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.

Development of a biorefinery scheme for the valorization of olive mill wastewaters and grape pomaces

In the Mediterranean area, olive mill wastewater (OMW) and grape pomace (GP) are among the major agro-industrial wastes produced. These two wastes have a high organic load and high phytotoxicity. Thus, their disposal in the environment can lead to negative effects. Second-generation biorefineries are dedicated to the valorization of biowaste by the production of goods from such residual biomasses. This approach can combine bioremediation approaches to the generation of noble molecules, biomaterials and energy. The main aim of this thesis work was to study the anaerobic digestion of OMW and GP under different operational conditions to produce volatile fatti acids (VFAs) (first stage aim) and CH4 (second stage aim). To this end, a packed-bed biofilm reactor (PBBR) was set up to perform the anaerobic acidogenic digestion of the liquid dephenolized stream of OMW (OMWdeph). In parallel, the solid stream of OMW (OMWsolid), previously separated in order to allow the solid phase extraction of polyphenols, was addressed to anaerobic methanogenic digestion to obtain CH4. The latter experiment was performed in 100ml Pyrex bottles which were maintained at different temperatures (55-45-37°C). Together with previous experiments, the anaerobic acidogenic digestion of fermented GP (GPfreshacid) and dephenolized and fermented GP (GPdephacid) was performed in 100ml Pyrex bottles to estimate the concentration of VFAs achievable from each aforementioned GPs. Finally, the same matrices of GP and not pre-treated GP (GPfresh) were digested under anaerobic methanogenic condition to produce CH4. Anaerobic acidogenic and methanogenic digestion processes of GPs lasted about 33 days. Instead, the anaerobic acidogenic and methanogenic digestion process of OMWs lasted about 121 and 60 days, respectively. Each experiment was periodically monitored by analysing volume and composition of produced biogas and VFA concentration. Results showed that VFAs were produced in higher concentrations in GP compared to OMWdeph. The overall concentration of VFAs from GPfreshacid was approximately 39.5 gCOD L-1, 29 gCOD L-1 from GPdephacid, and 8.7 gCOD L-1 from OMWdeph. Concerning the CH4 production, the OMWsolid reached a high biochemical methane potential (BMP) at a thermophilic temperature (55°) than at mesophlic ones (37-45°C). The value reached was about 358.7 mlCH4 gSVsub-1. In contrast, GPfresh got a high BMP but at a mesophilic temperature. The BMP was about 207.3 mlCH4 gSVsub-1, followed by GPfreshacid with about 192.6 mlCH4 gSVsub-1 and lastly GPdephacid with about 102.2 mlCH4 gSVsub-1. In summary, based on the gathered results, GP seems to be a better carbon source for acidogenic and methanogenic microrganism compared to OMW, because higher amount of VFAs and CH4 were produced in AD of GP than OMW. In addition to these products, polyphenols were extracted by means of a solid phase extraction (SPE) procedure by another research group, and VFAs were utilised for biopolymers production, in particular polyhydroxyalkanoates (PHAs), by the same research group in which I was involved.

Processo biotecnologico a cellule immobilizzate per la produzione di acidi grassi volatili da acque di vegetazione

Le acque di vegetazione (AV) costituiscono un serio problema di carattere ambientale, sia a causa della loro elevata produzione sia per l’ elevato contenuto di COD che oscilla fra 50 e 150 g/l. Le AV sono considerate un refluo a tasso inquinante fra i più elevati nell’ambito dell’industria agroalimentare e la loro tossicità è determinata in massima parte dalla componente fenolica. Il presente lavoro si propone di studiare e ottimizzare un processo non solo di smaltimento di tale refluo ma anche di una sua valorizzazione, utlizzandolo come materia prima per la produzione di acidi grassi e quindi di PHA, polimeri biodegradabili utilizzabili in varie applicazioni. A tale scopo sono stati utilizzati due bioreattori anaerobici a biomassa adesa, di identica configurazione, con cui si sono condotti due esperimenti in continuo a diverse temperature e carichi organici al fine di studiare l’influenza di tali parametri sul processo. Il primo esperimento è stato condotto a 35°C e carico organico pari a 12,39 g/Ld, il secondo a 25°C e carico organico pari a 8,40 g/Ld. Si è scelto di allestire e mettere in opera un processo a cellule immobilizzate in quanto questa tecnologia si è rivelata vantaggiosa nel trattamento continuo di reflui ad alto contenuto di COD e carichi variabili. Inoltre si è scelto di lavorare in continuo poiché tale condizione, per debiti tempi di ritenzione idraulica, consente di minimizzare la metanogenesi, mediata da microrganismi con basse velocità specifiche di crescita. Per costituire il letto fisso dei due reattori si sono utilizzati due diversi tipi di supporto, in modo da poter studiare anche l’influenza di tale parametro, in particolare si è fatto uso di carbone attivo granulare (GAC) e filtri ceramici Vukopor S10 (VS). Confrontando i risultati si è visto che la massima quantità di VFA prodotta nell’ambito del presente studio si ha nel VS mantenuto a 25°C: in tale condizione si arriva infatti ad un valore di VFA prodotti pari a 524,668 mgCOD/L. Inoltre l’effluente in uscita risulta più concentrato in termini di VFA rispetto a quello in entrata: nell’alimentazione la percentuale di materiale organico presente sottoforma di acidi grassi volatili era del 54 % e tale percentuale, in uscita dai reattori, ha raggiunto il 59 %. Il VS25 rappresenta anche la condizione in cui il COD degradato si è trasformato in percentuale minore a metano (2,35 %) e questo a prova del fatto che l’acidogenesi ha prevalso sulla metanogenesi. Anche nella condizione più favorevole alla produzione di VFA però, si è riusciti ad ottenere una loro concentrazione in uscita (3,43 g/L) inferiore rispetto a quella di tentativo (8,5 g/L di VFA) per il processo di produzione di PHA, sviluppato da un gruppo di ricerca dell’università “La Sapienza” di Roma, relativa ad un medium sintetico. Si può constatare che la modesta produzione di VFA non è dovuta all’eccessiva degradazione del COD, essendo questa nel VS25 appena pari al 6,23%, ma piuttosto è dovuta a una scarsa concentrazione di VFA in uscita. Questo è di buon auspicio nell’ottica di ottimizzare il processo migliorandone le prestazioni, poiché è possibile aumentare tale concentrazione aumentando la conversione di COD in VFA che nel VS25 è pari a solo 5,87%. Per aumentare tale valore si può agire su vari parametri, quali la temperatura e il carico organico. Si è visto che il processo di acidogenesi è favorito, per il VS, per basse temperature e alti carichi organici. Per quanto riguarda il reattore impaccato con carbone attivo la produzione di VFA è molto ridotta per tutti i valori di temperatura e carichi organici utilizzati. Si può quindi pensare a un’applicazione diversa di tale tipo di reattore, ad esempio per la produzione di metano e quindi di energia.

Study of a wind-wave numerical model and its integration with ocean and oil-spill numerical models

The ability to represent the transport and fate of an oil slick at the sea surface is a formidable task. By using an accurate numerical representation of oil evolution and movement in seawater, the possibility to asses and reduce the oil-spill pollution risk can be greatly improved. The blowing of the wind on the sea surface generates ocean waves, which give rise to transport of pollutants by wave-induced velocities that are known as Stokes’ Drift velocities. The Stokes’ Drift transport associated to a random gravity wave field is a function of the wave Energy Spectra that statistically fully describe it and that can be provided by a wave numerical model. Therefore, in order to perform an accurate numerical simulation of the oil motion in seawater, a coupling of the oil-spill model with a wave forecasting model is needed. In this Thesis work, the coupling of the MEDSLIK-II oil-spill numerical model with the SWAN wind-wave numerical model has been performed and tested. In order to improve the knowledge of the wind-wave model and its numerical performances, a preliminary sensitivity study to different SWAN model configuration has been carried out. The SWAN model results have been compared with the ISPRA directional buoys located at Venezia, Ancona and Monopoli and the best model settings have been detected. Then, high resolution currents provided by a relocatable model (SURF) have been used to force both the wave and the oil-spill models and its coupling with the SWAN model has been tested. The trajectories of four drifters have been simulated by using JONSWAP parametric spectra or SWAN directional-frequency energy output spectra and results have been compared with the real paths traveled by the drifters.

Development of a colorimetric indicator label for food oxidation based on hexanal detection

In this work, a colorimetric indicator for food oxidation based on the detection of hexanal in gas-phase, has been developed. In fact, in recent years, the food packaging industry has evolved towards new generation of packaging, like active and intelligent. According to literature (Pangloli P. et al. 2002), hexanal is the main product of a fatty acid oxidation: the linoleic acid. So, it was chosen to analyse two kinds of potato chips, fried in two different oils with high concentration of linoleic acid: olive oil and sunflower oil. Five different formulas were prepared and their colour change when exposed to hexanal in gas phase was evaluated. The formulas evaluations were first conducted on filter paper labels. The next step was to select the thickener to add to the formula, in order to coat a polypropylene film, more appropriate than the filter paper for a production at industrial scale. Three kinds of thickeners were tested: a cellulose derivative, an ethylene vinyl-alcohol and a polyvinyl alcohol. To obtain the final labels with the autoadhesive layer, the polypropylene film with the selected formula and thickener was coat with a water based adhesive. For both filter paper and polypropylene labels, with and without autoadhesive layer, the detection limit and the detection time were measured. For the selected formula on filter paper labels, the stability was evaluated, when conserved on the dark or on the light, in order to determine the storage time. Both potato chips samples, stocked at the same conditions, were analysed using an optimised Headspace-Solid Phase Microextraction-Gas Chromatography-Mass Spectrometry (HS-SPME-GC-MS) method, in order to determine the concentration of volatilized hexanal. With the aim to establish if the hexanal can be considered as an indicator of the end of potato chips shelf life, sensory evaluation was conducted each day of HS-SPME-GC-MS analysis.

Attenuation of thermal radiation from flare through water curtains on offshore platform.

Flaring has been widely used in the upstream operation of the oil and gas industry, both onshore and offshore. It is considered a safe and reliable way to protect assets from overpressure and the environment from toxic gas using combustion. However, there are drawbacks to using flares, such as vibration and thermal radiation. Excessive contact with thermal radiation is harmful to offshore personnel and equipment. Research organizations and companies have invested time and money to combat this. Many technologies have been developed so far to reduce the risk of thermal radiation, one of them being the water curtain system. Several tests were done to see the effectiveness of the water curtain system in mitigating thermal radiation in an offshore environment. Each test varied in the flare output, wind speed, and the size of water droplets size of the water curtain. Later, the results of each test were compared and analyzed. The results showed that a water curtain system could be a solution to excessive thermal radiation that comes from an offshore flare. Moreover, the water curtain with smaller water droplets diameter gives a more favorable result in reducing thermal radiation. These results suggest that, although it offers simplicity and efficiency, designing an efficient water curtain system requires deep study. Various conditions, such as wind speed, flare intensity, and the size of the water droplets, plays a vital role in the effectiveness of the water curtain system in attenuating thermal radiation.