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.

Laboratory verification of predicted permanent deformation in asphalt materials following climate change.

In the past a change in temperature of 5°C most often occurred over intervals of thousands of years. According to estimates by the IPCC, in the XXI century is expected an increase in average temperatures in Europe between 1.8 and 4.0°C in the best case caused by emissions of carbon dioxide and other GHG from human activities. As well as on the environment and economic context, global warming will have effects even on road safety. Several studies have already shown how increasing temperature may cause a worsening of some types of road surface damages, especially rutting, a permanent deformation of the road structures consisting in the formation of a longitudinal depression in the wheelpath, mostly due to the rheological behavior of bitumen. This deformation evolves during the hot season because of the heating capacity of the asphalt layers, in fact, the road surface temperature is up to 24°C higher than air. In this thesis, through the use of Wheeltrack test, it was studied the behavior of some types of asphalt concrete mixtures subjected to fatigue testing at different temperatures. The objectives of this study are: to determine the strain variation of different bituminous mixture subjected to fatigue testing at different temperature conditions; to investigate the effect of aggregates, bitumen and mixtures’ characteristics on rutting. Samples were made in the laboratory mostly using an already prepared mixtures, the others preparing the asphalt concrete from the grading curve and bitumen content. The same procedure was performed for each specimen: preparation, compaction using the roller compactor, cooling and heating before the test. The tests were carried out at 40 - 50 - 60°C in order to obtain the evolution of deformation with temperature variation, except some mixtures for which the tests were carried out only at 50°C. In the elaboration of the results were considered testing parameters, component properties and the characteristics of the mixture. Among the testing parameters, temperature was varied for each sample. The mixtures responded to this variation with a different behavior (linear logarithmic and exponential) not directly correlated with the asphalt characteristics; the others parameters as load, passage frequency and test condition were kept constant. According to the results obtained, the main contribution to deformation is due to the type of binder used, it was found that the modified bitumen have a better response than the same mixtures containing traditional bitumen; to the porosity which affects negatively the behavior of the samples and to the homogeneity ceteris paribus. The granulometric composition did not seem to have interfered with the results. Overall has emerged at working temperature, a decisive importance of bitumen composition, than the other characteristics of the mixture, that tends to disappear with heating in favor of increased dependence of rutting resistance from the granulometric composition of the sample considered. In particular it is essential, rather than the mechanical characteristics of the binder, its chemical properties given by the polymeric modification. To confirm some considered results, the maximum bulk density and the air voids content were determined. Tests have been conducted in the laboratories of the Civil Engineering Department at NTNU in Trondheim according to European Standards.

Crystallization and morphology of the PLLA phase within random poly (L-lactide-ran-ɛ-caprolactone)

This work has mainly focused on the poly (L-lactide) (PLLA) which is a material for multiple applications with performances comparable to those of petrochemical polymers (PP, PS, PET, etc. ...), readily recyclable and also compostable. However, PLLA has certain shortcomings that limit its applications. It is a brittle, hard polymer with a very low elongation at break, hydrophobic, exhibits low crystallization kinetics and takes a long time to degrade. The properties of PLLA may be modified by copolymerization (random, block, and graft) of L-lactide monomers with other co-monomers. In this thesis it has been studied the crystallization and morphology of random copolymers poly (L-lactide-ran-ε-caprolactone) with different compositions of the two monomers since the physical, mechanical, optical and chemical properties of a material depend on this behavior. Thermal analyses were performed by differential scanning calorimetry (DSC) and thermogravimetry (TGA) to observe behaviors due to the different compositions of the copolymers. The crystallization kinetics and morphology of poly (L-lactide-ran-ε-caprolactone) was investigated by polarized light optical microscopy (PLOM) and differential scanning calorimetry (DSC). Their thermal behavior was observed with crystallization from melt. It was observed that with increasing amounts of PCL in the copolymer, there is a decrease of the thermal degradation. Studies on the crystallization kinetics have shown that small quantities of PCL in the copolymer increase the overall crystallization kinetics and the crystal growth rate which decreases with higher quantities of PCL.

Dynamics of inorganic carbon and carbonate saturation in the Gulf of Cádiz (SW Spain)

The study of inorganic carbon chemistry of the coastal ocean is conducted in the Gulf of Cádiz (GoC). Here we describe observations obtained during 4 sampling cruises in March, June, September and November 2015. The primary data set consists of state-of-the-art measurements of the keystone parameters of the marine CO2 system: Total Alkalinity (TA), pH, dissolved inorganic carbon (DIC). We have then calculated aragonite and calcite saturation state. The distribution of inorganic carbon system parameters in the north eastern shelf of the Gulf of Cádiz showed temporal and spatial variability. River input, mixing, primary production, respiration and remineralization were factors that controlled such distributions. Data related to carbonate saturation of calcite and aragonite reveal the occurrence of a supersaturated water; in any case, both species increased with distance and decreased with depth. The carbon system parameters present a different behaviour close to the coast to offshore ad at deeper water. In this area six water masses are clearly identified by their different chemical properties: Surface Atlantic Water, North Atlantic Central Water (NACW) and Mediterranean Water (MOW). Moreover, with this work the measurement of calcium in seawater is optimize, allowing a better quantification for future work of the saturation state of CaCO3.