Improving non-destructive techniques for stone weathering research in situ Katrin Wilhelm Kellogg College Thesis submitted for the degree of Doctor of Philosophy of Science University of Oxford 01/06/2016 Abstract "In time, and with water, everything changes" (Leonardo da Vinci in Kemp, 2006). In the field of cultural built heritage these changes often eventually result in loss of unique irreplaceable sites. This loss is considered to have an effect on societies as heritage is an important part of cultural identity and future development. In order to prolong the life of built heritage structures and preserve the collective memory they represent the weathering behaviour of the materials needs to be understood. Stone is a very common component of built heritage, especially limestone which is the focus of this thesis. Stone weathering behaviour can be investigated under controlled laboratory conditions, but results do not entirely reflect its behaviour under real world conditions (because of complex weathering histories and spatial heterogeneity found on real built heritage). Therefore, it is necessary to complement the laboratory approach with in situ investigations. For in situ investigation a variety of methods is available ranging from destructive to non-destructive (NDT) and sophisticated and expensive to more simple and economical. This thesis is based on the key principle of built heritage conservation i.e. to preserve as much original fabric as possible and keep destructive sampling to a minimum. Furthermore, to allow for wider application on a bigger scale and more frequently, the focus has been on non-destructive, portable, and economical methods. However, standards and good practice guides for these methods have not yet been developed. Thus, the overall aim of this thesis was to develop reliable methodologies for these methods in order to quantify the extent and rate of limestone heritage decay in situ under real world conditions. The thesis has three objectives. Objective 1 improved the application of selected NDT methods under laboratory conditions, focusing on sampling protocols (e.g. sample sizes) and reliability of data generated. Innovative aspects of research for this objective include extending their application (converting some drawbacks into advantages), combining them and applying modern statistical methods to the data evaluation. With this approach information on stone surface and subsurface properties was gained. This assists to capture stone weathering behaviour trajectory more holistically by investigating processes preceding total stone mass loss (erosion). Objective 2 applied the improved NDT methods to a time series of dated Portland limestone gravestones covering 1 to 248 years of exposure in order to evaluate the changing rate of surface property changes. The method proposed here provides a novel application of surface hardness data for quantifying stone deterioration rates over short- and long-term. Further, QC 50 (the regression coefficient for 0.50 quantile regression) is introduced as novel robust measure for surfaces property changes. Is was found that depending on the time scale of investigation weathering behaviour is either defined as non-linear (whole period of 248 years) or linear (periods <100 years). It was found that stone weathering behaviour in cases needs to be investigated below block scale due to spatial variances. Objective 3 applied the NDT methods to diagnose the nature and causes of catastrophic limestone deterioration observed after a harsh winter at the archaeological site of Dülük Baba Tepesi, South Turkey. The cause for catastrophic stone decay in situ were reconstructed using NDT techniques and past climate data reports. This provides a novel application to infer the cause of catastrophic decay in situ by combining moisture uptake characteristics with robust data evaluation for surface and subsurface hardness data with past meteorological data. It was concluded that the Hellenistic-Roman structures are too vulnerable to be exposed to the prevalent environment without any further preservation measures. Similar to the ‘scientific toolkit’ recommended by Meneely et al. (2009) for more sophisticated methods (e.g. 3D laser scan, ground penetrating radar etc.) the methods evaluated in this thesis are seen as a contribution to a potential ‘scientific toolkit of low-cost methods’ which could be complemented with other methods like ultrasound velocity measurements, drilling resistance etc. Thus, this study shows that the improved methods may assist in both 1) understanding heritage stone weathering under real world conditions (without damaging them by sample taking, whilst capturing surface/subsurface changes); and 2) more frequent investigation of the state of preservation/deterioration of stone heritage on-site in order to detect ongoing deterioration at an early stage. ii Acknowledgments Heartfelt thanks are due to my supervisor, Professor Heather Viles, who inspired me to undertake this DPhil. Her unmatched passion for weathering and gadgets was central to many of the ideas in this thesis, and her unfaltering support, patience and enthusiasm were truly appreciated every step of the way. I acknowledge the financial and material help provided by Proceq ©, the Engineering and Physical Sciences Research Council (EPSRC) and the German DAAD, the Oxford University Estates Services and the British Geological Survey without which I would not have been able to conduct this research. Thanks are also given to Dr Martin Coombes, for his scientific rigour and encouragement, and for very fruitful conceptual and methodological discussions. Troy Sternberg provided a fantastic platform off which to bounce ideas, and Jerome Mayaud is thanked deeply for his infinite help and support in the field, with formatting and for being always there when needed. The loyal support of all my friends, particularly The Ladies, never faltered to believe in me, and for that I thank them from the bottom of my heart. I would also like to acknowledge all my fellow departmental postgraduates, who helped forge a real sense of community within OUCE. Finally, thanks go to my sister and chosen family, for the enduring love that has helped see me through. iii Table of contents 1. Introduction............................................................................................................. 1 1.1. Introducing the challenge –heritage at risk ...................................................... 1 1.2. Limestone .......................................................................................................... 3 1.3. Challenges to quantifying stone weathering behaviour ................................. 5 1.4. Methods to quantify weathering behaviour in situ ....................................... 12 1.4.1 Long-term time series ............................................................................... 12 1.4.2 Portable methods ..................................................................................... 12 1.4.3 Non-destructive methods ......................................................................... 14 1.4.4 Missing standards and guides for good practice (Methodology improvements required) .......................................................................... 17 1.5. Thesis aims, objectives and Research questions ............................................ 21 1.5.1 Objective 1 – Low impact hardness testing and handheld moisture meters – Improving and developing guides for good practice under controlled laboratory conditions on limestone samples ........................ 25 1.5.2 Objective 2 – Determine deterioration rates of limestone heritage with partly-known weathering history with the improved methods developed in objective 1 ........................................................................... 27 1.5.3 Objective 3 – Diagnosing the cause and nature of catastrophic deterioration of limestone under complex field conditions with the improved methods from objective 1 and 2 .............................................. 27 1.6. Thesis structure ............................................................................................... 28 2. Literature Review ................................................................................................. 30 2.1. Terminology ..................................................................................................... 30 2.2. Nature, Causes and controls for limestone weathering behaviour .............. 33 2.2.1 Intrinsic factors affecting stone weathering – Limestone properties ...35 2.2.2 Extrinsic factors and impacts .................................................................. 46 2.2.3 Synergy between intrinsic and extrinsic factors: limestone weathering behaviour and weathering-stress history ................................................55 2.3. Quantifying stone decay – Non-destructive testing on-site .................. 63 2.3.1 Time series ................................................................................................ 64 2.3.2 Laboratory vs in situ, standard tests, durability, resilience, time and scale .......................................................................................................... 64 2.3.3 Measuring weathering extent and rate .................................................. 65 2.3.4 Non- destructive testing in situ ............................................................... 67 2.4. Data evaluation – parametric vs. non-parametric statistics ................