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.

Stabilimenti a rischio di incidente rilevante: Novità apportate dal D.Lgs. 105/2015

A partire dal 1° giugno 2015 è stato adottato ufficialmente in Europa il Regolamento 1272/2008/CE relativo alla classificazione, all'etichettatura e all'imballaggio delle sostanze e miscele pericolose, noto con il termine di Regolamento CLP. La data del 1° giugno 2015 coincide anche con il termine ultimo prescritto per il recepimento da parte degli Stati membri dell’Unione Europea della Direttiva 2012/18/UE sul controllo dei pericoli di incidenti rilevanti connessi con determinate sostanze pericolose. Dunque, come recepimento della sopracitata direttiva, il 29 luglio 2015 è stato emanato in Italia il D.Lgs. 105/2015, che ha introdotto numerose novità indotte non solo dalla direttiva da cui discende, ma anche e soprattutto dal fatto che il Legislatore italiano ha colto l’occasione per legiferare su alcuni aspetti attuativi della direttiva, così da produrre quello che viene identificato in ambito nazionale come Testo Unico per il rischio di incidente rilevante. La variazione più evidente apportata dal D.Lgs. 105/2015 rispetto alla norma precedente è l’adeguamento dell’allegato 1 al Regolamento CLP; l’allegato 1 elenca le sostanze e le categorie di sostanze pericolose con i corrispondenti valori soglia da utilizzare per valutare l’assoggettabilità degli stabilimenti al Decreto. A fronte dell’emanazione del D.Lgs. 105/2015, l’impatto dell’adeguamento è controverso e non noto a priori: nonostante la classificazione degli stabilimenti assoggettabili si mantenga sempre su due livelli, non è da escludersi il possibile passaggio di uno stabilimento da una situazione a rischio basso ad una a rischio alto o viceversa oil suo ingresso o la sua fuoriuscita dal campo di applicazione del Decreto. Altri elementi innovativi introdotti dal D.Lgs. 105/2015 sono relativi ai contenuti del Rapporto di Sicurezza, che deve essere redatto e trasmesso dai Gestori degli stabilimenti a maggior rischio: viene disposta per generici stabilimenti la possibilità di adottare per l’analisi preliminare del rischio metodologie alternative al metodo ad indici finora esclusivamente previsto dalla norma italiana. Inoltre, nel testo del D.Lgs. 105/2015 vengono ufficialmente indicati i riferimenti a due metodi semplificati (uno per il suolo e sottosuolo e uno per le acque superficiali) per la valutazione del rischio di contaminazione ambientale causato da rilasci rilevanti di idrocarburi liquidi e/o sostanze eco-tossiche da depositi. Per quanto riguarda il rischio di incidenti tecnologici innescati da fenomeni naturali (rischio NaTech), la nuova norma sancisce la libertà di scelta da parte dei Gestori della metodologia di valutazione da adottare con riferimento allo stato dell’arte in materia. Al fine di applicare una prima valutazione delle novità introdotte dal D.Lgs. 105/2015, si è considerata l’applicazione di alcune valutazioni previste dal Decreto a due casi di studio reali: come primo caso si è scelto uno Stabilimento che effettua principalmente l’attività di produzione e deposito nel settore degli esplosivi e come secondo caso uno Stabilimento che produce e confeziona prodotti per la nutrizione e difesa vegetale rappresentati per lo più da fertilizzanti organo-minerali e agrofarmaci.