University of Wollongong Research Online University of Wollongong Thesis Collection 1954-2016 University of Wollongong Thesis Collections 2015 Applications of clumped-isotope palaeothermometry Florian W. Dux University of Wollongong, [email protected] Follow this and additional works at: https://ro.uow.edu.au/theses University of Wollongong Copyright Warning You may print or download ONE copy of this document for the purpose of your own research or study. The University does not authorise you to copy, communicate or otherwise make available electronically to any other person any copyright material contained on this site. You are reminded of the following: This work is copyright. Apart from any use permitted under the Copyright Act 1968, no part of this work may be reproduced by any process, nor may any other exclusive right be exercised, without the permission of the author. Copyright owners are entitled to take legal action against persons who infringe their copyright. 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For further information contact the UOW Library: [email protected] Applications of clumped-isotope palaeothermometry This thesis is submitted in partial fulfilment of the requirements of the degree of DOCTOR OF PHILOSOPHY from UNIVERSITY OF WOLLONGONG by FLORIAN W. DUX BSc (Hons) Adv. SCHOOL OF EARTH AND ENVIRONMENTAL SCIENCES 2015 I | Page II | Page CERTIFICATION I declare that this thesis, submitted in partial fulfilment of the requirements for the award of Doctor of Philosophy, in the School of Earth and Environmental Sciences, University of Wollongong, is wholly my own work unless otherwise referenced or acknowledged. The document has not been submitted for qualifications at any other academic institution. Florian W. Dux 31 March 2015 III | Page "I have not failed. I've just found 10,000 ways that won't work." Thomas A. Edison IV | Page Acknowledgements Thank you to the University of Wollongong and the School of Earth and Environmental Sciences for providing me with the opportunity to undertake my university studies from undergraduate to PhD. To my supervisors, Allan Chivas and Adriana Garcìa. I would like to thank you for the opportunity to undertake this study and send me on a path of becoming geochemist. I thank Allan for the suggestion and providing the facilities to study clumped isotopes, this has allowed me to pursue an analytical technique that has the potential to revolutionise the way we calculate palaeotemperatures. Thank you Adriana for the support and encouragement and revisions of many versions of chapters and papers. Thank you to all the administrative staff at the University of Wollongong, Denise and Wendy for your logistical help to cut through the university system. Thank you to our head of school Zenobia Jacobs and Laurie Chisolm and previously Colin Murray- Wallace, for providing a wonderful working environment. Thank you to all the technical staff in the department, Jose, Heidi, Terry for their help with samples, maps and supplies. A big thanks goes to Lili Yu and Helen Price for their assistance with ICP-MS analyses and laboratory work, I could not have done it alone. I would like to thank Paul Carr, Brian Jones and Bruce Selleck for providing the glendonite samples as well as invaluable field notes and insight. The Riversleigh fieldwork was funded by ARC grant LP0989969. In addition, I would like to thank Michael Archer, Suzanne Hand, Karen Black, Jon Woodhead, Ian Graham, Henk Godthelp, Elena Platonova and others for their help and guidance in the field at Riversleigh. I would like to acknowledge the Australian Museum for providing the Sydney Harbour shell samples and for allowing me access to their extensive collection. I would also like to acknowledge David Fink and ANSTO in their assistance in the dating of the Sydney Harbour shells (ANSTO grant 04/029). V | Page David Wheeler, my partner in geochemical crime, from your knowledge of mass spectrometers to fixing whatever Murphies Law decides to break on a given day this would not have been possible without your wisdom, thank you. To my fellow PhD companions, thank you for your help, support, jokes, and lending an ear when I just wanted someone to complain to. I wish you all well and hope you reach your goal and Ilaroy. I would like to thank my family, mum Sabine, dad Rüdiger, brother Henrik and my grandmother Johanna (Momo), for all your support and encouragement over the years from my undergraduate studies to the toils of my honours and the journey of my PhD. Without your washing of clothes, countless dinners and wise words this would not have been possible. Thank you to my close friends, whether you are far away or close, you have helped me through all of this. Thank you to Ken and Margaret Kermode for accepting me into your family and home. Finally thank you to my rock, light and angel, Stephanie. Words cannot describe how much I appreciate your presence in these last years. You have kept me sane and have made me a better person. Thank you from the bottom of my heart. VI | Page Abstract Abstract Standard palaeotemperature equations, used to interpret the formation conditions of carbonate materials, are generally problematic. This is due to the need to know both the δ18O value of the water and the precipitated carbonate to complete the equation. The clumped-isotope method overcomes these uncertainties by examining the affinity of heavy isotopes bonding (13C18O16O 47 12 16 16 44 = CO2) in favour of bonding to lighter isotopes ( C O O = CO2) in evolved CO2 from carbonates. This process of “clumping” is sensitive to ambient temperature, so can be used to determine palaeotemperature, but is independent of bulk isotopic composition of the original water. Measured values (Δ47) are expressed as per mil variation of the relative abundance of an isotopologue compared to the theoretical predicted relative abundance based on a stochastic random distribution. Clumped-isotope analysis utilises an ultra-high sensitive gas-source dual inlet mass spectrometer and measures all six masses of CO2 simultaneously (i.e. 44, 45, 46, 47, 48 and 49) to an accuracy of ± 0.01 per mil (‰) (i.e. CO2 mass 47/44 ratio). These high levels of accuracy and precision were achieved by using an updated form of the original clumped isotope method with a Thermo FinniganTM MAT 253. Long analysis times (approximately 4 hours) and long integration times (26 seconds) were used to determine carbonate formation temperatures with errors of ± 2 °C. This required manual CO2 gas collection by vacuum line extraction with cryogenic purification. Temperature stability was maintained by a temperature-controlled water bath (± 0.1 °C) during the carbonate reaction. Ambient room air-temperature for the mass-spectrometer was also controlled (± 0.1 °C). An improved gas chromatographic (GC) purification step, using an AgilentTM 7890A gas chromatograph with customised sample inlet system and trapping system, was used to remove hydrocarbon and chloride contamination. Analysis of inter-laboratory standards and comparisons to calibrated standard gases, heated gas samples and standard water equilibration samples were used for standardisation of all unknown samples. Three different types of carbonate precipitates were analysed for their applicability to the “clumped-isotope” palaeothermometer. Results demonstrate that Permian cold-water carbonates, also termed glendonites, provide clumped isotope temperatures of 1.9 ± 2.0 to 9.8 ± 4.9 °C. These temperatures represent cold-water climatic conditions in the Permian within the Sydney Basin, Australia. Late Neogene glendonites from the Taymyr Peninsula, Russia, also provide cold-water temperature conditions of 6.5 ± 4.1 °C. Calculated formation temperatures correlate well to VII | Page Abstract published modern glendonite formation conditions. This shows that the clumped isotope method is able to determine some glendonite formation temperatures. This allows us to directly infer the environmental conditions at the time of formation. However, it is also apparent that post- depositional alteration by heating through burial and fluid-rock interaction has a profound effect on the palaeotemperature results. Carbonates from cave deposits from the Riversleigh fossil area, Australia, include speleothem deposits (flow stone, cave pearls, calcite rafts and travertine rim pools). Speleothem precipitates were used to calculate an ambient formation temperature of 19.6 ± 4.8 °C. This indicates the ambient temperature in the Riversleigh area in the Middle Miocene. Additionally, a stalagmite speleothem was analysed providing a calculated formation temperature ~10 °C higher than carbonate in the immediate surrounding area. This confirms previous work showing that non- equilibrium precipitated speleothem material registers low Δ47 values and thus calculated formation temperatures that are too high. Calcite rafts and flowstones from Riversleigh also exhibit temperature discrepancies of ~7 to 9 °C. Molluscs were one of the first materials to be analysed by the clumped isotope method. This study investigates a mollusc assemblage dredged from Sydney Harbour, Australia with dates between 570 ± 80 and 7980 ± 80 years BP (AMS 14C) (i.e. much of the Holocene). These molluscs were analysed to provide insight into the temperature variation of Sydney Harbour during the Holocene.