The Rational Development of Improved Methods for the Removal of Oil Contamination from Wildlife and Rocky Foreshore Utilizing Magnetic Particle Technology A thesis submitted for the degree of Doctor of Philosophy by Munaweera Thanthirige Kasup Munaweera Victoria University College of Engineering and Science September 2015 Declaration I, Munaweera Thanthirige Kasup Munaweera, declare that this thesis entitled “The Rational Development of Improved Methods for the Removal of Oil Contamination from Wildlife and Rocky Foreshore utilizing Magnetic Particle Technology” is no more than 100,000 words in length, exclusive of tables, figures, appendices, bibliography, references and footnotes. This thesis contains no material that has been submitted previously, in whole or in part, for the award of any other academic degree or diploma. This research has been conducted in collaboration with a number of partners, whose contributions have been appropriately acknowledged throughout. Thus, except where otherwise indicated, this thesis is my own work. Signature Date:………………………03 September 2015 i Journal publications, conference proceedings and conference presentations relevant to the scope of this thesis Refereed Journal Publications Bigger, SW, Munaweera, K, Ngeh, LN, Dann, P, Orbell, JD 2013, ‘Mathematical model for the sequential pick-up of chemical contaminants by magnetic particles’, Journal of Environmental Engineering, vol. 139, pp. 796-802. Ngeh, LN, Orbell, JD, Bigger, SW, Munaweera, K, Dann, P 2012, ‘Magnetic cleansing for the provision of a quick clean to oiled wildlife’, World Academy of Science and Technology, vol. 72, pp. 1091-1093. Conferences Orbell, JD, Bigger, SW, Ngeh, LN, Munaweera, K, Dann, P, Jessup, R, Healy, MT, ‘Providing a ‘quick wash’ to oil contaminated wildlife using magnetic particle technology’, Effects of Oil on Wildlife, 10th International Conference, Tallinn, Estonia, 5–9th October, 2009. Platform presentation. Munaweera, K, Le, O, Ngeh, LN, Bigger, SW, Orbell, JD, Jessop, R, Dann, P, ‘An assessment of the relative effectiveness of olive oil, methyl oleate and methyl soyate as pre- treatment agents for the rehabilitation of oiled birds’, the Oamaru Penguin Symposium, Kingsgate Hotel Brydone, Oamaru, New Zealand, 24–25th June, 2009. Poster presentation. Orbell, JD, Bigger, SW, Ngeh, LN, Munaweera, K, Jessop, R, Healy, R, Dann, P, ‘The development of prototype magnetic particle technology (MPT) equipment for providing a “quick clean” to oil contaminated wildlife’, the 7th International Penguin Conference, Boston, Massachusetts, USA, 29 Aug - 4 Sept, 2010. Poster presentation. ii Munaweera, K, Ngeh, LN, Bigger, SW, Orbell, JD, Dann, P, ‘Towards a rational choice of pre-treatment agents for the cleansing of oiled wildlife’, the Australian Wildlife Rehabilitation Conference (“Continuous Improvement”), Townsville, Australia, 16–20th July, 2012. Platform presentation and refereed proceedings. Ngeh, LN, Orbell, JD, Bigger, SW, Munaweera, K, ‘Magnetic cleansing’ for the provision of a ‘quick clean’ to oiled wildlife. International Conference on Wildlife Ecology’, Rehabilitation and Conservation, Phuket, Thailand, 24–25th December, 2012. Platform presentation and refereed proceedings. Media output ‘The Project’, Channel 10, Telecast on 23 May 2013. ‘Science dust off penguins for an 80th birthday’, The Age, 04 March 2011. Awards The collaborative research teams based at Victoria University and the Phillip Island Nature Parks, of which this research program formed a part, were awarded the 2013 Banksia Award (Business and Not-for-Profits – In Collaboration Award; “Magic Wand” Oiled Penguin Recovery Technology). The following statement was released: “This initiative stood out in the Judge’s opinion based on its innovation, effectiveness and opportunity for a broad-scale solution to a global problem. Combined with its effective communication techniques to educate the public on the risks of oil spills and recovery strategies”. The above collaboration also contributed to the award of a $250K grant to the the Penguin Foundation to further develop this technology in via the joint research and development program that is ongoing between Victoria University and the Phillip Island Nature Parks. Note: Conference presentations and several oil removal videos using MPT are provided in one of the pocketed CDs. iii Abstract Oil contamination of ecosystems and wildlife presents a formidable challenge to environmental remediators, including wildlife rescuers and rehabilitators. Quite apart from the diversity of polluting events, existing clean-up methods and technologies have remained essentially unchanged over the years. For example, the method of choice for the treatment of oiled wildlife is still based on the transportation of affected animals to treatment facilities and the use of surfactants and copius amounts of warm water to remove the contamination. Although such techniques have themselves been developed to a high degree over the years, with a number of notable success stories, such operations are often very labour intensive and, not being portable, cannot be applied to the animals upon first encounter, either at remote locations or in holding bays. This means that victims are often left for long periods of time in contact with toxic and/or corrosive chemicals. In spite of such requirements for improvements in wildlife rehabilitation methods and technologies, there is a paucity of scientific and engineering research into alternatives. This thesis is part of a program that exploits the use of oil ad(b)sorbing magnetic particle technology (MPT) in order to research the best methods and equipment to remove oil from a number of relevant substrates - including feathers, fur and rock surfaces. In this regard, the refinement of portable MPT equipment for the provision of a ‘quick clean’ to contaminated wildlife in the field has been pursued. This includes the development and testing of an optimal magnetic harvesting device, an investigation of the particle characteristics that promote a high initial removal of contaminant and the development, in collaboration with industrial design advisors, of the ‘backpack concept’ for a portable kit. Thus the final iteration of the magnetic harvesting device “the wand” is considered to be perfected and prototype equipment is ready for implementation in the event of an incident. The most appropriate particle size distribution and grade for the most efficient “quick removal” of the most volatile constituents has been established. A more sophisticated understanding of the contaminant removal phenomenon is crucial to the development of improved magnetic particles e.g. that have both enhanced initial removal characteristics for the ‘quick clean’ approach, as well as for achieving an optimum final removal (ideally 100%). This has been addressed via the development of a mathematical model, benchmarked to experimental data, for the sequential pick-up of chemical iv contaminants – as is appropriate for such applications. As well as providing insight into the physical basis for the pick-up phenomenon, this model also suggests an effective means for assessing the efficiency of removal. Experiments have been conducted in order to further investigate what physical and chemical characteristics of the particles themselves are important for determining critical pick-up properties, such as initial pick-up efficiency and final removal. Hence, properties such as average particle size, particle size distribution, surface characteristics, surface coating, porosity and apparent density have been investigated. In this regard, an optimal average particle size range (i.e. preferably > 5µm and < 100 µm) and the importance of capillary effects (as reflected in the mathematical form of the removal isotherm) have been characterized. In practice, related to the problem of efficient removal is the frequent necessity to use pre- treatment agents (PTAs) for recalcitrant contaminants. Where the use of a PTA is indicated, existing detergent-based protocols usually rely on anecdotal evidence for the choice of a suitable agent - such as olive oil or methyl soyate. There have been very few, if any, scientific investigations into what the optimum PTA for a given scenario (of contaminant type and bird species) might be and what might be the most appropriate point of PTA application during the cleansing process. This thesis has researched the further development of a quantitative assay, based on MPT together with the mathematical modelling, whereby the relative efficacy of potential PTAs can be conveniently assessed for specific situations. This method has been applied to the evaluation of a range of pre-treatment candidates with respect to the removal of different oil types from feathers. This work has clearly demonstrated that the choice of the most appropriate PTA is both oil and substrate dependent and also depends upon the point of PTA application. It has also been demonstrated that the PTA assay may be used to develop potentially more effective PTAs, including PTA blends, for specific applications. An important consideration for this work is to test the hypothesis that the relative PTA efficacies - as determined by the MPT assay, carry over with fidelity to PTA-assisted detergent based methods; so that recommendations can be reliably made to the rehabilitation community at large. Experiments have therefore been designed and conducted in order to test this hypothesis for eight different PTAs. Thus parallel, semi-quantitative, detergent-based