Bioremediation of diesel contaminated soils : an investigation into the effects of biosurfactant and organic matter amendments

The aim of this study was to investigate the effects of biosurfactants and organic matter amendments on the bioremediation of diesel contaminated soil. Two strains of Pseudomonas aeruginosa with the ability to produce biosurfactant were isolated from a water and soil sample in Co. Sligo. The first strain, Isolate A, produced a biosurfactant which contained four rhamnose containing compounds, when grown in proteose peptone glucose ammonium salts medium with glucose as the carbon source. Two of the components were identified as rhamnolipid 1 and 2 whilst the other two components were unidentified. The second strain, Isolate GO, when grown in similar conditions produced a biosurfactant which contained only rhamnolipid 2. The type of aeration system used had a significant effect on the abiotic removal of diesel from soil. Forced aeration at a rate of 120L 02/kg soil/ hour resulted in the greatest removal. Over a 112 day incubation period this type o f aeration resulted in the removal o f 48% o f total hexane extractable material. In relation to bioremediation of the diesel contaminated sandy soil, amending the soil with two inorganic nutrients, KH2PO4 and NÜ4N03, significantly enhanced the removal of diesel, especially the «- alkanes, when compared to an unamended control. The biosurfactant from Isolate A and a biosurfactant produced by Pseudomonas aeruginosa NCIMB 8628 (a known biosurfactant producer), when applied at a concentration of three times their critical micelle concentration, had a neutral effect on the biodégradation o f diesel contaminated sandy soil, even in the presence o f inorganic nutrients. It was deduced that the main reason for this neutral effect was because they were both readily biodegraded by the indigenous microorganisms. The most significant removal of diesel occurred when the soils were amended with two organic materials plus the inorganic nutrients. Amendment of the diesel contaminated soil with spent brewery grain (SBG) removed significantly more diesel than amendment with dried molassed sugar beet pulp (DMSBP). After a 108 day incubation period, amendment of the diesel contaminated soil with DMSBP plus inorganic nutrients and SBG plus inorganic nutrients resulted in 72 and 89% removal of diesel range organics (DRO), in comparison to 41% removal of DRO in an inorganic nutrient amended control. The first order kinetic model described the degradation of the different diesel components with high correlation and was used to calculate Vi lives. The V2 life, of the total «-alkanes in the diesel was reduced from 40 days in the control to 8.5 and 5.1 days in the presence of DMSBP and SBG, respectively. The V2 life o f the unresolved complex mixture (UCM) in the diesel contaminated soil was also significantly reduced in the presence o f the two organics. DMSBP and SBG addition reduced UCM V2 life to 86 and 43 days, respectively, compared to 153 days in the control. The component of diesel whose removal was enhanced the greatest through the organic material amendments was the isoprenoid, pristane, a compound which until recently was thought to be nonbiodegradable and was used as an inert biomarker in oil degradation studies. The V2 life of pristane was reduced from 533 days in the nutrient amended control to 49.5 and 19.5 days in DMSBP and SBG amended soils. These results indicate that the addition o f the DMSBP and SBG to diesel contaminated soil stimulated diesel biodégradation, probably by enhancing the indigenous diesel degrading microbial population to degrade diesel hydrocarbons, whilst the addition o f biosurfactants had no enhanced effect on the bioremediation process.

An evaluation of septic tank effluent movement in soil and groundwater systems

Recent studies have shown that septic tank systems are a major source of groundwater pollution. Many public health workers feel that the most cri^cal aspect of the use of septic tanks as a means of sewage disposal is the contamination of private water wells with attendant human health hazards. In this study the movement and attenuation of septic tank effluents in a range of soil/overburden types and hydrogeological situations was investigated. The suitability of a number of chemical and biological tracer materials to monitor the movement of septic tank effluent constituents to groundwater sources was also examined. The investigation was divided into three separate but inteiTelated sections. In the first section of the study the movement of septic tank effluent from two soil treatment systems was investigated by direct measurements of soil nutrient concentrations and enteric bacterial numbers in the soil beneath and downgradient of the test systems. Two sites with different soil types and hydrogeological characteristics were used. The results indicated that the attenuation of the effluent in both of the treatment systems was incomplete. Migration of nitrate, ammonium, phosphate and fecal bacteria to a depth of 50 cm beneath the inverts of the distribution tiles was demonstrated on all sampling occasions. The lateral migration of the pollutants was less pronounced, although on occasions high nutrients levels and fecal bacterial numbers were detected at a lateral distance of 4.0 m downgradient of the test systems. There was evidence that the degree and extent of effluent migration was increased after periods of heavy or prolonged rainfall when the attenuating properties of the treatment systems were reduced as a result of saturation of the soil. The second part of the study examined the contamination of groundwaters downgradient of septic tank soil treatment systems. Three test sites were used in the investigation. The sites were chosen because of differences in the thicknesses and nature of the unsaturated zone available for effluent attenuation at each of the locations. A series of groundwater monitoring boreholes were installed downgradient of the test systems at each of the sites and these were sampled regularly to assess the efficiency of the overburden material in reducing the polluting potential of the wastewater. Effluent attenuation in the septic tank treatment systems was shown to be incomplete, resulting in chemical and microbiological contamination of the groundwaters downgradient of the systems. The nature and severity of groundwater contamination was dependent on the composition and thickness of the unsaturated zone and the extent of weathering in the underlying saturated bedrock. The movement of septic tank effluent through soil/overburdens to groundwater sources was investigated by adding a range of chemical and biological tracer materials to the three septic tank systems used in section two of the study. The results demonstrated that a single tracer type cannot be used to accurately monitor the movement of all effluent constituents through soils to groundwater. The combined use of lithium bromide and endospores of Bacillus globigii was found to give an accurate indication of the movement of both the chemical and biological effluent constituents.

Training and development in Irish technology companies

The sustained economic growth that has been experienced in the Irish economy in recent years has relied, to a large extent, on the contribution and performance of those industry sectors that possess the ability to provide high-value-added products and services to domestic and international markets. One such contributor has been the Technology sector. However, the performance of this sector relies upon the availability of the necessary capabilities and competencies for Technology companies to remain competitive. The Expert Group on Future Skills Needs have forecasted future skills shortages in this sector. The purpose of this research has been to examine the extent to which Irish Technology companies are taking measures to meet changing skills requirements, through training and development interventions. Survey research methods (in the form of a mail questionnaire, supported by a Web-based questionnaire) have been used to collect information on the expenditure on, and approach to, training and development in these companies, in addition to the methods, techniques and tools/aids that are used to support the delivery of these activities. The contribution of Government intervention has also been examined. The conclusions have been varied. When the activities of the responding companies are considered in isolation, the picture to emerge is primarily positive. Although the expenditure on training and development is slightly lower than that indicated in previous studies, the results vary by company size. Technical employees are clearly the key focus of training provision, while Senior Managers and Directors, Clerical and Administrative staff and Manual workers are a great deal more neglected in training provision. Expenditure on, and use of, computer-based training methods is high, as is the use of most of the specified techniques for facilitating learning. However, when one considers the extent to which external support (in the form of Government interventions and cooperation with other companies and with education and training providers) is integrated into the overall training practices of these companies, significant gaps in practice are identified. The thesis concludes by providing a framework to guide future training and development practices in the Technology sector.

What value can be attached to a concept of mystery and has it a place in contemporary Western culture?

The idea for this thesis arose from a chain of reactions first set in motion by a particular experience. In keeping with the contemporary need to deconstruct every phenomenon it seemed important to analyse this experience in the hope of a satisfactory explanation. The experience referred to is the aesthetic experience provoked by works of art. The plan for the thesis involved trying to establish whether the aesthetic experience is unique and individual, or whether it is one that is experienced universally. Each question that arises in the course of this exploration promotes a dialectical reaction. I rely on the history of aesthetics as a philosophical discipline to supply the answers. This study concentrates on the efforts by philosophers and critical theorists to understand the tensions between the empirical and the emotional, the individual and the universal responses to the sociological, political and material conditions that prevail and are expressed through the medium of art. What I found is that the history of aesthetics is full of contradictory evidence and cannot provide a dogmatic solution to the questions posed. In fact what is indicated is that the mystery that attaches to the aesthetic experience is one that can also apply to the spiritual or transcendent experience. The aim of this thesis is to support the contribution of visual art in the spiritual well being of human development and supports the uniqueness of the evaluation and aesthetic judgement by the individual of a work of art. I suggest that mystery will continue to be of value in the holistic development of human beings and this mystery can be expressed through visual art. Furthermore, this thesis might suggest that what could be looked at is whether a work of art may be redemptive in its affect and offset the current decline in affective religious practice.

The spatial analysis and speciation of uranium and thorium series radionuclides in the soil of the Cronamuck Valley, County Donegal, Ireland

This thesis details the findings of a study into the spatial distribution and speciation of 238U, 226Ra and 228Ra in the soils of the Cronamuck valley, County Donegal . The region lies on the north-eastern edge of the Barnesmore granite and has been the subject of uranium prospecting efforts in the past. The results of the project provide information on the practicability of geostatistical techniques as a means of estimating the spatial distribution of natural radionuclides and provide insight into the behaviour of these nuclides and their modes of occurrence and enrichment in an upland bog environment. The results of the geostatistical survey conducted on the area indicate that the primary control over the levels of the studied nuclides in the soil of the valley is the underlying geology. Isopleth maps of nuclide levels in the valley indicate a predominance of elevated nuclide levels in the samples drawn from the granite region, statistical analysis of the data indicating that levels of the nuclides in samples drawn from the granite are greater than levels drawn from the non-granite region by up to a factor of 4.6 for 238U and 4.9 for 226Ra. Redistribution of the nuclides occurs via drainage systems within the valley, this process being responsible for transport of nuclides away from the granite region resulting in enrichment of nuclides in soils not underlain by the granite. Distribution of the nuclides within the valley is erratic, the effect of drainage f lows on the nuclides resulting in localized enriched areas within the valley. Speciation of the nuclides within one of the enriched areas encountered in the study indicates that enrichment is as a result of saturation of the soil with drainage water containing trace amounts of radionuclides. 238U is primarily held within the labile fractions (exchangeable cat ions + easily oxidisable organics + amorphous iron oxides ) of the soil , 226Ra being associated with the non- labile fractions, most probably the resistant organic material. 228Ra displays a significant occurrence in both the labile and non- labile fractions. The ability of the soil to retain uranium appears to be affected largely by the redox status of the soil, samples drawn from oxidizing environments tending to have little or no uranium in the easily oxidisable and amorphous iron oxide fractions. This loss of uranium from oxidised soil samples is responsible for the elevated 226Ra /238U disequilibrium encountered in the enriched areas of the valley. Analysis of the data indicates that samples displaying elevated 226Ra/238U ratios also exhibit elevated 228Ra/238U ratios indicating a loss of uranium from the samples as opposed to an enrichment of 226Ra.

The role of biomass and biorefineries in a sustainable future

Some o f the biggest issues facing humanity in the 21st century include energy security, global warming and resource scarcity. These issues will affect every nation and Ireland is no exception. There is much research underway to uncover technologies that will allow the world to overcome such problems, but none offer the flexibility o f biomass. Unlike other sustainable technologies, which offer a solution to one or at most two o f the above problems, biomass as demonstrated by the author, can play a part in mitigating all o f the above problems. It has been known for some time that biomass can be used in various ways as a form o f renewable energy, but with the development o f biorefineries biomass can be used to produce material as well as fuel products. In this report the author has looked at the viability and benefits o f biomass, bioenergy and biorefining in Ireland. The author has demonstrated that such technologies when implemented correctly are sustainable from an economic, environmental and societal point o f view. The author has shown in this thesis that abundant supplies o f biomass make bio re fineries a viable business opportunity in Ireland and has shown how a number o f biorefinery scenarios have the potential to be extremely profitable. The author has evaluated the profitability o f material product-based bio re fineries as well as fuel productbased configurations. The author demonstrated that value-added co-products help to make bio refineries profitable even when excise-relief is not granted on bio fuels. In this thesis the author has revealed some o f the problems that bioenergy and biorefineries have had to overcome to date and examines challenges that remain for bioenergy and biorefining, and looks at the future opportunities for bio fuels. This report concludes that biomass and biorefining has exciting business potential while offering unique opportunities to mitigate the problems o f the future.

Acoustic emission analysis of the effect of a 2D wedge shaped blade on the compact bone cutting process

Surgeons may use a number of cutting instruments such as osteotomes and chisels to cut bone during an operative procedure. The initial loading of cortical bone during the cutting process results in the formation of microcracks in the vicinity of the cutting zone with main crack propagation to failure occuring with continued loading. When a material cracks, energy is emitted in the form of Acoustic Emission (AE) signals that spread in all directions, therefore, AE transducers can be used to monitor the occurrence and development of microcracking and crack propagation in cortical bone. In this research, number of AE signals (hits) and related parameters including amplitude, duration and absolute energy (abs-energy) were recorded during the indentation cutting process by a wedge blade on cortical bone specimens. The cutting force was also measured to correlate between load-displacement curves and the output from the AE sensor. The results from experiments show AE signals increase substantially during the loading just prior to fracture between 90% and 100% of maximum fracture load. Furthermore, an amplitude threshold value of 64dB (with approximate abs-energy of 1500 aJ) was established to saparate AE signals associated with microcracking (41 – 64dB) from fracture related signals (65 – 98dB). The results also demonstrated that the complete fracture event which had the highest duration value can be distinguished from other growing macrocracks which did not lead to catastrophic fracture. It was observed that the main crack initiation may be detected by capturing a high amplitude signal at a mean load value of 87% of maximum load and unsteady crack propagation may occur just prior to final fracture event at a mean load value of 96% of maximum load. The author concludes that the AE method is useful in understanding the crack initiation and fracture during the indentation cutting process.

Optimising the design and manufacture of a customised, prescription fit, Maxillo-facial prosthesis

This thesis is a continuation of the Enterprise-Ireland Research Innovation Fund (RIF) Project entitled’ "Design and Manufacturing of Customised Maxillo-Facial Prostheses" The primary objective of this Internal Research Development Program (IRDP) project was to investigate two fundamental design changes 1 To incorporate the over-denture abutments directly into the implant. 2 To remove the restraining wings by the addition of screws, which affix the. implant to the dense material of the jawbone. The prosthetic was redesigned using the ANSYS Finite Element Analysis software program and analysed to* • Reduce the internal von Mises stress distribution The new prosthetic had a -63.63 % lower von Mises stress distribution when compared with the original prosthetic. • Examine the screw preload effects. A maximum relative displacement of 22 6 * lO^mm between the bone and screw was determined, which is well below the critical threshold of micromotion which prevents osseointegration • Investigate the prosthetic-bone contact interface. Three models of the screw, prosthesis, and bone, were studied. (Axisymmetnc, quarter volume, and full volume), a recommended preload torque of 0 32 Nm was applied to the prosthetic and a maximum von Mises stress of 1.988 MPa was predicted • Study the overdenture removal forces. This analysis could not be completed because the correct plastic multilinear properties of the denture material could not be established The redesigned prosthetic was successfully manufactured on a 3-axis milling machine with an indexing system The prosthetic was examined for dimensional quality and strength The research established the feasibility of the new design and associated manufacturing method.

Investigation into the potential for establishing a self-sustainable wetland ecosystem over pyritic mine tailings

Research was conducted to investigate the potential for ecologically engineering a sustainable wetland ecosystem over pyritic mine tailings to prevent the generation of acid mine drainage. Ecological engineering is technology with the primary goal being the creation of self-sustainable ecological systems. Work involved the design and construction of a pilot-scale wetland system comprising three wetland cells, each covering 100 m2. Approximately forty tonnes of pyritic mine tailings were deposited on the base of the first cell above a synthetic liner, covered with peat, flooded and planted with emergent wetland macrophytes Typha latifolia, Phragmites australis, and Juncus effusus. The second cell was constructed as a conventional free water surface wetland, planted identically, and used as a reference wetland/experimental control. Wetland monitoring to determine long-term sustainability focused on indicators of ecosystem health including ecological, hydrological, physico-chemical, geochemical, and biotic metrics. An integrated assessment was conducted that involved field ecology in addition to ecological risk assessment. The objective of the field ecology study was to use vegetative parameters as ecological indicators for documenting wetlands success or degradation. The goal of the risk assessment was to determine if heavy-metal contamination of the wetland sediments occurred through metal mobilisation from the underlying tailings, and to evaluate if subsequent water column chemistry and biotic metal concentrations were significantly correlated with adverse wetland ecosystem impacts. Data were used to assess heavy metal bioavailability within the system as a function of metal speciation in the wetland sediments. Results indicate hydrology is the most important variable in the design and establishment of the tailings wetland and suggest a wetland cover is an ecologically viable alternative for pyritic tailings which are feasible to flood. Ecological data indicate that in terms of species richness and diversity, the tailings-wetland was exhibiting the ecological characteristics of natural wetlands within two years. Ata indicate that pH and conductivity in the tailings-wetland were not adversely impacted by the acid-generating potential or sulphate concentration of the tailings substrate and its porewater. Similarly, no enhanced seasonal impacts from sulphate or metals in the water column, nor adverse impacts on the final water quality of the outflows, were detected. Mean total metal concentrations in the sediments of the tailings-wetland indicate no significant adverse mobilisation of metals into the peat substrate from the tailings. Correlation analyses indicate a general increase in sediment metal concentration in this wetland with increasing water depth and pH, and a corresponding decrease in the metal concentrations of the water column. Sediment extractions also showed enrichment of Cd, Fe, Pb and Zn in the oxidisable fraction (including sulphides and organic matter) of the tailings-wetland sediments. These data suggest that adsorption and coprecipitation of metals is occurring from the water column of the tailings wetland with organic material at increasing depths under reducing conditions. The long-term control of metal bioavailability in the tailings wetland will likely be related to the presence and continual build-up of organic carbon binding sites in the developing wetland above the tailings. Metal speciation including free-metal ion concentration and the impact of physico-chemical parameters particularly pH and organic matter, were investigated to assess ecotoxicological risk. Results indicate that potentially bioavailable metals (the sum of the exchangeable and reducible fractions) within the tailings wetland are similar to values cited for natural wetlands. Estimated free-metal ion concentrations calculated from geochemical regression models indicate lower free-metal ion concentrations of Cd in the tailings wetland than natural wetlands and slightly higher free-metal ion concentrations of Pb and Zn. Increased concentrations of metals in roots, rhizomes and stems of emergent macrophytes did not occur in the tailings wetland. Even though a substantial number of Typha latifolia plants were found rooting directly into tailings, elevated metals were not found in these plant tissues. Phragmites also did not exhibit elevated metal concentrations in any plant tissues. Typha and Phragmites populations appear to be exhibiting metal-tolerant behaviour. The chemistry of the water column and sediments in Silvermines wetland were also investigated and were much more indicative of a wetland system impacted by heavy metal contamination than the tailings-wetland. Mean Dc, Fe, Mn, Pb and Zn concentrations in the water column and sediments of Silvermines wetlands were substantially higher than in the pilot wetlands and closely approximate concentrations in these matrices contaminated with metals from mining. In addition, mean sulphate concentration in Silvermines wetland was substantially higher and is closer to sulphate concentrations in waters associated with mining. Potentially bioavailable metals were substantially elevated in Silvermines wetland in comparison to the pilot wetlands and higher than those calculated for natural rive sediments. However, Fe oxy-hydroxide concentrations in Silvermines sediments are also much higher than in the pilot wetlands and this significantly impacts the concentration of free-metal ions in the sediment porewater. The free-metal ion concentrations for Pb and Zn indicate that Silvermines wetland is retaining metals and acting as a treatment wetland for drainage emanating from Silvermines tailings dam.

Optimisation of a surface mount technology process using a SnAgCu lead-free alloy

The impending introduction of lead-free solder in the manufacture of electrical and electronic products has presented the electronics industry with many challenges. European manufacturers must transfer from a tin-lead process to a lead-free process by July 2006 as a result of the publication of two directives from the European Parliament. Tin-lead solders have been used for mechanical and electrical connections on printed circuit boards for over fifty years and considerable process knowledge has been accumulated. Extensive literature reviews were conducted on the topic and as a result it was found there are many implications to be considered with the introduction of lead-free solder. One particular question that requires answering is; can lead-free solder be used in existing manufacturing processes? The purpose of this research is to conduct a comparative study of a tin-lead solder and a lead-free solder in two key surface mount technology (SMT) processes. The two SMT processes in question were the stencil printing process and the reflow soldering process. Unreplicated fractional factorial experimental designs were used to carry out the studies. The quality of paste deposition in terms of height and volume were the characteristics of interest in the stencil printing process. The quality of solder joints produced in the reflow soldering experiment was assessed using x-ray and cross sectional analysis. This provided qualitative data that was then uniquely scored and weighted using a method developed during the research. Nested experimental design techniques were then used to analyse the resulting quantitative data. Predictive models were developed that allowed for the optimisation of both processes. Results from both experiments show that solder joints of comparable quality to those produced using tin-lead solder can be produced using lead-free solder in current SMT processes.