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.

Talking through walls: a history of the murals in Northern Ireland

This dissertation examines how some fundamental events of the history of Ireland emerge through the art of the mural. It is divided into three chapters. The first chapter opens with a brief presentation of the mural as a form of art with a semiotic and sociological function, with a particular focus on the socio-political importance it has had and still has today in Ireland, where murals are a significant means of expressing ideals, protest and commemoration. A part of this chapter also provides data about the number of murals and their location, with a particular focus on the two cities of Belfast and Derry. This first chapter ends with the presentation of an initiative put forth by the Arts Council of Northern Ireland, called "Building Peace through the Arts: Re-Imaging Communities", and questions its implementation on the Irish soil. The second chapter provides a history of the murals in Northern Ireland, from the Unionist's early depictions of King Billy in occasion of the 12 July annual celebrations to the Republican response. This will be supported by an explanation of the two events that triggered the start of the mural painting for both factions: the Battle of the Boyne for the Loyalists and the 1981 hunger strike for the Republicans. In the third and last chapter of this dissertation, a key of the main themes, symbols, acronyms and dominant colours which can be found in Loyalist and Republican murals is provided. Furthermore, one mural for each faction is looked at more closely, with an analysis of the symbols which are present in it.

Validazione di modelli per la simulazione del film di combustibile liquido a parete in motori ad accensione comandata

Le normative antinquinamento sempre più stringenti in termini di emissioni prodotte da un MCI hanno reso necessario lo studio e lo sviluppo di modelli predittivi in grado quindi di simulare tutto ciò che avviene all’interno della camera di combustione; allo scopo di ottimizzare quello che è un prodotto industriale e che pertanto va venduto. Il presente elaborato di tesi si è quindi incentrato sull’impatto che uno spray di combustibile, iniettato ad alta pressione, ha su pareti calde e fredde, analizzando tutto ciò che concerne l’eventuale sviluppo di wall-film prodotto come la relativa massa, area, spessore e raffreddamento della parete per via della propria interazione con il film a parete. Sono stati prima di tutto studiati i fenomeni fisici in atto e successivamente analizzati i modelli implementati nel codice di calcolo commerciale utilizzato STAR-CD, in particolare il modello di boiling, il modulo 1D-CHT ed il modello di impatto Bai-ONERA; il tutto facendo riferimento a esperimenti, già condotti, presenti in letteratura.

Graphite for lithium-ion batteries: mineral analysis and global Material Flow Analysis

Graphite is a mineral commodity used as anode for lithium-ion batteries (LIBs), and its global demand is doomed to increase significantly in the future due to the forecasted global market demand of electric vehicles. Currently, the graphite used to produce LIBs is a mix of synthetic and natural graphite. The first one is produced by the crystallization of petroleum by-products and the second comes from mining, which causes threats related to pollution, social acceptance, and health. This MSc work has the objective of determining compositional and textural characteristics of natural, synthetic, and recycled graphite by using SEM-EDS, XRF, XRD, and TEM analytical techniques and couple these data with dynamic Material Flow Analysis (MFA) models, which have the objective of predicting the future global use of graphite in order to test the hypothesis that natural graphite will no longer be used in the LIB market globally. The mineral analyses reveal that the synthetic graphite samples contain less impurities than the natural graphite, which has a rolled internal structure similar to the recycled one. However, recycled graphite shows fractures and discontinuities of the graphene layers caused by the recycling process, but its rolled internal structure can help the Li-ions’ migration through the fractures. Three dynamic MFA studies have been conducted to test distinct scenarios that include graphite recycling in the period 2022-2050 and it emerges that - irrespective of any considered scenario - there will be an increase of synthetic graphite demand, caused by the limited stocks of battery scrap available. Hence, I conclude that both natural and recycled graphite is doomed to be used in the LIB market in the future, at least until the year 2050 when the stock of recycled graphite production will be enough to supersede natural graphite. In addition, some new improvement in the dismantling and recycling processes are necessary to improve the quality of recycled graphite.

Traffic Signal Optimization of Urban Arterial Network by Vehicle-to-Infrastructure

Urbanization has occasionally been linked to negative consequences. Traffic light system in urban arterial networks plays an essential role to the operation of transport systems. The availability of new Intelligent Transportation System innovations paved the way for connecting vehicles and road infrastructure. GLOSA, or the Green Light Optimal Speed Advisory, is a recent integration of vehicle-to-everything (v2x) technology. This thesis emphasized GLOSA system's potential as a tool for addressing traffic signal optimization. GLOSA serves as an advisory to drivers, informing them of the speed they must maintain to reduce waiting time. The considered study area in this thesis is the Via Aurelio Saffi – Via Emilia Ponente corridor in the Metropolitan City of Bologna which has several signalized intersections. Several simulation runs were performed in SUMOPy software on each peak-hour period (morning and afternoon) using recent actual traffic count data. GLOSA devices were placed on a 300m GLOSA distance. Considering the morning peak-hour, GLOSA outperformed the actuated traffic signal control, which is the baseline scenario, in terms of average waiting time, average speed, average fuel consumption per vehicle and average CO2 emissions. A remarkable 97% reduction on both fuel consumption and CO2 emissions were obtained. The average speed of vehicles running through the simulation was increased as well by 7% and a time saved of 25%. Same results were obtained for the afternoon peak hour with a decrease of 98% on both fuel consumption and CO2 emissions, 20% decrease on average waiting time, and an increase of 2% in average speed. In addition to previously mentioned benefits of GLOSA, a 15% and 13% decrease in time loss were obtained during morning and afternoon peak-hour, respectively. Towards the goal of sustainability, GLOSA shows a promising result of significantly lowering fuel consumption and CO2 emissions per vehicle.