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HISTORIC DYE ANALYSIS: METHOD DEVELOPMENT AND NEW APPLICATIONS IN CULTURAL HERITAGE LORE GERTRUD TROALEN DOCTOR OF PHILOSOPHY SCHOOL OF CHEMISTRY THE UNIVERSITY OF EDINBURGH 2013 DECLARATION I declare that this thesis is my own composition, that the work described herein has been carried out by me, unless otherwise stated, and that it has not been submitted in any previous application for a higher degree. This thesis describes the results of research carried out since the 1st January 2009, the date of my admission as a research student. The work was conducted in the School of Chemistry, The University of Edinburgh, under the supervision of Dr Alison N. Hulme and Prof. Hamish McNab and in the Conservation and Analytical Research department of the National Museums of Scotland, under the supervision of Dr James Tate. The use of data from this thesis in any publications must therefore be referenced accordingly. Signed: 29th March 2013 ............................................................... Date: LTroalen .................................................. ii To My Parents, Thank You iii ACKNOWLEDGMENTS This project was supported by the Science and Heritage Programme (AHRC / EPSRC Grant ref. CDA08/411), and financial assistance was also provided by Glasgow Museums and National Museums Scotland. I would like first to warmly thank Dr Alison N. Hulme for her supervision and for her enthusiasm during the four years of this research that made the project very enjoyable and such a learning experience. It causes great sadness that Prof Hamish McNab who was co-supervising this work is not with us today and I would like to thank him for all his contribution and inspiration during the first half of the project. Many aspects of this research, especially on porcupine quill work analysis, came from exciting discussion we all had in the first year of the project, and I hope that he would have enjoyed reading the outcomes – and some of the answers - in this thesis. I am immensely grateful to Dr Jim Tate, previously Head of Conservation and Analytical Research department at National Museums Scotland for supporting my career break and also for sharing his broad knowledge and expertise on the analysis of museum objects. This research would have not been possible without colleagues in the museum institutions: at the Burrell Collection, I am grateful to Helen M. Hughes, Sarah Foskett and Patricia Collins for providing access to the Sheldon tapestries; at National Museums Scotland, I would like to thank Henrietta Lidchi and Chantal Knowles for authorising the sampling of the porcupine quill references and Jill Plitnikas for extra samples collected during conservation treatment; at the Bodleian Library, I would like to thank David Howell, for providing access to the Sheldon tapestry maps and Julie Travis for assisting me in the sampling. I would also like to thank at the University of Edinburgh Dr Lorna Eades for carrying out the ICP-OES measurements, as well as Dr Perdita Barran and Ashley Phillips for Mass Spectrometric experiments. I am grateful to Dr Lorraine Gibson at Strathclyde University, for helpful discussion on UPLC method development, and Andrew Simpson, iv from Waters UK, for his cheerful and generous technical support to both HPLC and UPLC systems. Some experiments were carried out at the LC2RMF in Paris, through a research grant provided by Eu-CHARISMA project. I would like to thank the scientific team at AGLAE accelerator especially Thomas Calligaro, Lucile Beck, Laurent Pichon and Claire Pacheco; but also Stefan Röhrs and Carolina Gutiérrez for discussion on PIXE data. Finally, I would like also to acknowledge colleagues in the C&AR department for their support and encouragement, especially Diana de Bellaigue, Victoria Hanley, Lynn McClean and Jane Clark; and at the University of Edinburgh the postgraduate students from the Hulme group, McNab group and Barran group, I enjoyed working alongside such talented young researchers and being able to exchange ideas on some of my experiments. Last but not least, I would like to thank my friends and my wonderful family, especially my parents, for their unfailing support. v ABSTRACT A review of the main natural dyes (particularly yellow flavonoids and red anthraquinones) and proteinaceous substrates used in Historical Tapestries and North American porcupine quill work was undertaken, and is summarised in Chapter 1. The analysis of natural dyes which have been used on museum artefacts other than textiles has received little systematic study, particularly those of non-European origin. In this research, the use of Ultra Performance Liquid Chromatography (UPLC) for study of natural dyes found on historical textiles and ethnographical objects decorated with porcupine quill work is explored; this required a transfer of existing analytical protocols and methodology. The advantages of using Ultra Performance Liquid Chromatography (UPLC) was evaluated through a method development based on the separation and quantification of ten flavonoid and anthraquinone dyes as described in Chapter 2. These methods were then applied to the characterisation of the dye sources found on a group of sixteenth century historical tapestries which form an important part of the Burrell Collection in Glasgow and are believed to have been manufactured in an English workshop (Chapter 3) and also to the analysis of some late nineteenth century North American porcupine quill work from a collection owned by National Museums Scotland (Chapter 5); allowing exciting conclusions to be drawn in each case about the range of dyestuffs used in their manufacture. The second aim of this research was the development of methodology for the non- invasive quantification of metal ion residues on porcupine quill substrates. This was achieved through a comparative study of reference porcupine quills prepared in-house with dyebaths containing a range of metal ion concentrations (copper and tin). The concentration of metal ions sorbed by the porcupine quills was then quantified with Inductively Coupled Plasma (ICP) coupled to Optical Emission Spectrometry (OES) and non-invasive Particle Induced X-Ray Emission analysis (PIXE) coupled with Rutherford vi Backscattering Spectrometry (RBS) as described in Chapter 4. The responses provided by the different methods were compared and they were then applied to the study of micro-samples collected from mid-nineteenth century Northern Athapaskan porcupine quill work. Unexpectedly, the use of UPLC analysis and RBS-PIXE analysis allowed the characterisation of traded European natural dyes used with metallic mordants (copper and tin) on these samples, highlighting how European contact impacted on traditional Athapaskan porcupine quill work in the late nineteenth century (Chapter 5). The work of this thesis has been covered in the following publications and presentations: Publications: 1 Troalen, L., Phillips, A., Hughes, H., Barran, P. E., Tate, J., Hulme, A. N.: Ultra Performance Liquid Chromatographic separation of natural dyestuffs: Application to early 17th century English tapestries. In preparation (work described in chapter 2) Presentations 1 42nd IUPAC Congress, Glasgow - UK (2009), poster: Characterisation and provenance of Natural dyestuffs by PDA-HPLC analysis: the case of the Sheldon tapestry workshop at Barcheston in the mid-16th century. 2 Glasgow Museum Annual Conference, Glasgow – UK (2009), presentation: Characterisation and provenance of Natural dyestuffs by PDA-HPLC analysis: the case of the Sheldon tapestry workshop at Barcheston in the mid-16th century. 3 29th DHA meeting (Dyes in history and Archaeology), Lisbon – Portugal (2010), presentation: English tapestry workshops in the mid-16th century: characterisation and provenance through PDA-HPLC analysis. vii 4 31st DHA meeting (Dyes in history and Archaeology), Antwerp – Belgium (2012), poster: English tapestry workshops in the mid-16th century: characterisation and provenance through PDA-HPLC and UPLC analysis. 5 31st DHA meeting (Dyes in history and Archaeology), Antwerp – Belgium (2012), presentation: Thorny Questions About the Athapaskan Porcupine Quill work Collection at. National Museums Scotland. viii TABLE OF ABBREVIATIONS NMS National Museums Scotland UoE The University of Edinburgh HPLC High Performance Liquid Chromatography UPLC Ultra Performance Liquid Chromatography PDA Photo Diode Array Detector LOD Limit of Detection LOQ Limit of Quantification Rt Retention Time ESI-MS Electrospray Ionisation Mass Spectrometry QTOF2 Quadrupole Time of Flight MeOH Methanol DMSO Dimethyl sulfoxide TFA Trifluoroacetic acid ICP-OES Inductively Coupled Plasma coupled to Optical Emission Spectroscopy