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.

Salume arricchito in acidi grassi polinsaturi omega-3: controllo di parametri chimici qualitativi e compositivi in relazione ad un possibile incremento di ossidabilita’ della frazione lipidica durante la shelf-life

Questa relazione finale è incentrata sul lavoro sperimentale richiesto dalla collaborazione con l’azienda Natural Salumi ed ha come obiettivo principale quello di verifica dei parametri qualitativi e compositivi di una nuova tipologia di salume in fase di studio. L’azienda ha infatti messo a punto un nuovo “prodotto funzionale” addizionando componenti aventi attività nutraceutica al salame ottenuto da sole parti magre di suino (tipo NaturalFetta) e si propone di arricchire il proprio prodotto con acidi grassi polinsaturi della serie omega-3 (da olio di semi di lino), noti per gli effetti benefici esercitati sulla salute umana. Sul prodotto di nuova formulazione si effettueranno sia la determinazione della percentuale lipidica mediante metodo ufficiale Soxhlet ed automatizzato Soxtec, al fine di individuare il quantitativo totale della parte grassa, che una caratterizzazione del profilo quali-quantitativo in acidi grassi, fondamentale per verificare la conformità con i requisiti indicati dal Reg. 1924/06 (e successivi come il Reg. UE 432/2012) previsti per le indicazioni da inserire in etichetta (claims) per i prodotti arricchiti con acidi grassi polinsaturi (PUFA). La determinazione del profilo in acidi grassi e, nello specifico, del contenuto in acido -linolenico, sarà realizzata mediante gascromatografia previa estrazione della frazione lipidica dei salumi con metodo di Folch modificato, che prevede un'estrazione solido-liquido. La concentrazione di acido alfa-linolenico sarà inoltre monitorata durante tutto il periodo di shelf-life del prodotto (45 gg) al fine di valutare eventuali variazioni durante la conservazione. Per soddisfare quest’ultima finalità, le analisi saranno eseguite sia all’inizio (T0) che alla fine (T1) della vita commerciale del prodotto. Le stesse analisi verranno inoltre condotte sia sul prodotto a formulazione classica che su un prodotto del tutto simile, commercializzato da un’altra azienda e considerato come leader di mercato. In relazione ad un possibile aumento di ossidabilità della frazione lipidica, sarà realizzato un controllo dei parametri chimici, qualitativi e compositivi, con particolare riferimento ai prodotti di ossidazione del colesterolo (date le loro implicazioni in ambito biomedico). La maggiore presenza in formulazione di acidi grassi polinsaturi potrebbe infatti favorire un incremento dei COPs (Cholesterol Oxidation Products), che saranno separati, identificati e quantificati mediante la procedura SPE/GC-MS (estrazione e purificazione in fase solida accoppiata ad analisi gascromatografica con rivelazione mediante spettrometria di massa).

Anaerobic oxidation of ethanol over spinel mixed oxides: the first step in the steam-iron process for H2 production

The future hydrogen demand is expected to increase, both in existing industries (including upgrading of fossil fuels or ammonia production) and in new technologies, like fuel cells. Nowadays, hydrogen is obtained predominantly by steam reforming of methane, but it is well known that hydrocarbon based routes result in environmental problems and besides the market is dependent on the availability of this finite resource which is suffering of rapid depletion. Therefore, alternative processes using renewable sources like wind, solar energy and biomass, are now being considered for the production of hydrogen. One of those alternative methods is the so-called “steam-iron process” which consists in the reduction of a metal-oxide by hydrogen-containing feedstock, like ethanol for instance, and then the reduced material is reoxidized with water to produce “clean” hydrogen (water splitting). This kind of thermochemical cycles have been studied before but currently some important facts like the development of more active catalysts, the flexibility of the feedstock (including renewable bio-alcohols) and the fact that the purification of hydrogen could be avoided, have significantly increased the interest for this research topic. With the aim of increasing the understanding of the reactions that govern the steam-iron route to produce hydrogen, it is necessary to go into the molecular level. Spectroscopic methods are an important tool to extract information that could help in the development of more efficient materials and processes. In this research, ethanol was chosen as a reducing fuel and the main goal was to study its interaction with different catalysts having similar structure (spinels), to make a correlation with the composition and the mechanism of the anaerobic oxidation of the ethanol which is the first step of the steam-iron cycle. To accomplish this, diffuse reflectance spectroscopy (DRIFTS) was used to study the surface composition of the catalysts during the adsorption of ethanol and its transformation during the temperature program. Furthermore, mass spectrometry was used to monitor the desorbed products. The set of studied materials include Cu, Co and Ni ferrites which were also characterized by means of X-ray diffraction, surface area measurements, Raman spectroscopy, and temperature programmed reduction.

Organic/inorganic polyoxometalate-based hybrids for oxidation catalysis and energy conversion

This thesis work has been carried out during the Erasmus exchange period at the “Université Paris 6 – Pierre et Marie Curie”, in the “Edifices PolyMétalliques – EPOM” team, leaded by Prof. Anna Proust, belonging to the “Institut Parisien de Chimie Moléculaire”, under the supervision of Dr. Guillaume Izzet and Dr. Geoffroy Guillemot. The redox properties of functionalized Keggin and Dawson POMs have been exploited in photochemical, catalytic and reactivity tests. For the photochemical purposes, the selected POMs have been functionalized with different photoactive FGs, and the resulting products have been characterized by CV analyses, luminescence tests and UV-Vis analyses. In future, these materials will be tested for hydrogen photoproduction and polymerization of photoactive films. For the catalytic purposes, POMs have been firstly functionalized with silanol moieties, to obtain original coordination sites, and then post-functionalized with TMs such as V, Ti and Zr in their highest oxidation states. In this way, the catalytic properties of TMs were coupled to the redox properties of POM frameworks. The redox behavior of some of these hybrids has been studied by spectro-electrochemical and EPR methods. Catalytic epoxidation tests have been carried out on allylic alcohols and n-olefins, employing different catalysts and variable amounts of them. The performances of POM-V hybrids have been compared to those of VO(iPrO)3. Finally, reactivity of POM-VIII hybrids has been studied, using styrene oxide and ethyl-2-diazoacetate as substrates. All the obtained products have been analyzed via NMR techniques. Cyclovoltammetric analyses have been carried out in order to determine the redox behavior of selected hybrids.

Selective photo-oxidation of glucose

Biomass transformation into high-value chemicals has attracted attention according to the “green chemistry” principles. Low price and high availability make biomass one of the most interesting renewable resources as it provides the means to create sustainable alternatives to the oil-derived building blocks of the chemical industry In recent year, the need for alternative environmentally friendly routes to drive chemical reactions has in photocatalytic processes an interesting way to obtain valuable chemicals from various sources using the solar light as energy source. The purpose of this work was to use supported noble metal nanoparticles in the selective photo-oxidation of glucose through using visible light. Glucose was chosen as model molecule because it is the cheapest and the most common monosaccharide. Few studies about glucose photo oxidation have been conducted so far, and reaction mechanism is still not totally explained. The aim of this work was to systematically analyze and assess the impact of several parameters (eg. catalyst/substrate ratio, reaction time, effect of the solvent and light source) on the reaction pathway and to monitor the product distribution in order to draw a general reaction scheme for the photo oxidation of glucose under visible light. This study regards the reaction mechanism and the influence of several parameters, such as solvent, light power and substrate concentration. Furthermore, the work focuses on the influence of gold and silver nanoparticles and on the influence of metal loading. The glucose oxidation was monitored through the mass balance and the products selectivity. Reactions were evaluated in terms of glucose conversion, mass balance and selectivities towards arabinose and gluconic acid. In conclusion, this study is able to demonstrate that the photo oxidation of glucose under visible light is feasible; the full identification of the main products allows, for the first time, a comprehensive reaction mechanism scheme.

3D electrocatalysts for the selective glucose oxidation

Nowadays, one of the most important scientific and environmental concern is to reduce global dependence on fossil fuels. The use of lignocellulosic biomass makes it possible to produce important platform molecules such as D-glucose, which is used to synthesize high value-added chemical products such as gluconic acid (GO) and glucaric acid (GA). Moreover, the electrocatalytic oxidation of glucose shows advantages compared to the classical synthesis route, such as the use of non-toxic reactants and milder conditions, making the process greener and more sustainable. In this work, electrocatalysts based on open-cell Ni metal foams were investigated for the glucose electrooxidation. They were used as supplied, oxidized at 500°C and 600°C, and after electrodeposition of Ni(OH)2. The electrocatalysts were characterized by cyclic voltammetry in NaOH solution 0.1M and in a basic D-glucose solution with different glucose concentrations (10mM and 50mM). The effect of the potential applied, the glucose concentration and the reaction time on conversion, selectivity and faradic efficiency were also investigated. 3D Ni electrocatalyst showed promising activity in the conversion of glucose towards gluconic acid, the sample calcined at 500°C showing the best results.

Extraction of antioxidants from corn by-products for applications in bio-based polymer matrices

The objective of this dissertation is the evaluation of the exploitability of corn cobs as natural additives for bio-based polymer matrices, in order to hone their properties while keeping the fundamental quality of being fully bio-derived. The first part of the project has the purpose of finding the best solvent and conditions to extract antioxidants and anti-degrading molecules from corn cobs, exploiting room and high-temperature processes, traditional and advanced extraction methods, as well as polar and nonpolar solvents. The extracts in their entirety are then analysed to evaluate their antioxidant content, in order to select the conditions able to maximise their anti-degrading properties. The second part of the project, instead, focuses on assessing chemical and physical properties of the best-behaving extract when inserted in a polymeric matrix. To achieve this, low-density polyethylene (LDPE) and poly (butylene succinate – co – adipate) (PBSA) are employed. These samples are obtained through extrusion and are subsequently characterised exploiting the DSC equipment and a sinusoidally oscillating rheometer. In addition, extruded polymeric matrices are subjected to thermal and photo ageing, in order to identify their behaviour after different forms of degradation and to assess their performances with respect to synthetically produced anti-degrading additives.

Electrochemical oxidation of Kraft and Dealkaline lignin to produce value-added chemicals on Nickel electrocatalysts

One of the most important scientific and environmental issues is reducing global dependence on fossil sources and one of the solutions is to use biomass as feedstock. In particular, the use of lignocellulosic biomass to obtain molecules with considerable commercial importance is gaining more and more interest. Lignin, the most recalcitrant part of lignocellulosic biomass, is a valuable source of sustainable and renewable aromatic molecules, currently produced from petrochemical processes. Vanillin, one of the most important aromatic aldehydes on an industrial level, can be obtained through catalytic lignin oxidation. An alternative to the conventional catalytic oxidation process is the electro-catalytic process, which can be carried out at ambient temperature and pressure, using water as solvent, and it can be considered as a renewable energy storage. In this thesis, the electrocatalytic oxidation of Kraft and Dealkaline lignin in NaOH was investigated over Ni foam catalysts. The effect of the reaction parameters (i.e. time, applied potential, lignin concentration, NaOH concentration, and temperature) on the yields of vanillin and other valuable products was evaluated. After the screening of the reaction conditions, a systematic study of the contribution of the homogeneous reaction (lignin depolymerization due to the basic solvent) to the yield of the product was accomplished. Finally, considering the obtained results, an alternative reaction procedure was proposed.