the bacteria medium. In the first experiment quantitative analysis was carried out to achieve forces required to reject bacteria without considering dielectric environment limitations as bacteria and medium frequency dependence. In the second experiment applied voltages was characterized by droplets contact angle measurements and put to the live bacteria tests. The project resulted on promising results for DEP application due to its wide range of frequency that can be used to make a “general” bacteria rejecting; but in terms of practicality, EWOD probably have higher potential for success but more experiments are needed to verify if can prevent biofilm adhesion besides the Teflon non-adhesive properties (including limitations as Teflon breakthrough, layer sensitivity) at incubation times larger than 24 hours.

Study of the sensitivity of the XENON1T experiment with the profile likelihood method

Oggi sappiamo che la materia ordinaria rappresenta solo una piccola parte dell'intero contenuto in massa dell'Universo. L'ipotesi dell'esistenza della Materia Oscura, un nuovo tipo di materia che interagisce solo gravitazionalmente e, forse, tramite la forza debole, è stata avvalorata da numerose evidenze su scala sia galattica che cosmologica. Gli sforzi rivolti alla ricerca delle cosiddette WIMPs (Weakly Interacting Massive Particles), il generico nome dato alle particelle di Materia Oscura, si sono moltiplicati nel corso degli ultimi anni. L'esperimento XENON1T, attualmente in costruzione presso i Laboratori Nazionali del Gran Sasso (LNGS) e che sarà in presa dati entro la fine del 2015, segnerà un significativo passo in avanti nella ricerca diretta di Materia Oscura, che si basa sulla rivelazione di collisioni elastiche su nuclei bersaglio. XENON1T rappresenta la fase attuale del progetto XENON, che ha già realizzato gli esperimenti XENON10 (2005) e XENON100 (2008 e tuttora in funzione) e che prevede anche un ulteriore sviluppo, chiamato XENONnT. Il rivelatore XENON1T sfrutta circa 3 tonnellate di xeno liquido (LXe) e si basa su una Time Projection Chamber (TPC) a doppia fase. Dettagliate simulazioni Monte Carlo della geometria del rivelatore, assieme a specifiche misure della radioattività dei materiali e stime della purezza dello xeno utilizzato, hanno permesso di predire con accuratezza il fondo atteso. In questo lavoro di tesi, presentiamo lo studio della sensibilità attesa per XENON1T effettuato tramite il metodo statistico chiamato Profile Likelihood (PL) Ratio, il quale nell'ambito di un approccio frequentista permette un'appropriata trattazione delle incertezze sistematiche. In un primo momento è stata stimata la sensibilità usando il metodo semplificato Likelihood Ratio che non tiene conto di alcuna sistematica. In questo modo si è potuto valutare l'impatto della principale incertezza sistematica per XENON1T, ovvero quella sulla emissione di luce di scintillazione dello xeno per rinculi nucleari di bassa energia. I risultati conclusivi ottenuti con il metodo PL indicano che XENON1T sarà in grado di migliorare significativamente gli attuali limiti di esclusione di WIMPs; la massima sensibilità raggiunge una sezione d'urto σ=1.2∙10-47 cm2 per una massa di WIMP di 50 GeV/c2 e per una esposizione nominale di 2 tonnellate∙anno. I risultati ottenuti sono in linea con l'ambizioso obiettivo di XENON1T di abbassare gli attuali limiti sulla sezione d'urto, σ, delle WIMPs di due ordini di grandezza. Con tali prestazioni, e considerando 1 tonnellata di LXe come massa fiduciale, XENON1T sarà in grado di superare gli attuali limiti (esperimento LUX, 2013) dopo soli 5 giorni di acquisizione dati.

Investigation of petabyte-scale data transfer performances with PhEDEx for the CMS experiment

PhEDEx, the CMS transfer management system, during the first LHC Run has moved about 150 PB and currently it is moving about 2.5 PB of data per week over the Worldwide LHC Computing Grid (WLGC). It was designed to complete each transfer required by users at the expense of the waiting time necessary for its completion. For this reason, after several years of operations, data regarding transfer latencies has been collected and stored into log files containing useful analyzable informations. Then, starting from the analysis of several typical CMS transfer workflows, a categorization of such latencies has been made with a focus on the different factors that contribute to the transfer completion time. The analysis presented in this thesis will provide the necessary information for equipping PhEDEx in the future with a set of new tools in order to proactively identify and fix any latency issues. PhEDEx, il sistema di gestione dei trasferimenti di CMS, durante il primo Run di LHC ha trasferito all’incirca 150 PB ed attualmente trasferisce circa 2.5 PB di dati alla settimana attraverso la Worldwide LHC Computing Grid (WLCG). Questo sistema è stato progettato per completare ogni trasferimento richiesto dall’utente a spese del tempo necessario per il suo completamento. Dopo svariati anni di operazioni con tale strumento, sono stati raccolti dati relativi alle latenze di trasferimento ed immagazzinati in log files contenenti informazioni utili per l’analisi. A questo punto, partendo dall’analisi di una ampia mole di trasferimenti in CMS, è stata effettuata una suddivisione di queste latenze ponendo particolare attenzione nei confronti dei fattori che contribuiscono al tempo di completamento del trasferimento. L’analisi presentata in questa tesi permetterà di equipaggiare PhEDEx con un insieme di utili strumenti in modo tale da identificare proattivamente queste latenze e adottare le opportune tattiche per minimizzare l’impatto sugli utenti finali.