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.

Ricerca ed applicazione di nuovi metodi di progettazione meccanica e di industrial design

The present dissertation relates to methodologies and technics about industrial and mechanical design. The author intends to give a complete idea about the world of design, showing the theories of Quality Function Deployment and TRIZ, of other methods just like planning, budgeting, Value Analysis and Engineering, Concurrent Engineering, Design for Assembly and Manufactoring, etc., and their applications to five concrete cases. In these cases there are also illustrated design technics as CAD, CAS, CAM; Rendering, which are ways to transform an idea into reality. The most important object of the work is, however, the birth of a new methodology, coming up from a comparison between QFD and TRIZ and their integration through other methodologies, just like Time and Cost Analysis, learned and skilled during an important experience in a very famous Italian automotive factory.

DESIGN OF A LIQUID FUEL INJECTOR FOR ALTERNATIVE FUEL STUDIES IN AN ATMOSPHERIC MODEL GAS TURBINE COMBUSTOR

A new liquid-fuel injector was designed for use in the atmospheric-pressure, model gas turbine combustor in Bucknell University’s Combustion Research Laboratory during alternative fuel testing. The current liquid-fuel injector requires a higher-than-desired pressure drop and volumetric flow rate to provide proper atomization of liquid fuels. An air-blast atomizer type of fuel injector was chosen and an experiment utilizing water as the working fluid was performed on a variable-geometry prototype. Visualization of the spray pattern was achieved through photography and the pressure drop was measured as a function of the required operating parameters. Experimental correlations were used to estimate droplet sizes over flow conditions similar to that which would be experienced in the actual combustor. The results of this experiment were used to select the desired geometric parameters for the proposed final injector design and a CAD model was generated. Eventually, the new injector will be fabricated and tested to provide final validation of the design prior to use in the combustion test apparatus.

Design, Construction, and Validation of an Atmospheric Combustor for Alternative Fuel Studies

An atmospheric combustion apparatus was designed through several iterations for Bucknell University's combustion laboratory. The final design required extensive fine-tuning of the fuel and air systems and repeated tests to arrive at a satisfactory procedure to transfer from gaseous to liquid fuel operation. Measurement of exhaust emissions were obtained under tests of gaseous methane and liquid heptane were operation in order to validate the functionality of the combustion apparatus, the fuel transition procedure, and emissions analyzer systems. The emission concentrations of CO, CO2, NOx, 02, S02, and unburned hydrocarbons from a multianalyzer and HFID analyzer were obtained for a range of equivalence ratios. The results verify the potential for future alternative fuel tests and illuminate necessary alterations for further liquid fuel studies.

The intracellular Ig fold: a robust protein scaffold for the engineering of molecular recognition

Protein scaffolds that support molecular recognition have multiple applications in biotechnology. Thus, protein frames with robust structural cores but adaptable surface loops are in continued demand. Recently, notable progress has been made in the characterization of Ig domains of intracellular origin--in particular, modular components of the titin myofilament. These Ig belong to the I(intermediate)-type, are remarkably stable, highly soluble and undemanding to produce in the cytoplasm of Escherichia coli. Using the Z1 domain from titin as representative, we show that the I-Ig fold tolerates the drastic diversification of its CD loop, constituting an effective peptide display system. We examine the stability of CD-loop-grafted Z1-peptide chimeras using differential scanning fluorimetry, Fourier transform infrared spectroscopy and nuclear magnetic resonance and demonstrate that the introduction of bioreactive affinity binders in this position does not compromise the structural integrity of the domain. Further, the binding efficiency of the exogenous peptide sequences in Z1 is analyzed using pull-down assays and isothermal titration calorimetry. We show that an internally grafted, affinity FLAG tag is functional within the context of the fold, interacting with the anti-FLAG M2 antibody in solution and in affinity gel. Together, these data reveal the potential of the intracellular Ig scaffold for targeted functionalization.

Design and Use of an Alternative Fuel Testing Apparatus and Assessment of the Feasibility of Biodiesel

Petroleum supply and environmental pollution issues constantly increase interest in renewable low polluting alternative fuels. Published test results show decreased pollution with similar power output and fuel consumption from Internal Combustion Engines (ICE) burning alternative fuels. More specifically, diesel engines burning biodiesel derived from plant oils and animal fats not only reduce harmful exhaust emissions but are renewable and environmentally friendly. To validate these claims and assess the feasibility of alternative fuels, independent engine dynamometer and emissions testing was performed. A testing apparatus capable of making relevant measurements was designed, built, and used to test and determine the feasibility of biodiesel. The apparatus marks the addition of a valuable testing tool to the University and provides a foundation for future experiments. This thesis will discuss the background of biodiesel, testing methods, design and function of the testing apparatus, experimental results, relevant calculations, and conclusions.

Design and Preliminary Results of an Atmospheric-Pressure Model Gas Turbine Combustor Utilizing Varying CO2 Doping Concentration in CH4 to Emulate Biogas Combustion

Utilization of biogas can provide a source of renewable energy in both heat and power generation. Combustion of biogas in land-based gas turbines for power generation is a promising approach to reducing greenhouse gases and US dependence on foreign-source fossil fuels. Biogas is a byproduct from the decomposition of organic matter and consists primarily of CH4 and large amounts of CO2. The focus of this research was to design a combustion device and investigate the effects of increasing levels of CO2 addition to the combustion of pure CH4 with air. Using an atmospheric-pressure, swirl-stabilized dump combustor, emissions data and flame stability limitations were measured and analyzed. In particular, CO2, CO, and NOx emissions were the main focus of the combustion products. Additionally, the occurrence of lean blowout and combustion pressure oscillations, which impose significant limitations in operation ranges for actual gas turbines, was observed. Preliminary kinetic and equilibrium modeling was performed using Cantera and CEA for the CH4/CO2/Air combustion systems to analyze the effect of CO2 upon adiabatic flame temperature and emission levels. The numerical and experimental results show similar dependence of emissions on equivalence ratio, CO2 addition, inlet air temperature, and combustor residence time. (C) 2014 Elsevier Ltd. All rights reserved.

Design and implementation of a 3D computer game controller using inertial MEMS sensors

Though 3D computer graphics has seen tremendous advancement in the past two decades, most available mechanisms for computer interaction in 3D are high cost and targeted for industry and virtual reality applications. Recent advances in Micro-Electro-Mechanical-System (MEMS) devices have brought forth a variety of new low-cost, low-power, miniature sensors with high accuracy, which are well suited for hand-held devices. In this work a novel design for a 3D computer game controller using inertial sensors is proposed, and a prototype device based on this design is implemented. The design incorporates MEMS accelerometers and gyroscopes from Analog Devices to measure the three components of the acceleration and angular velocity. From these sensor readings, the position and orientation of the hand-held compartment can be calculated using numerical methods. The implemented prototype is utilizes a USB 2.0 compliant interface for power and communication with the host system. A Microchip dsPIC microcontroller is used in the design. This microcontroller integrates the analog to digital converters, the program memory flash, as well as the core processor, on a single integrated circuit. A PC running Microsoft Windows operating system is used as the host machine. Prototype firmware for the microcontroller is developed and tested to establish the communication between the design and the host, and perform the data acquisition and initial filtering of the sensor data. A PC front-end application with a graphical interface is developed to communicate with the device, and allow real-time visualization of the acquired data.

Design of a lab scale direct-filtration system and its application in process lab

The Environmental Process and Simulation Center (EPSC) at Michigan Technological University started accommodating laboratories for an Environmental Engineering senior level class CEE 4509 Environmental Process and Simulation Laboratory since 2004. Even though the five units that exist in EPSC provide the students opportunities to have hands-on experiences with a wide range of water/wastewater treatment technologies, a key module was still missing for the student to experience a full cycle of treatment. This project fabricated a direct-filtration pilot system in EPSC and generated a laboratory manual for education purpose. Engineering applications such as clean bed head loss calculation, backwash flowrate determination, multimedia density calculation and run length prediction are included in the laboratory manual. The system was tested for one semester and modifications have been made both to the direct filtration unit and the laboratory manual. Future work is also proposed to further refine the module.

Enzyme engineering of aminotransferases for improved activity and thermostability

The production by biosynthesis of optically active amino acids and amines satisfies the pharmaceutical industry in its demand for chiral building blocks for the synthesis of various pharmaceuticals. Among several enzymatic methods that allow the synthesis of optically active aminoacids and amines, the use of minotransferase is a promising one due to its broad substrate specificity and no requirement for external cofactor regeneration. The synthesis of chiral compounds by aminotransferases can be done either by asymmetric synthesis starting from keto acids or ketones, and by kinetic resolution starting from racemic aminoacids or amines. The asymmetric synthesis of substituted (S)-aminotetralin, an active pharmaceutical ingredient (API), has shown to have two major factors that contribute to increasing the cost of production. These factors are the raw material cost of biocatalyst used to produce it and product loss during biocatalyst separation. To minimize the cost contribution of biocatalyst and to minimize the loss of product, two routes have been chosen in this research: 1. To engineer the aminotransferase biocatalyst to have greater specific activity, and 2. Improve the engineering of the process by immobilization of biocatalyst in calcium alginate and addition of cosolvents. An (S)-aminotransferase (Mutant CNB03-03) was immobilized, not as purified enzyme but as enzyme within spray dried cells, in calcium alginate beads and used to produce substituted (S)-aminotetralin at 50 °C and pH 7 in experiments where the immobilized biocatalyst was recycled. Initial rate of reaction for cycle 1 (6 hr duration) was determined to be 0.258 mM/min, for cycle 2 (20 hr duration) it decreased by ~50% compared to cycle 1, and for cycle 3 (20 hr duration) it decreased by ~90% compared to cycle 1 (immobilized preparation consisted of 50 mg of spray dried cells per gram of calcium alginate). Conversion to product for each cycle decreased as well, from 100% in cycle 1 (About 50 mM), 80% in cycle 2, and 30% after cycle 3. This mutant was determined to be deactivated at elevated temperatures during the reaction cycle and was not stable enough to allow multiple cycles in its immobilized form. A new mutant aminotransferase was isolated by applying error-prone polymerase chain reaction (PCR) on the gene coding for this enzyme and screening/selection: CNB04-01. This mutant showed a significant improvement in thermostability in comparison to CNB03-03. The new mutant was immobilized and tested under similar reaction conditions. Initial rate remained fairly constant (0.2 mM/min) over four cycles (each cycle with a duration of about 20 hours) with the mutant retaining almost 80% of initial rate in the fourth cycle. The final product concentrations after each cycle did not decrease during recycle experiments. Thermostability of CNB04-01 was much improved compared to CNB03-03. Under the same reaction conditions as stated above, the addition of co-solvents was studied in order to increase substituted tetralone solubility. Toluene and sodium dodecylsulfate (SDS) were used. SDS at 0.01% (w/v) allowed four recycles of the immobilized spray dried cells of CNB04-01, always reaching higher product concentration (80-85 mM) than the system with toluene at 3% (v/v) -70 mM-. The long term activity of immobilized CNB04-01 in a system with SDS 0.01% (w/v) at 50 °C, pH 7 was retained for three cycles (20 to 24 hours each one), reaching always final product concentration between 80-85 mM, but dropping precipitously in the fourth cycle to a final product concentration of 50 mM. Although significant improvement of immobilization on productivity and stability were observed using CNB04-01, another observation demonstrated the limitations of an immobilization strategy on reducing process costs. After analyzing the results of this experiment it was seen that a sudden drop occurred on final product concentration after the third recycle. This was due to product accumulation inside the immobilized preparation. In order to improve the economics of the process, research was focused on developing a free enzyme with an even higher activity, thus reducing raw material cost as well as improving biomass separation. A new enzyme was obtained (CNB05-01) using error-prone PCR and screening using as a template the gene derived from the previous improved enzyme. This mutant was determined to have 1.6 times the initial rate of CNB04-01 and had a higher temperature optimum (55°). This new enzyme would allow reducing enzyme loading in the reaction by five-fold compared to CNB03-03, when using it at concentration of one gram of spray dried cells per liter (completing the reaction after 20-24 hours). Also this mutant would allow reducing process time to 7-8 hours when used at a concentration of 5 grams of spray dried cells per liter compared to 24 hours for CNB03-03, assuming that the observations shown before are scalable. It could be possible to improve the economics of the process by either reducing enzyme concentration or reducing process time, since the production cost of the desired product is primarily a function of both enzyme concentration and process time.

Design, construction, and testing of a research quality electric machine testbed

With energy demands and costs growing every day, the need for improving energy efficiency in electrical devices has become very important. Research into various methods of improving efficiency for all electrical components will be a key to meet future energy needs. This report documents the design, construction, and testing of a research quality electric machine dynamometer and test bed. This test cell system can be used for research in several areas including: electric drives systems, electric vehicle propulsion systems, power electronic converters, load/source element in an AC Microgrid, as well as many others. The test cell design criteria, and decisions, will be discussed in reference to user functionality and flexibility. The individual power components will be discussed in detail to how they relate to the project, highlighting any feature used in operation of the test cell. A project timeline will be discussed, clearly stating the work done by the different individuals involved in the project. In addition, the system will be parameterized and benchmark data will be used to provide the functional operation of the system. With energy demands and costs growing every day, the need for improving energy efficiency in electrical devices has become very important. Research into various methods of improving efficiency for all electrical components will be a key to meet future energy needs. This report documents the design, construction, and testing of a research quality electric machine dynamometer and test bed. This test cell system can be used for research in several areas including: electric drives systems, electric vehicle propulsion systems, power electronic converters, load/source element in an AC Microgrid, as well as many others. The test cell design criteria, and decisions, will be discussed in reference to user functionality and flexibility. The individual power components will be discussed in detail to how they relate to the project, highlighting any feature used in operation of the test cell. A project timeline will be discussed, clearly stating the work done by the different individuals involved in the project. In addition, the system will be parameterized and benchmark data will be used to provide the functional operation of the system.

Design of high fidelity building energy monitoring system

Building energy meter network, based on per-appliance monitoring system, willbe an important part of the Advanced Metering Infrastructure. Two key issues exist for designing such networks. One is the network structure to be used. The other is the implementation of the network structure on a large amount of small low power devices, and the maintenance of high quality communication when the devices have electric connection with high voltage AC line. The recent advancement of low-power wireless communication makes itself the right candidate for house and building energy network. Among all kinds of wireless solutions, the low speed but highly reliable 802.15.4 radio has been chosen in this design. While many network-layer solutions have been provided on top of 802.15.4, an IPv6 based method is used in this design. 6LOWPAN is the particular protocol which adapts IP on low power personal network radio. In order to extend the network into building area without, a specific network layer routing mechanism-RPL, is included in this design. The fundamental unit of the building energy monitoring system is a smart wall plug. It is consisted of an electricity energy meter, a RF communication module and a low power CPU. The real challenge for designing such a device is its network firmware. In this design, IPv6 is implemented through Contiki operation system. Customize hardware driver and meter application program have been developed on top of the Contiki OS. Some experiments have been done, in order to prove the network ability of this system.

INVESTIGATION OF AIR JIGGING AND AIR CLASSIFICATION TO RECOVER METALLIC PARTICLES FROM ANALYTICAL SAMPLES

Analyzing “nuggety” gold samples commonly produces erratic fire assay results, due to random inclusion or exclusion of coarse gold in analytical samples. Preconcentrating gold samples might allow the nuggets to be concentrated and fire assayed separately. In this investigation synthetic gold samples were made using similar density tungsten powder and silica, and were preconcentrated using two approaches: an air jig and an air classifier. Current analytical gold sampling method is time and labor intensive and our aim is to design a set-up for rapid testing. It was observed that the preliminary air classifier design showed more promise than the air jig in terms of control over mineral recovery and preconcentrating bulk ore sub-samples. Hence the air classifier was modified with the goal of producing 10-30 grams samples aiming to capture all of the high density metallic particles, tungsten in this case. Effects of air velocity and feed rate on the recovery of tungsten from synthetic tungsten-silica mixtures were studied. The air classifier achieved optimal high density metal recovery of 97.7% at an air velocity of 0.72 m/s and feed rate of 160 g/min. Effects of density on classification were investigated by using iron as the dense metal instead of tungsten and the recovery was seen to drop from 96.13% to 20.82%. Preliminary investigations suggest that preconcentration of gold samples is feasible using the laboratory designed air classifier.

DESIGN AND IMPLEMENT DYNAMIC PROGRAMMING BASED DISCRETE POWER LEVEL SMART HOME SCHEDULING USING FPGA

With the development and capabilities of the Smart Home system, people today are entering an era in which household appliances are no longer just controlled by people, but also operated by a Smart System. This results in a more efficient, convenient, comfortable, and environmentally friendly living environment. A critical part of the Smart Home system is Home Automation, which means that there is a Micro-Controller Unit (MCU) to control all the household appliances and schedule their operating times. This reduces electricity bills by shifting amounts of power consumption from the on-peak hour consumption to the off-peak hour consumption, in terms of different “hour price”. In this paper, we propose an algorithm for scheduling multi-user power consumption and implement it on an FPGA board, using it as the MCU. This algorithm for discrete power level tasks scheduling is based on dynamic programming, which could find a scheduling solution close to the optimal one. We chose FPGA as our system’s controller because FPGA has low complexity, parallel processing capability, a large amount of I/O interface for further development and is programmable on both software and hardware. In conclusion, it costs little time running on FPGA board and the solution obtained is good enough for the consumers.