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Kamrun Nahar Doctor of Philosophy November 2015 A Low Cost Method for Glyphosate Analysis, and Site Investigation and Modelling of Glyphosate Fate and Transport from Genetically Modified Canola Farmland in Parkes, NSW, Australia Kamrun Nahar A dissertation in fulfilment of the requirements for the degree of Doctor of Philosophy School of Engineering and Information Technology The University of New South Wales Canberra, Australia November 2015 ORIGINALITY STATEMENT 'I hereby declare that this submission is my own work and to the best of my knowledge it contains no materials previously published or written by another person , or substantial proportions of material which have been accepted for the award of any other degree or diploma at UNSW or any other educational institution, except where due acknowledgement is made in the thesis. Any contribution made to the research by others, with whom I have worked at UNSW or elsewhere, is explicitly acknowledged in the thesis. I also declare that the intellectual content of this thesis is the product of my own work, except to the extent that assistance from others in the project's design and conception or in style, presentation and linguistic expression is acknowledged.' Signed ..........._. ~ --· .. -: .. ... ... .... .......... ...... Date .... .. .. -~ .T./ _1 _1 / ~Jj /.~ ... .... ........... COPYRIGHT STATEMENT 'I hereby grant the University of New South Wales or its agents the right to archive and to make available my thesis or dissertation in whole or part in the University libraries in all forms of media, now or here after known, subject to the provisions of the Copyright Act 1968. I retain all proprietary rights, such as patent rights. I also retain the right to use in future works (such as articles or books) all or part of this thesis or dissertation. I also authorise University Microfilms to use the 350 word abstract of my thesis in Dissertation Abstract International (this is applicable to doctoral theses only). I have either used no substantial portions of copyright material in my thesis or I have obtained permission to use copyright material; where permission has not been granted I have applied/will apply for a partial restriction of the digital copy of my thesis or dissertation.' Signed ............. ... ~ ........... ............ ..... .... ..... ..... ... Date .......... ...... R,.?./t?l<X.P.!?. .... ....... .... .. .... ...... ... .. AUTHENTICITY STATEMENT 'I certify that the Library deposit digital copy is a direct equivalent of the final officially approved version of my thesis. No emendation of content has occurred and if there are any minor variations in formatting, they are the result of the conversion to digital format.' Signed • •••• •• • • ••••••••• fO'f .......~.. .. .... ..... .. .... .. ......... .. ...... Date ... ........... .. .... .~ . !.!.~.~. .!~.~-~?. ....... ......... ... ...... PLEASE TYPE THE UNIVERSITY OF NEW SOUTH WALES Thesis/Dissertation Sheet Surname or Family name: NAHAR First name: KAMRUN Other name/s: Abbreviation for degree as given in the University calendar: PhD School: School of Engineering and Information Technology Faculty: Title: A Low Cost Method for Glyphosate Analysis, and Site Investigation and Modelling of Glyphosate Fate and Transport from Genetically Modified Canola Farmland in Parkes, NSW, Australia Abstract 350 words maximum: (PLEASE TYPE) Since 2000, the use of a glyphosate, a broad-spectrum herbicide, has increased dramatically due to the cultivation of genetically modified crops in Australia. The research conducted for this thesis analysed glyphosate in environmental samples obtained from an agricultural area in Parkes, NSW, and its fate and transport in an agricultural system. Firstly, a low-cost analytical method for glyphosate analysis was established in soils and waters, to avoid the need for much more expensive analytical methods such as High Performance Liquid Chromatography. The method was calibrated against a commercially available enzyme-linked immunosorbent assay (ELISA) method, for the analysis of glyphosate which involves derivatisation with 9-Fluorenylmethyl chloroformate (FMOC-chloride) and measurement of the emissions acquisition at 310 nm with excitation wavelengths of 268 nm. Using linear regression techniques, the calibration curves showed linearity for ranges from 10 µg/L to 25000 µg/L and 10 µg/L to 1,000 µg/L (Models I and III respectively) with good reproducibility (recovery 108.3±20.8; R2=0.997 and 115.230±25.852; R2=0.998 respectively). Secondly, a site investigation was conducted of farmland cultivated with GM canola in the Parkes region, New South Wales, Australia, which involved the sampling of surface waters and soils and glyphosate analysis. The sampled soils are loams under the USDA system (clay 13.8-15.8%, silt 39-43%, sand 41.2-47.2%) and were collected according to the Australian National Environmental Protection Measure sampling protocol. The found glyphosate levels ranged between I 0 and 67 µg/L in waters and 0.10 and 0.575 mg/kg in soils, with aqueous levels lying below Australian and international drinking water guidelines. However, some exceeded the Canadian Freshwater Guideline for the Protection of Aquatic Life of 65 µg/L and most exceeded the South African chronic guideline of 0.3 µg/L. Thirdly, glyphosate sorption isotherms were constructed by batch tests on several soils from the study site and fitted with linear and non-linear Langmuir, Freundlich and Redlich-Peterson isotherms and desorption tests performed using a O. IM KH2P04 solution. Column-leaching experiments were also conducted on glyphosate-dosed and were modelled using the one-dimensional transport model HYDRUS- 1D with sorption and degradation. Finally, the findings are incorporated into a conceptual model of glyphosate transport pathways and environmental receptors. Declaration relating to disposition of project thesis/dissertation I hereby grant to the University of New South Wales or its agents the right to archive and to make available my thesis or dissertation in whole or in part in the University libraries in all forms of media, now or here after known, subject to the provisions of the Copyright Act 1968. I retain all property rights, such as patent rights. I also retain the right to use in future works (such as articles or books) all or part of this thesis or dissertation. I also authorise University Microfilms to use the 350 word abstract of my thesis in Dissertation Abstracts International (this is applicable to doctoral theses only). 27 Nov 2015 ~- ... ...... .........~ .. ..... : ...... .. ....... .. Signature Witness Date The University recognises that there may be exceptional circumstances requiring restrictions on copying or conditions on use. Requests for restriction for a period of up to 2 years must be made in writing. Requests for a longer period of restriction may be considered in exceptional circumstances and re uire the a roval of the Dean of Graduate Research. FOR OFFICE USE ONLY Date of completion of requirements for Award: THIS SHEET IS TO BE GLUED TO THE INSIDE FRONT COVER OF THE THESIS This thesis is dedicated to my family I Acknowledgements The author wishes to express her sincere gratitude and appreciation to her research supervisor Dr Robert Niven for his valuable guidance, inspiration, suggestions and continuous support through the course of the study. The author also wishes to express her sincere gratitude to her research co-supervisor, Associate professor Dr Tapabrata Ray for the valuable advices given during the course of her study. The Laboratory facilities provided by the School of Physical, Environmental and Mathematical Sciences at The University of New South Wales, Canberra are gratefully acknowledged. The author wishes to express her sincere gratitude to Associate Professor Dr Stuart Pearson for his guidance and invaluable help from the beginning of the research. The author gratefully acknowledges Professor Dr Hans Riesen, for his valuable time and contribution towards the experimental part of the research. A special ‘thanks’ goes to Ms Kate Badek for her assistance in the Laboratory and Field works from the beginning of the research. Many thanks to the following people for their assistance and support during the course of this study and preparation of this thesis Dr David Paull, for his good and helpful suggestions and enormous help and support during the author’s candidature. Dr A.F.M. Mokhlesur Rahman for his good suggestions and support Denise Russell - this work presented in this thesis would not have been possible without her help and support II Mr Jim Baxter, David Sharp, Matthew Barrett and Peter Palmer for their assistance during the laboratory testings The author would like to thank her colleagues Ms Yasmin A. M. A. Abdelraouf, Mohammad Shakhaout H. Khan, and Md Sayem Uddin for their helpful suggestions and sharing knowledge so willingly. The most important “thank you” goes to my dear husband, Md. Wahid Ferdous. Thank you for your love, for your endless patience, for comforting and encouraging me during the challenging periods. The author wishes to thank her parents who lived far away from here, for their love and support throughout the period of research. This acknowledgement will not be complete without extending sincere gratitude and appreciation to the School of Engineering and Information Technology at University of New South Wales, Canberra for providing me with financial support and assistance to carry out this study. III Abstract To reduce the world’s dependency on fossil fuels and greenhouse gas emissions,
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