Speleothems from Warm Climates – Holocene Records from the Caribbean and Mediterranean Regions

Meighan Boyd

Department of Physical Geography Stockholm University 2015 © Meighan Boyd ISSN 1653-7211 ISBN 978-91-7649-246-8

Paper I © Meighan Boyd Paper II © Open Access. First published in the USA in International Journal of Speleology. Paper III © Oxbow Books Paper IV © Meighan Boyd Paper V © Meighan Boyd Paper VI © Meighan Boyd

Cover illustration: Lake in Alepotrypa Cave, Photo by Giorgos Maneas Published papers typeset by respective publishers, reprinted with permission Printed by Holmbergs, Malmö 2015 Distributor: Department of Physical Geography, Stockholm University Doctoral dissertation 2015 Meighan Boyd Department of Physical Geography Stockholm University Abstract

This thesis contributes to increased knowledge on Holocene climate and environmental variability from two complex and sparsely studied areas. Using a speleothem from Gasparee Cave, Trinidad, as a paleoclimate archive, the local expression of the 8.2 ka (thousand years before 1950) climate event and associated patterns of the inter-tropical convergence zone (ITCZ) and rainfall is provided. Subsequent speleothem studies using multi-proxy analysis of stalagmites from Kapsia Cave and Alepotrypa Cave, Greece, provide records of climate, vegetation and human induced changes in the cave environment during parts of the Holocene. The speleothems from the well-studied Neolithic habitation site, Alepotrypa Cave, have produced a climate and habitation record which covers the period of 6.3-1.0 ka. The cave was inhabited between 8.0-5.2 ka and was closed by a tectonic event, which has preserved the settlement. The stable oxygen record shows the first well-dated and robust expression of the 4.2 ka dry event in the Peloponnese, places the timing of the 3.2 ka dry event within an ongoing dry period, and shows a final dry event at 1.6 ka. The North Atlantic as well as more regional drivers, such as the North Sea Caspian Pattern Index is proposed to, in a complex interplay, govern many of the climate trends and events observed. Trace element variation after the site is abandoned indicate what is interpreted as two volcanic eruptions, the Minoan eruption of Thera (Santorini) around 3.6 ka and the 2.7 ka eruption of Somma (Vesuvius). Variations in trace elements during the habitation period show clear human influence, indicating an association with specific cave activities. One of the most interesting prospects for continued work on Alepotrypa Cave is this successful marriage of speleothem studies and archeology. A framework of dates which constrain some behavior of people living in the cave is only the beginning, and there is great potential to continue finding new clues in the speleothem data.

Keywords: Stable isotopes; U-Th dating; trace elements; stalagmite; speleothem; Mid- Holocene; Caribbean; ITCZ; rapid climate change; climate; Eastern Mediterranean; Peloponnese; Santorini; Neolithic; Alepotrypa Cave Sammanfattning

Denna avhandling bidrar till ökad kunskap om klimatets variationer och miljön i två geografiskt skilda områden på låga breddgrader och under tidsperioder inom den Holo- cena epoken. Genom att använda en droppsten (stalagmit) från Gasparee-grottan, Trini- dad, som ett paleoklimatarkiv, har det bland annat varit möjligt att visa att Trinidad upplevde torrare förhållanden under den snabba klimatförändring som observerats ske för 8200 år sedan på många platser i världen. Denna torrare klimatsituation i Trinidad föreslås vara ett resultat av en sydlig förflyttning av den intertropiska konvergenszonen. Övriga stalagmiter som studerats för denna avhandling kommer från Kapsia-grottan och Alepotrypa-grottan som finns på Peloponnesos-halvön i Grekland. Resultaten däri- från speglar dels klimat- och vegetationsvariatoner och dels graden av mänsklig aktivitet, under tiden för ca 8000 år sedan till för 1000 år sedan. Alepotrypa-grottan är känd för att vara en av de större Neolitiska boplatserna i Grekland. Isotop- och spårämne- sanalyser av stalagmiterna har bidragit med ny kunskap om tidpunkten för mänsklig aktivitet, hur människorna påverkade grott-miljön samt hur klimatet varierat efter det att grottan, genom en tektonisk händelse, stängdes för människans inverkan. Snabba klimatförändringar, för 4200 och 3200 år sedan, observerade i andra regioner, rekonstru- eras här för första gången på Peloponnesos. En snabb förändring mot torrare förhål- landen observeras även för 1600 år sedan. De klimatstyrande processerna föreslås vara en kombination av storskaliga processer som den nordatlantiska oscillationen och mer regionala processer som det så kallade North Sea Caspian Pattern Index. Variationer i spårämnen i stalagmiterna efter att Alepotrypa-grottan stängdes kan kopplas till två vulkaniska utbrott, nämligen det Minoiska utbrottet av Thera på ön Santorini kring 3600 år sedan och utbrottet av Somma (Vesuvius) kring 2700 år sedan. Spårämnesvariationer under bo-perioden ger tydliga indikationer på människans påverkan på grottmiljön och som delvis kan länkas till specifika aktiviteter, som eldning av dynga i grottan. Avhan- dlingen är ett resultat av en framgångsrik kombination av klimatstudier och arkeologisk kunskap och utgör ett viktigt underlag för fördjupat interdisciplinärt forskningssamar- bete i Alepotrypa-grottan. Contents

1. Introduction 1 1.1. Aims and objectives of the thesis...... 4 2. Site selection, speleothems, and analytical techniques 5 2.1. Caribbean...... 5 2.2. Mediterranean ...... 6 3. Speleothems as climate archives 11 3.1. Caves and speleothem formation...... 11 3.2. Proxy types...... 12 4. The samples 17 4.1. Gasparee Cave ...... 17 4.2. Kapsia Cave...... 17 4.3. Alepotrypa Cave...... 17 5. Analytical Methods 27 5.1. Stable isotopes ...... 27 5.2. U-Th Dating . 27 5.3. Petrographic and SEM images . 30 5.4. Modern-day cave environment...... 30 5.5. Trace elements...... 31 6. Results 33 6.1. Constraining the timing of a rapid climate change. 33 6.2. Moving on from the Caribbean – Novel techniques applied to challenging material. 35 6.3. Alepotrypa Cave – Combining methods to broaden the approach to speleothem studies...... 36 6.4. Mid-Holocene Climate in the Peloponnese . 43 7. Discussion and Supporting Data 45 7.1. The Caribbean. 45 7.2. Speleothems in the Peloponnese. 46 8. Final remarks – Perspectives on future research 57 9. Conclusions 59 10. Acknowledgements 61 11. References 65 12. Supplementary material 75

Speleothems from Warm Climates – Holocene Records from the Caribbean and Mediterranean Regions

Meighan Boyd Department of Physical Geography, Stockholm University, Sweden

List of papers This doctoral thesis consists of this summary and the following papers, which are referred to by their Roman numerals in the text.

Paper I Boyd, M., Holmgren, K., Shaw, P., Hoffmann, D., Mangini, A., Mudelsee, M., Spötl, C. manuscript. Early Holocene patterns of rainfall, vegetation and soil conditions, inferred from a southern Caribbean stalagmite.

Paper II Finné, M., Kylander, M., Boyd, M., Sundkvist, H.S., Löwemark, L. 2015. Can XRF scanning of speleothems be used as a non-destructive method to identify paleoflood events in caves? International Journal of Speleology, 44, 17-23.

Paper III Boyd, M. and Holmgren, K. in press. Speleothems from Alepotrypa Cave: Towards climate reconstruction. In: Alepotrypa Cave in the Mani, Greece: A festschrift to honor Dr. G. Papathanasopoulos on the occasion of his 90th birthday. 2015. eds. Α. Papathanasiou, M. Galaty, P. Karkanas, W. Parkinson, D. Pullen, Oxbow Books

Paper IV Boyd, M., Karkanas, P., Papathanasiou, A., Hoffmann, D., Holmgren, K.manuscript. U-Th dating of calcite on human bones from Alepotrypa Cave, Greece.

Paper V Boyd, M., Holmgren, K., Finné, M., Hoffman, D., Jochum, K.P., Karkanas, P., Papathanasiou, A., Scholz, D., Stoll, B., Spötl, C. manuscript. Stable isotopes and phosphorus patterns in calcite stalagmites from Alepotrypa Cave, Peloponnese, Greece as indicators of Holocene changes in rainfall and vegetation. Paper VI Boyd, M., Hoffman, D., Jochum, K.P., Karkanas, P., Krusic, P.J., Papathanasiou, A., Scholz, D., Stoll, B., and Holmgren, K. manuscript. Trace elements as recorders of human activity and environmental indicators at Alepotrypa Cave, Greece.

Author contributions

Paper I Conceived and designed by KH, PS, and MB. MB wrote the paper in close collaboration with KH and PS. Stable isotope lab work carried out by MB under the guidance of CS. Dating of material by AM and DH, statistical analysis by MM. All authors contributed with commenting on the manuscript.

Paper II Conceived and designed by MF, MB, HSS, MK and LL. MF wrote the paper and designed figures following discussions with MK. MB, HSS and LL contributed to discussion around interpretations and commented on the manuscript. Lab work conducted by MF, MB with supervision and help from MK and LL.

Paper III Written by request by MB with input and editing from KH.

Paper IV Conceived and designed, and written by MB with input from PK and AP on archeological issues. Lab work carried out by DH.

Paper V Conceived and written by MB through discussion and comments from KH. Lab work performed by MB and made possible by the generous donation of lab time by DH, CS, KPJ and DS. Improvements in structure and discussion on interpretation from MF. Work made possible through collaboration with PK and AP, and support from their archeological data.

Paper VI Conceived and written by MB with support and comments from KH, PJK, and KPJ. Lab work performed by MB and made possible by the generous donation of lab time by DH, KPJ, BS and DS. Statistics and MATLAB work contributed by PJK. Work made possible through collaboration with PK and AP and support from their archeological data. 1. Introduction

Speleothems (secondary cave carbonates, e.g. stalagmites and flowstones) provide a number of proxy records of past climate and cave environment variability. As they be- have as a closed system, speleothems can be dated using very precise radiometric decay methods, which makes them ideal for use in paleoclimate reconstruction. They occur in carbonate bedrock all over the world in locations where temperatures are above freezing for at least part of the year. They fill a particularly important gap in the global climate record map by providing a terrestrial climate data in tropical regions where other archives of high-resolution, such as ice cores, are extremely rare. Low latitudes are traditionally underrepresented in climate research and are therefore subject to greater uncertainties in climate scenario modeling, and speleothems from these regions are particularly valuable as climate proxies. Models predicting future humidity patterns, rainfall seasonality, intensity of precipitation levels and atmospheric moisture require paleoclimate data as test cases to see how well the model produces known conditions. The lack of long-term observational data is a source of uncertainty when trying to constrain models (Knutti and Sedláček, 2012), and without accurate modelling results it will be difficult to secure water supplies and to mitigate potential inundation, flooding, and salinization which lead to severe impacts on ecosystems, infrastructure, agricultural production and human health. To help improve the spatial and temporal availability of paleoclimate data in these sparsely studied regions, speleothems were collected from Gasparee Cave, Trinidad and Tobago, and from Alepotrypa Cave, Greece (Fig. 1). The former lies directly on the present northernmost position of the Intertropical convergence zone (ITCZ), experiencing a dry warm climate from January-June, and wetter conditions from July-December, providing a seasonal distribution of rainfall. The latter experiences the dry hot summers and cool wet winters common in the coastal eastern Mediterranean, also with a distinct seasonal change in precipitation regime. Both of these regions are densely populated, and also face large challenges in the face of predicted global climate change. For this reason, and to address the uncertainty in the models stated by the Intergovernmental Panel on Climate Change (IPCC) in its 5th assessment report, more paleoclimate data from the tropics and Mediterranean regions could help to minimize uncertainty caused by large amounts of natural variability in the regions (Christensen et al., 2013). Through additional paleoclimate data sets to test climate models, it will be possible to improve the accuracy of modelled future climate scenarios, which is vital for planning and adaptation strategies to be effective. An unusual and exciting aspect of the project is that Alepotrypa Cave is a well-studied and unique site of a Neolithic human settlement. In order to understand how past popula- tions coped with and adapted to climate change, it is ideal to combine paleoclimate studies with archeological excavations, in particular if those climate proxies studied provide

1 -80° W -30° W 20° E

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Figure 1. Map showing the two study sites. A) Gasparee Cave, Trinidad and Tobago. B) Pelopon- nese Peninsula, Greece.

a high chronological resolution and are of a length which is capable of capturing climate events of both long and short duration and frequency. By capturing the amplitude and frequency of climate variation and climate change and providing a secure chronology of the extent of these events, it is possible to untangle the complexity of how humans in the past have moved, adapted, or simply carried on in the face of droughts, cold periods and other challenges. The climate of the Earth has varied and changed from a completely ice-covered snow- ball Earth to hothouse conditions. Massive changes on geological time scales concerning the arrangement of continents have often been tied to such changes. Within the quaternary period the climate of the earth more closely resembles that of today, owing to continental and oceanic extents which closely resemble those of the present. The state of

2 understanding about past climate is constantly improving, and through the use of paleoclimate proxies, researchers have been able to produce long records of past climate from a multitude of sources. Marine sediment cores and ice cores have provided significant advances in the understanding of large-scale circulation patterns and climate variability, allowing for the recognition of glacial/interglacial cycles and their connection of insolation changes resulting from variation in the orbit of the Earth (Berger and Loutre, 1991). Orbital forcing is not the only factor influencing climate, with sunspot activity, ocean and atmospheric circulation, and more recently, anthropogenic input of aerosols and greenhouse gases into the atmosphere also being involved (Kaufmann et al., 2011). In order to test and disentangle the complexities and influence of these factors, and to test the reliability of climate models, paleoclimate proxy data are used. Climate archives such as tree rings, corals, ice cores, lake, bog, marine sediments, and speleothems are storage vehicles for past climate information. Each archive type can provide multiple proxies, including stable isotopes (e.g. δ13C, δ18O), pollen, tephra particles, macro and microfossils such as seeds and diatoms, variation of trace elements, and growth rings or layer thickness. Each proxy may be related to a different climate variable (or variables) and can preserve information about these variables at different resolutions, represent single events, seasonal variation, and annual or decadal cycles and so on. It is by disentangling the complex processes which control the chemical and physical properties of climate archives that we can identify which climate signals are found therein. We can then use paleoproxies, which provide climate data back beyond the time for which em- pirical observations are available, to contribute to a deeper understanding of the climate picture. By providing climate modelers with high-resolution climate reconstructions of the past, it is possible to test performance of models and also to see how well they reflect known conditions as a given point. Accurate future climate scenarios require testing against known values, and this is vital to meet the requests of policymakers and citizens who are facing an increasingly uncertain climate situation in the future. The IPCC has identified the tropics and Mediterranean as an area where people are expected to experience major challenges in the face of climate change (Christensen et al., 2013). Sea-level rise leading to inundation of coastal areas, saltwater intrusion, increased severe storms, extreme temperatures, and a concentration of rainfall into short intense events with more arid conditions prevailing are all potential consequences of climate change. Overall, the coverage of paleoclimate research in these regions leaves much to be resolved. The prevalence of marine studies, which do not capture local to regional variation, and the relative lack of long, high-resolution terrestrial datasets presents an excellent opportunity for work with speleothems to greatly contribute to understanding of climate in these regions. For speleothems, advances in dating techniques have opened the door for better chronologies based on accurate and highly resolved dating (Hoffmann et al., 2009). As speleothems are a well-protected archive type due to the properties of the cave environment, they can survive for many hundreds of thousands of years (van Breukelen et al., 2008; Bajo et al., 2012), and provide near-continuous climate records.

3 1.1. Aims and objectives of the thesis This project is the result of the combination of studies of speleothems from Gasparee Cave, Trinidad, and Kapsia Cave and Alepotrypa Cave, Greece. The unique human history at Alepotrypa Cave presents both challenges and new opportunities when working with speleothems from this site, and these have both come to play a large role in the thesis work. The aim of this thesis is to increase the spatial coverage of Holocene paleoclimate data from terrestrial archives in the Caribbean and Mediterranean, and to apply speleothem studies to the unique questions which are presented at archeological sites. The dual region nature of the project has resulted in two main foci.

Climate and climate variability • Are speleothems from each site suitable for paleoclimate reconstruction? • If so, what do speleothems from each site contribute to increase our knowledge and understanding of past climate conditions in the regions? These questions are addressed by Papers I and V.

Changing cave environments • Which methods can be used to see how changes in the cave environment are expressed in speleothems? • Which techniques can be applied to speleothems to reduce uncertainties in the archeological timeline of the Neolithic habitation at Alepotrypa Cave? These questions are addressed by Papers II, III, IV and VI.

4 2. Site selection, speleothems, and analytical techniques

In order to study changes in the climate system, and to understand the governing processes behind observed changes, a wide spatial coverage is required. Sites which lie on borders between climate zones, e.g. the ITCZ or monsoon regions, can provide insights into the extent and placement of these strong influences over time. Research from Oman (Fleitmann et al., 2007), China (Dykoski et al., 2005; Cosford et al., 2008; Zhang et al., 2013) and South and Central America (Leduc et al., 2009; Schmidt and Spero, 2011) have contributed to a more complete understanding of the dynamics of the ITCZ. The placement and extent of the ITCZ controls the rainfall of many tropical regions, and so understanding ITCZ response to other changes in the climate system is vital if we are to be able to predict future climate change scenarios with less uncertainty. Both the Caribbean and Mediterranean (Fig. 1) experience moderate temperatures and receive highly seasonal rainfall, and are situated in complex regions with many topographical factors affecting rainfall distribution. The geographical and climatological setting of these sites indicates they could provide important insight into the occurrence of what are considered global climate events.

2.1. Caribbean The Caribbean region is dominated by ocean surface, with the climate being dominated by the interaction of oceanic and atmospheric systems. The southern islands are strongly influenced by the annual passage of the ITCZ (Mangini et al., 2007). Easterly trade winds combine with the ITCZ and provide the greatest influences on climate on the island of Trinidad. From May to December these winds reach their greatest strength, and precipitation is at a maximum. Relatively high topographical relief influences wind exposure and causes orographic effects leading to significant local variation in precipitation. The Caribbean low level jet, and North Atlantic high-pressure combine with subsidence caused by convection in Central America to influence weather patterns of the region (Gamble and Curtis, 2008; Wang et al., 2008). The island of Trinidad, 5128 km2, is located between 10°N and 11°N latitude, and between 61°W and 62°W longitude. It extends around 80 km from north to south, and 60 km from east to west and at its closest point is only 15 km offshore from Venezuela. Average annual precipitation near the cave site is 1500 mm (Trinidad Meteorological Service). Rainfall variation within the Caribbean is strongly controlled by topographical effects, with many islands having strong rainfall gradients from east to west.

5 2.1.1. Gasparee Cave The entrance to Gasparee Cave is situated within Gaspar Grande Island (Fig. 2) with an entrance at 30 m above sea level (a.s.l). The bedrock of the area is Cretaceous Laventille Formation limestone, and Gasparee Cave likely formed during the Pleistocene. Today, it is the most visited show cave in Trinidad. Vegetation on Gaspar Grande Island is dominated by deciduous seasonal forest of the Bursera-Lonchocarpus association (Day and Chenoweth, 2004), and the island has thin soil coverage with many bedrock exposures. The lower parts of the cave lie at sea level, and the saltwater lagoon in the cave is influenced by tidal movement through connections to the Gulf of Paria. It is decorated mainly with flowstones and columns, though some modern stalagmites are seen around the rim of the saltwater lagoon, which is a popular swimming spot for cave visitors. Preliminary investigations indicate that the cave extends well below the current sea level. Influenced by karst processes in more modern times, the cave has several large roof openings formed by collapses, and the cave is today open to the outer environment. Visitors enter the cave by descending 30 m of stairs in one of these collapse openings to the main chamber. The stalagmite, called GC2, formed in a space created by roof collapse toward the back of the cave, and was collected with its tip above the current tidal range.

2.2. Mediterranean The Mediterranean region hosts a high density of archeological studies in comparison to many other populated regions, but boasts comparatively few robust paleoclimate reconstructions (Finné, 2014). It is also a region where the human impact on the environment is evident reaching back for many thousands of years (Wick et al., 2003; Jalut et al., 2009). It can be seen in the form of vegetation type change (e.g. introduction of the olive

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0 750 1,500 km Figure 2. Map showing the location of Gasparee Cave on Gaspar Grande Island, off the northern west coast of Trinidad.

6 trees, Olea), agricultural animal husbandry, irrigation, and aqueducts. In order for human societies to develop and thrive in an arid climate prone to extreme changes in water availability, adaptation strategies must have been employed (Weiss and Bradley, 2001). The present-day climate of Greece is generally characterized as Mediterranean, with hot dry summers and mild wet winters. Temperatures are highest in the costal southern regions, with a gradient in temperature showing cooler annual averages on a northerly path, and also with increasing altitude and distance from the coast (Harding et al., 2009; Dotsika et al., 2010). Precipitation also changes spatially across the Mediterranean basin, and is highly influenced by the orographic effects of the mountain ranges, with the western Mediterranean receiving more rain. Within the eastern Mediterranean region, a precipitation gradient ranges from over 2000 mm per year to less than 120 mm per year (Rohling et al., 2009). Precipitation is strongly associated with cyclogenesis in the Atlan- tic and western Mediterranean, and is strongly seasonal, with 70-80% of rainfall occurring between October and April. The main precipitation driver is the winter southward shift in the subtropical high-pressure systems. During the summer, the more northerly position of these highs causes a subsidence of air over the eastern Mediterranean, preventing cloud formation and severely limiting precipitation. By contrast, the winter conditions see an increase in the intrusion of North Atlantic synoptic low-pressure systems, bringing moist air into centers of cyclogenesis in the Gulf of Genoa, the Ionian Sea, and Cyprus (Kutiel and Benaroch, 2002; Argiriou and Lykoudis, 2006; Harding et al., 2009). Most cyclones passing over the Peloponnese have tracked southeastward from the Gulf of Genoa, though the same system of North Atlantic origin can experience consecutive cyclogenesis at all three centers (Trigo et al., 2002). Together, these systems bring precipitation to the eastern parts of the basin. The North Atlantic low-pressure systems are tied to the mode of the North Atlantic Oscillation (NAO), with NAO+ phases bringing cooler and drier conditions to the Eastern Mediterranean (Xoplaki et al., 2004; Harding et al., 2009). NAO- conditions bring warmer wetter conditions, as this mode allows for a greater penetration of the low-pressure systems. Another factor affecting the regional climate is the North Sea Caspian Pattern Index (NCP) (Kutiel et al., 2002; Kutiel and Benaroch, 2002) which has a marked effect on temperature in the western Peloponnese throughout the year. NCP mode is also responsible for precipitation changes over other parts of Greece, Turkey, and the Eastern Medi- terranean. A NCP- mode brings wetter conditions to most of Greece, along with warmer temperatures, as warmer moist air flows inland from the Ionian Sea. With NCP+ cooler drier continental air with a northeasterly wind brings cooler drier continental air into the Peloponnese but shows comparatively little influence on precipitation in the western Peloponnese (Kutiel et al., 2002; Kutiel and Benaroch, 2002). The Mediterranean Oscilla- tion (MO), which is defined by the pressure differences between stations at Algiers and Cairo, produces a see-saw of conditions between the western and eastern Mediterranean (Harding et al., 2009). For Greece, this results in more frequent southerly flow of cool air during a positive MO phase. Winter surface air temperatures are strongly related to the MO, when low-pressure systems are passing through the area, but no significant correla- tion is seen with summer surface air temperatures (Nastos et al., 2011).

2.2.1. Kapsia Cave The Peloponnese peninsula (Fig. 3) makes up the southern part of mainland Greece, and is rich in archeological sites, such as Franchthi Cave which includes Upper Paleolithic through Mesolithic deposits (Vitelli, 1999; Stiner and Munro, 2011; Colonese et al., 2013), and evidence of Neanderthals from Lakonis (Panagopoulou et al., 2004). The proxim-

7 ity to the Hellenic arc contributes to high influences of tectonics on the Peloponnesian landscape, with high mountains at the central areas, to lowland river valleys which are found along the coast. Kapsia Cave is located in the central Peloponnese (N37.623°, E22.354°) close to the city of Tripoli. The cave entrance is located around 700 m a.s.l. at the base of the Mainalo Mountains. The cave is located on the Mantinea Plain, which is drained by five sinkholes, one of which lies directly outside the natural cave entrance. In 2004 an artificial entrance was made in the cave and it was developed as a tourist attraction, and from 2010 onwards the cave has been open for visitors. The proximity to the sinkhole makes the cave vulnerable to flooding events when the sinkhole becomes plugged, and the most recent of these occurred in 2001. Over a meter of clay has been deposited in the cave by these floods, and there is a high-water mark seen on the cave walls in clay deposits related to massive flooding in the past. A more detailed description of the cave and associated speleothem studies there can be found in Finné (2014).

2.2.2. Alepotrypa Cave Alepotrypa Cave is located on Diros Bay on the western side of the Mani Peninsula (N36.638°, E22.380°), on a promontory which is around 2 km wide, and it has maximum thickness of around 200 m. The modern-day cave entrance sits around 30 m a.s.l. and is set back about 50 m from the current seafront. Orographic effects from the nearby 1000 m a.s.l. peaks of the Taygetos Mountains induce rainfall on the western side of the peninsula. Average rainfall and temperatures 64 km from the site at the nearby Methoni station for the period 1951-2008 are around 700 mm ± 150 mm per year, with over 90% of precipitation occurring between October and April, giving a negative water balance between May and September. Temperature is

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! Kapsia Cave 37° N ! ± Alepotrypa Cave 36° N 0 250 500 km Figure 3. Map of the Peloponnese showing the location of Kapsia and Alepotrypa caves.

8 moderated by the sea, and the average annual temperature is 18.0 ± 0.4°C, with summer temperatures averaging 23.2 ± 2.5°C for May-September and winter average temperatures of 11.9 ± 1.4°C for December-February.

Vegetation above the cave is of C3 type, with old non-producing olive groves, and much thorny scrub dominating the area. On the steeper slopes vegetation is more sparse, but directly above the cave, the dominance of thorny scrub makes passage impossible. The area immediately around Alepotrypa Cave includes Glyfada Cave and the Neo- lithic archeological site of Ksagounaki. At the time of its discovery by Petrocheilou of the Greek Speleological Society in 1958, the cave only had a very narrow opening. The presence of Neolithic artifacts and a settlement site within the cave led to the site becoming the object of development as a promising tourist attraction. While not as highly decorated as its neighbor, Glyfada Cave (which is very popular with tourists), it was altered and much of the entrance chamber was modified to permit access. However, the site was recognized as having a great importance and so development was halted when management was taken over in AD 1970 by the Greek Ministry of Culture. Since AD 1970 the cave has been the site of ongoing excavation. The cave seems to have been an important center for Neolithic culture in the Pelo- ponnese. It has been determined that occupation of the site began around 8.0 ka, and continued until abandonment of the site around 5.2 ka (Papathanasiou et al., 2000; Pa- pathanasiou, 2009; Papathanasopoulos, 2011). A tectonic event closed the cave either in conjunction with or shortly after this time as settlement deposits are, with the exception of work conducted after AD 1958, undisturbed (Paper IV, this volume). The history of the occupation of the cave is still being studied, but occupants explored the entirety of the mapped and much of the unmapped passageways. Throughout the cave, burials and ossuaries were found, and these have provided much evidence of human health and cul- tural habits relating to internment (Papathanasiou et al., 2000; Papathanasopoulos, 2011). Evidence of extensive trade networks supplying goods from across the Aegean is seen at the site, and finds of silver and copper jewelry, imported pottery, and obsidian give some insight into the wealth and importance of the Alepotrypa settlement (Papatha- nasopoulos, 2011). One possible explanation for the choice of the cave for settlement is the availability of fresh water through the very dry summer months. Within the cave a large brackish lagoon and several groundwater pools are found. Despite a negative summer water balance there is active dripping at many sites within the cave at the end of the dry season, and this combined with moderate temperatures and good defensive position would contribute to its appeal. The preservation of pottery from the site is outstanding, and many of the finds may be viewed in the Neolithic Museum of Diros adjacent to the cave entrance. Work by The Diros Project, a collaboration of the Ephorate of Paleoanthropology and Speleology with the American Field Museum, has produced more data on the extent and complexity of the Ksagounaki settlement just north of the cave entrance, and results from this project will be detailed in the forthcoming volume1 which includes Paper III from this thesis. The Diros Project continues the work of G. Papathanasopoulos who has headed work at the cave for many years.

1 Papathanasiou, A., Galaty, M., Karkanas, P., Parkinson, W., Pullen, W. 2015. Alepotrypa Cave in the Mani, Greece: A festschrift to honor Dr. G. Papathanasopoulos on the occasion of his 90th birthday. Oxbow Books, Oxford

9 10 3. Speleothems as climate archives

3.1. Caves and speleothem formation Caves, most often found in limestone and dolomite bedrock, are a common feature in karstic landscapes. Named after the type locality in Slovenia, karstic landscapes are characterized by high porosity, fracturing, and dissolution pathways leaving very little surface water flow and drainage. Precipitation (either rain or snow, and then melt water upon thawing) and surface waters move through the bedrock. The vadose zone (including soil, epikarst and transmission zones), where waters can move through either fracture, fissure or seepage flows, sits above the water-saturated phreatic zone (Williams, 2008). The upper epikarst, along with the soil zone, functions as the primary source for CO2 in cave drip waters. Within the epikarst, high partial pressure of carbon dioxide (pCO2) is present as a result of biological respiration, and decomposition of organic materials (Fairchild and Baker, 2012) water in this zone is made slightly acidic. This slightly acidic water then moves through the limestone bedrock where it dissolves carbonate minerals, causing the water to become supersaturated in calcium while a high pCO2 is present. As the waters percolate deeper into the bedrock, they enter into areas of lower partial pressure, like caves. When the water seeps out into the cave pCO2 is lower, causing carbon dioxide to degas from the water and resulting in the precipitation of calcium carbonate (CaCO3) as speleothems (Fairchild et al., 2006) (Fig 5). While many other minerals can form speleothems, the most common ones are composed of calcite. The term speleothem (Greek:spelaion , cave; thema, deposit) is used to describe sec- ondarily precipitated deposits within caves, but in the context of climate studies this term generally refers to either flowstone or stalagmite deposits. The most common formations which appear in the literature regarding climate proxy studies include: • stalactites - which form on the roof of the cave chambers and extend towards the cave floor • flowstones - which form on the walls and floors of the cave, deposited by the flow of water • stalagmites - those formations deposited on the cave floor by water dripping (usually) from feeder soda straw stalactites Of these three, it is stalagmites which are most frequently used for paleoclimate proxy studies as the layering of stalagmites is generally less complex than that of either stalactites or flowstones.

11 3.2. Proxy types The waters entering the cave environment are the carriers of climate information. As caves generally present a stable environment (eg. reflecting average mean outside surface air temperature), changes in the water entering the cave reflect changes at the surface. Seasonal variation can be reflected in the changing chemistry of the drip water, the rate of dripping, and in the rate of speleothem growth (Borsato et al., 2007; Baldini et al., 2008; Sherwin and Baldini, 2011; Frisia et al., 2012; Hartland et al., 2012). These in turn can be enhanced by changes in cave pCO2 which can be driven by increasing temperature differences between the cave air and the outside air driving ventilation of the cave (Spötl et al., 2005).

3.2.1. Stable oxygen and carbon isotopes in speleothems Stable isotopes (variations of chemical elements with different neutron numbers but the same number of protons which do not undergo radioactive decay) in climate systems provide a valuable variety of climate proxies. In many archives they are used to trace the source of dust and pollutants (Belli et al., 2013), the source of precipitation (Cruz Jr et al., 2006; Breitenbach et al., 2010), and amounts of precipitation (Fairchild and McMillan, 2007). The use of stable isotopes in speleothem studies has become more prevalent over the last 30 years as today only very small sample sizes are required for analysis, thus providing the potential for high-resolution climate studies. In speleothems, the most commonly used stable isotopes are carbon (C) and oxygen (O). Ratios of isotopes in carbonates are given as a δ parts per mille (‰) relative to the Vienna Pee Dee Belemnite (δ18O or δ13C ‰ V-PDB) standard, while water samples are relative to the Vienna Standard Mean Ocean Water (δ18O ‰ V-SMOW). The ratios are determined using the following formulas:

18 18 16 δ O ‰ V-PDB = (Rsample / Rstandard -1) × 1000 where R = O/ O 13 13 12 δ C ‰ V-PDB = (Rsample / Rstandard -1) × 1000 where R = C/ C

The water from which speleothems precipitate ultimately reflects the18 δ O of meteoric waters and therefore can reflect the 18δ O of precipitation (Rozanski et al., 1993; Lachniet, 2009). Carbon isotopes are more ambiguous than oxygen isotopes and are less frequently interpreted in speleothems. Contributing sources of δ13C in speleothems are the sources of

CO2 dissolving in the ground water, which include soil zone and vegetation, atmosphere, and bedrock. Of these, the soil zone and vegetation account for around 80-90% of the δ13C observed (Cosford et al., 2009). In order to preserve these signals, speleothem growth (precipitation of calcite) should occur under conditions which do not introduce additional fractionations of these stable isotopes (Hendy, 1971; McDermott, 2004; Fairchild et al., 2006; Lachniet, 2009). Such conditions are referred to as equilibrium or near-equilibrium conditions. Despite this being a textbook requirement for good proxy data, and possibly occurring in the cave environment, it has become apparent that such conditions are the exception rather than the rule (Kim and O’Neil, 1997; Mickler et al., 2004; Lachniet, 2009; Day and Henderson,

2011). Evaporative effects, open/closed bedrock dissolution, cavep CO2 levels which en- hance rapid degassing of CO2 from drip water, changing drip rate, prior calcite precipitation (PCP), and processes within the karst, epikarst and soil layers can all contribute

12 to fractionation before calcite precipitation on the speleothem surface, and can poten- tially complicate climate proxy interpretations (Bar-Matthews et al., 1996). To address this, monitoring studies at cave sites aim to improve the understanding of the processes which interplay during speleothem growth and to shed light on the relationship between the modern climate and cave records (Spötl et al., 2005; Mattey et al., 2008; Mattey et al., 2010; Baker et al., 2014). Both δ18O and δ13C will vary in what they represent at each individual cave site, and this needs to be tested in order to produce a good interpretation and climate proxy record. For example, the δ18O signal of precipitation can reflect precipitation amount, the so-called amount effect, where a more negative 18δ O indicates increased precipitation amount, or temperature, where a more negative δ18O indicates colder temperatures. In very broad terms, tropical and subtropical coastal speleothems often record an amount affect signature (e.g. Bar-Matthews et al., 1997; Lachniet et al., 2004; Griffiths et al., 2010). 13 δ C as an indicator of transitions between dominance of C3 or C4 is made possible due to the differences in the photosynthetic pathway used by the plants resulting in more 13 negative (C3) or less negative (C4) δ C values (Cosford et al., 2009). This mechanism provided the potential to observe changes in vegetation type between C3 and C4 plants above caves (Lee-Thorp et al., 2001; Holmgren et al., 2003). In the case of sparse vegetation cover, or low biological activity, speleothem δ13C values will be less negative. Less negative δ13C values can also result from kinetic effects such as evaporation, PCP, or rap- 13 id degassing of CO2, and so during drier conditions the δ C signal can be enhanced by a combination of factors all working to pull the signal in the same direction (Fairchild and McMillan, 2007). δ13C has also been used as a proxy for relative humidity in regions with high rainfall and steady temperature and vegetation assemblages (Göktürk et al., 2011).

3.2.2. Trace elements In other climate archives, such as ice cores and trees, trace elements are used to provide measurements of atmospheric fluxes, movement and source of air masses, and pollutants. They also provide information on dust abundance (Gabrielli et al., 2005). Tree ring trace element records can provide highly resolved archives of volcanic eruptions (Pear- son et al., 2009) and pollutants (Balouet et al., 2007). In addition to the well-established use of stable oxygen and carbon isotopes for environmental and climate proxies, speleothems can provide additional information in the form of the variations of trace elements (Hellstrom and McCulloch, 2000; Borsato et al., 2007; Fairchild and Treble, 2009). A number of methods are available for looking at trace element compositions of speleothems (Fairchild and Treble, 2009). In the work done for this thesis, both micro X-ray fluorescence spectrometry (µXRF)(Finné et al., 2015) and Laser Ablation Inductively Coupled Mass Spectrometry (LA-ICP-MS) were used (Jochum et al., 2012). While trace elements have not been as extensively studied as stable oxygen and carbon, they present an opportunity to study hydrological conditions, dust events, pollution, and volcanic activity at very high resolutions, but good interpretations are dependent on an increase in the number of modern-day cave monitoring studies to provide a better understanding of the exact controls on their behavior. Trace elements are present in the speleothem in several different forms. Magnesium (M), strontium (Sr), and barium (Ba) are often transported in solution as divalent cations and substitute out Ca in the crystal lattice of calcite. These are the most studied trace elements, with their behavior in solution and mineral form dependent on temperature, precipitation rate and crystal morphology (Fairchild and Treble, 2009). Other elements are transported with the drip water and occur as very fine colloidal particles (1 nm to 1 µm) (Zhou et al., 2008).

13 Caves present a complex environment with many factors influencing the trace element signal in the speleothem with bedrock and soil as primary sources of both calcium and trace elements. The various elements may have more than one source, as ground cover, vegetation (Cosford et al., 2009), sea spray (Baldini et al., 2015), and atmospheric particles are all potential sources (Ayalon et al., 1999; Fairchild and Treble, 2009). Water interactions with the bedrock can vary spatially throughout the cave system, and as interaction time of groundwater with the bedrock, and maximal dissolution occurs when pCO2 is highest, differences between fracture, seepage, and fissure flows can be revealed in the speleothem (Fairchild et al., 2000). In arid conditions, the possibility for prior calcite precipitation (PCP) is increased, and this can be seen in the covariation of Mg and Sr (Verheyden et al., 2000). Instances of high flow and flushing of colloidal transported elements, such as those carried by small detrital particles, (Hartland et al., 2012) is another aspect to consider. In cases of high flow and flushing, it would be expected that elements which are associated with these small particles would occur in higher concentrations directly in conjunction with a high infiltration occurrence (Fairchild and Treble, 2009). Phosphorus (P) (and phosphate) in speleothems has been related to environmental changes (Mason et al., 2007; Jones, 2009; Frisia et al., 2012). Mason et al. (2007) showed that P can be present in several forms within speleothems, incorporated into the calcite crystal in defects and also as phosphate inclusions.

3.2.3. Petrographic analysis and Scanning Electron Microscopy (SEM) Speleothem petrography, i.e. the identification and classification of crystal morphologi- cal changes within a speleothem, provides a valuable tool for the understanding of geo- chemical proxy data (Frisia et al., 2000). The development of the microstratigraphic log (Frisia, 2015) presents researchers with the opportunity to characterize fabrics with a standard framework.

Most speleothems are composed of CaCO3, in the form of calcite or aragonite. Within these two mineral types, variations in crystal fabric indicate a number of important environmental controlling factors (Frisia et al., 2000). It is this information which can provide a valuable basis for interpretations of stable isotope and trace element data. Calcite speleothems generally exhibit formation of crystals which are elongated with respect to the growth axis. The degree of crystal growth surface irregularities is generally no more than 10 µm, and these tend to occur between crystals. Irregularities allow for the formation of spaces termed inclusions, which can contain air and/or water. Fluid- filled inclusions can indicate changes in drip water chemistry or cave microclimate, as they can occur in discretely laminated formations. They are also a source of additional paleoproxy information through the use of δ18O thermometry performed on the tiny amounts of water trapped in these inclusions (McGarry et al., 2004). Laminations or banding can occur on seasonal, annual, or supraannual scales, particularly in regions with strong seasonal variations. Lamina can result from an influx of humic and fluvic -ac ids from the soil zone, generally occurring in the early winter months in boreal climates, from alterations between calcite and aragonite (termed couplets), from changes in cave pCO2 on a seasonal scale, and from changes in trace element composition of the drip waters (McMillan et al., 2005; Baker et al., 2008). However, not all lamina are seasonal or annual, and so great care must be used in making such interpretations (Shen et al., 2013). Calcite fabrics in speleothems have been studied and parallels between fabric and formation environments have been established (Frisia et al., 2000; Frisia, 2015). Initially, petrographic analysis may be used to ensure no post-depositional alteration has occurred in the speleothem, as this can result in element movement within the sample, and

14 erroneous and misleading data. Changes in fabric can indicate the presence of lamina, changes in cave microclimate, periods of increased ventilation, and influxes of detrital particles, stops in growth or hiatuses, corrosion events caused by acidic or undersatu- rated drip waters, and so on. Beyond the standard petrographic microscope, scanning electron microscopy (SEM) imaging is used to examine changes in surface morphology, elemental variation as well as microbe and soot particle presence (Cañveras et al., 2001; Jones, 2001; Jeong et al., 2003; Jones, 2009) within speleothems.

3.2.4. U-Th dating method To provide a useful paleoclimate record, a good chronology is paramount. The most common method for dating speleothems is uranium-thorium disequilibrium (U-Th) dating. This method provides an absolute date based on radioactive decay of uranium which has been incorporated into the crystal lattice of the speleothem calcite at the time the crystal formed. By determining the relative abundance of U and Th isotopes it is possible to use the ratio of the evolved nuclides to determine the age since the calcite was deposited. The uranium which occurs in speleothems is dissolved by percolating waters from within the bedrock, and so the amount of uranium in the host rock (and also the residence of the water within the bedrock) will be reflected in the uranium concentration in the speleothem. This method of dating is made possible by the different behavior of U and Th. Th is insoluble, and is primarily transported while adsorbed onto particles, such as dirt or clay (this is often called “detrital thorium” as it is not a daughter product of the radioactive decay of uranium within the calcite crystal). By contrast, U is highly soluble, allowing it to be transported in solution in the drip water and then incorporated into the calcite crystal lattice. Once the crystal has formed, the U within the lattice begins decaying into Th and the ratio of U to Th tells us how long ago the calcite formed. In the absence of detrital thorium, extremely precise dating is possible, and using U-Th it is possible to date samples up to around 600 ka with precision of between 0.1-1% for samples with low levels of detrital contamination (Fairchild and Baker, 2012). When selecting the area of the speleothem to take samples from for dating, it is important to consider that material from the smaller area will produce a date which has less uncertainty, and that sampling should occur along visible discreet lamina (layers). Fur- ther, the cleaner the sample (i.e. less detrital thorium) the smaller the uncertainty will be. When selecting places to sample from, it is standard to initially take a top, middle, and bottom date to provide an idea of the time over which the speleothem was growing. These samples should, if at all possible, be placed in layers or sections of the stalagmite which are without visible detrital (dirt) contamination, and which are dense and without voids. Once initial results have been obtained, samples can ideally be placed above and below any visible or suspected hiatuses (growth stops, often indicated by a change in color, texture, or change in crystal shapes). Ideally these initial dates will allow for the fine tuning of sample sizes to optimize both the preservation of the intact speleothem as much as possible, and also to improve efficiency in the lab portion of the analysis. With solid samples, taken using a wire or band saw, the sample may be first cleaned using an ultrasound bath to remove any surface detritus which can either have come from the cave environment or from handling the sample after collection. This type of pre-cleaning is only possible on solid samples, and so in cases where controlled sampling environments, such as laminar flow hoods, are not available, solid samples are preferable.

15 16 4. The samples

4.1. Gasparee Cave Stalagmite GC2 (Fig. 5, page 19) from Gasparee Cave, Gaspar Grande Island, Trinidad and Tobago was collected in two sections from a tidal saltwater lagoon in 2008 and 2010 (Fig. 6). The speleothem was not actively growing at the time of collection, though speleothem precipitation was active within the cave at other locations. GC2 measures 293 mm and is composed of white to brownish calcite, with evidence of corrosion on the outer surface of the speleothem. The sample was cut in half down the growth axis and two central slabs were made. One half of each was used for stable isotope, U-Th dating, and petrographic thin sections.

4.2. Kapsia Cave For an initial trace elements study, speleothems from Kapsia Cave were collected (Finné, 2014). Samples from Kapsia are visibly laminated, with porous whitish calcite. The sample from the lowest position in the cave, GK0901 contains a large number of clayey horizons between sections of white porous laminated calcite (Fig. 16, page 37). GK0901 was sawn in half down the growth axis, and two central slabs around 1 cm thick were made. This was used for µXRF analysis, while the facing central slab was used to make petrographic thin sections.

4.3. Alepotrypa Cave Five speleothems covering the period of the Mid-Holocene were analyzed from Alepo- trypa Cave (Fig. 4). At the time of collection none of these speleothems were situated under active drip sites. A1 (Fig. 7) and A2 (Fig. 8) were collected in May 2013. EH1 (Fig. 9) (Collected by P. Karkanas), A6 (Fig. 10), and A7 (Fig. 11) were collected in July 2014. Sample collection sites (Fig. 12) are situated at differing proximities to intense activity in the cave during the Neolithic habitation period. Color images of Fig. 7-11 are found on pages 20-24. A1 is composed of compact whitish to honey-colored calcite, with a black band around 121 mm distance from top (dft) which is interpreted as a hiatus. A2 is composed of similarly colored calcite but contains no visible hiatus features. EH1 has a striking variation in color and texture, from compact brown, to white and clear, and to very porous black. It contains two black layers, the lower of which we interpret as strong indications of human activity, and the upper of which is interpreted as relating to a hiatus occurring around the time of the collapse of the cave. A6 and A7 each contain two compact black

17 colored layers of calcite with clear to honey-colored calcite between, though in A6 this clear middle layer is much thicker. Above the upper black layer, which is interpreted as occurring simultaneously in all three specimens, compact clear/whitish to honey colored calcite is seen. EH1 is topped by a thin layer of white EH1 A1 A7 MA1 MA2 calcite, which dates to modern times. A2 A6 All specimens were sawn in half and two central 0 thick sections made, around 1 cm thick. 1 0 Modern speleothems, one from a staircase (MA1) and one next to A2 (MA2) were also collected, as was 2 0 a large Pleistocene age stalagmite (T1). Detailed de- scriptions and results from these specimens are not 3 0 presented. 4 0 5 0 6 0 7 0 8 0 Years before 2015 9 0 1 0 1 0 1 2 0 1 3 0 1 4 0 1 5 0 1 6 0 1 7 0 1 8 0 hiatus or slow growth high dating uncertanties well dated material 1 9 0 2 0 2 1 0 Figure 4. Time periods covered by stalagmites from Alepotrypa cave.

18 2 cm

Figure 5. Scan of thick section central slab from Gasparee Cave GC2 stalagmite.

Figure 6. Photograph of Gasparee Cave from entry staircase. Photograph shows light coming in the collapsed hole in the roof above the seawater lagoon within the cave. Brown color above the water surface shows the range of the tide within the cave. Photo: Fredrik Ljung

19 2 cm

Figure 7. Scan of stalagmite A1 indicating dating sample sites (yellow ovals), sample track for micromilling and LA-ICP-MS sampling. Dotted line indicates habitation period, rectangles indicate areas shown in petrographic thin section in Paper V. Black arrows indicate the layer of darker material which marks a growth hiatus.

20 Figure 8. Scan of stalagmite A2 indicating dating sample sites (yellow ovals) and isotope sampling track.

21 2 cm

Figure 9. Scan of stalagmite EH1 indicating dating sample sites (yellow ovals), micromilling track, and LA-IPC-MS analysis track overlap. Black arrows indicate the black layers mentioned in the text. Note the very porous black middle layer, indicated by the yellow line. This section is topped by clean white calcite, and thin black layer.

22 Figure 10. Scan of A6 stalagmite, indicating dating sample sites. Micomilling and LA-ICP-MS track overlap and are indicated by the black line. The yellow rectangle indicates the sampling site for SEM material, and the black arrows indicate the black layers discussed in the text.

23 Figure 11. Scan of stalagmite A7 with yellow oval indicating dating sample site. Black line indicates stable isotope sampling track, and yellow rectangle indicates area used for SEM mapping. Black arrows indicate black layers mentioned in the text.

24 Figure 12. Map of the front chambers of Alepotrypa Cave showing collection sites. Chamber G (Γ) and D (Δ) marked in Greek alphabet. Samples T1, A3, MA1 and MA2 have not been fully analyzed and are not presented here. (Map by R. Seifried).

25 26 5. Analytical Methods

In order to produce a good paleoclimate proxy record from speleothems a combination of techniques will produce the best results. Most commonly used in speleothem studies are U-Th dating and stable isotope studies, but trace elements and petrographic analysis are today seen as important signposts for robust interpretations. By combining absolute dating and high-resolution paleoproxy studies it is possible to achieve a high-quality climate archive from speleothems spanning well past the Holocene period, if growth conditions are favorable.

5.1. Stable isotopes Stalagmites from Gasparee Cave and Alepotrypa Cave (A1, A2, A6, A7, EH1) were sampled for 1 mm low-resolution stable isotope analysis using a Dremel hand drill with a 0.5 mm diamond-coated dental drill bit. Based on these initial results, micromill sampling at resolutions between 0.01 mm and 0.25 mm was conducted at University of Innsbruck, Austria. Samples of modern calcite from Alepotrypa cave were collected by placing glass slides and a granite pebble in the cave and removing them at the next cave visit. From each collection medium a small amount of calcite was taken using a scalpel. Stable isotope concentrations were measured on a Thermo Fisher Finnigan Delta- plusXL isotope ratio mass spectrometer equipped with an automated carbonate preparation system (Gasbench II) at the University of Innsbruck, Austria. Values are reported in δ notation relative to the V-PDB standard, with a precision better than 0.08‰ and 0.06‰ for δ18O and δ13C, respectively (Spötl and Vennemann, 2003).

5.2. U-Th Dating

5.2.1. Gasparee Cave For the Gasparee Cave stalagmite, initial dates at the top, middle, and bottom of the sample were produced by the thermo-ionization mass spectrometry method (TIMS). These provided a baseline for the size and placement of subsequent TIMS dating samples, and later for the placement of more precise MC-ICP-MS (multi-collector inductively coupled mass spectrometry) dating samples. 400 mg and 250 mg samples taken from solid 8 mm cores were analyzed at the Uni- versity of Heidelberg, with preparation chemistry following the procedures in Frank et al. (2000) and analyzed using a Finnigan MAT 262 RPQ mass spectrometer. Additional dates were made on 200 mg samples drilled using a diamond-tipped dental drill, and taken along discreet layers. Preparation chemistry was done following Hoff-

27 mann et al. (2007). Measurements of the purified fractions, also following procedures outlined in Hoffmann et al. (2007), were carried out at the National Research Centre for Human Evolution (CENIAH) in Burgos, Spain on a Neptune Thermo Finnigan multi- collector inductively coupled mass spectrometer (MC-ICP-MS). Detrital correction was done assuming a typical upper crustal composition with a 238U/232Th activity ratio for the detritus of 0.8 ± 0.4 (Wedepohl, 1995) and the 238U decay chain in secular equilibrium. Ages were calculated using the half-lives reported in Cheng et al. (2000).

5.2.2. Alepotrypa Cave For the Alepotrypa Cave speleothems, sample sizes ranged between 50 mg and 200 mg. Samples were taken using a Dremel hand drill fitted with a 0.9 mm diamond tipped dental drill bit. Initial dates from speleothem A1 (Fig. 7) were taken in 2013. These were placed in the top, middle (above hiatus) and bottom of the sample. In 2015, 12 additional dates were taken. Speleothem A2 (Fig. 8) was dated at the top, middle, and bottom of the stalagmite. Ad- ditional dating samples were not prioritized at this stage, as high-resolution dating and analysis of all samples was not feasible. Speleothem A6 (Fig. 10) was sampled at 6 sites, including one sample in the dark layer associated with human influence on the cave environment. Sample sizes were taken based on results from A1, with 150 mg and 100 mg samples. Speleothem EH1 (Fig. 9) was sampled in three sites, and speleothem A7 (Fig. 11) was sampled at its top to provide a youngest age.

Table 1. List of materials used in measuring conditions in Alepotrypa Cave and their accuracy, as stated by the manufacturers.

Measured Equipment Accuracy Remark parameter

Drip rate Digital stopwatch ± 1s

Relative humidity Vaisala HM70 ± 1.7% HMP75 probe of cave air

Cave air temperature – Vaisala HM70 ± 0.2°C HMP75 probe discrete ± 1.5% of range and

Cave air CO2 Vaisala GM70 ± 2% of GMP222 probe reading

Sunartis BKT380 Air pressure Mechanical barometer

28 a)

Figure 13. Photos of large human bone (a) D968 and animal horn (b) Z595 samples within the calcite crust (Photos: P. Karkanas). Inset are images of the smaller crust samples taken from these larger sections (Photos: D. Hoffmann). Note placement and size of cuts where final samples were extracted.

29 Three samples were taken from the widespread calcite crust which topped the materials of the Neolithic habitation sediment (Fig. 13). These samples were taken from calcite which grew on human bone (Fig. 13a) and a piece of animal horn (Fig. 13b). Samples were cut using a small band saw under a laminar flow hood. As these samples were solid slices and not powder, they were cleaned using an ultrasound bath prior to being dissolved for preparation chemistry. Preparation chemistry for all samples was done following Hoffmann et al. (2007). In brief, samples were dissolved in 7M HNO3, spiked, and organics were removed through the addition of H2O2 and (where necessary) centrifuging. Fractions of U and Th were separated using resins and purified. Measurements of the purified fractions following procedures outlined in Hoffmann et al. (2007) were carried out at the National Research Centre for Human Evolution (CENIAH) in Burgos, Spain and at the Max Planck Institute for Human Evolution in Leipzig, Germany, both on a Thermo Finnigan Neptune MC- ICP-MS. Detrital correction was done assuming a typical upper crustal composition with a 238U/232Th activity ratio for the detritus of 0.8 ± 0.4 (Wedepohl, 1995) and the 238U decay chain in secular equilibrium. Ages were calculated using the half-lives reported in Cheng et al. (2000).

5.3. Petrographic and SEM images Stalagmite A1 was analyzed in 16 20 µm thick petrographic slides on a standard Leica petrographic microscope at the University of Newcastle, Australia. Images were taken to identify hiatuses which would have implications for the age models. Additional analysis was done on material drilled from the black layers of stalagmites A6 and EH1, as well as thick section slices of A1 and A7, and a solid chip representing the bottom black layer of A6. Material drilled from the black layers of A6 and A7 was dissolved in 6% HCl and pre- pared following procedures in Dredge (2014), and placed onto aluminum stubs for analysis. Additional material was scraped from the black layers of A6 and EH1 and placed, untreated, onto carbon tape pins for analysis. SEM images showing contents of the black layers contained in stalagmites EH1, A6, and A7 were taken using a FY Quanta FEG650 Field Emission Gun and EDS Detector X- Maxs at 80 nm2 in a 0.9 millibar chamber using a large field detector at the Department of Geological Sciences, Stockholm University.

5.4. Modern-day cave environment

During field visits measurements were taken of air pressure, cave air CO2, temperature, and relative humidity. Drip rates at three sites in Alepotrypa Cave were measured using a stopwatch.

5.4.1. Water δ18O and δD Drip water samples were collected during field visits to Alepotrypa Cave and were analyzed for δ13C and δ13C using a Laser Water Isotope Analyzer at the Department of Geological Sciences, Stockholm University. Reproducibility was calculated to be better than 0.6‰ for δD and 0.15‰ for δ18O.

30 5.5. Trace elements

5.5.1. XRF The novel method of applying XRF core scanning was applied to a speleothem from Kap- sia Cave (Paper II). A polished thick section of speleothem GK0901 was scanned along the growth axis using the ITRAX µ-XRF core scanner at the Department of Geological Sciences at Stockholm University. Scans were conducted using a Molybdenum tube set to 30 kV and 30 mA with a step size of 200 µm and an exposure time of 40 s.

5.5.2. LA-ICP-MS This microanalysis technique was applied to samples A6 and A7, and EH1, using a high-resolution sector field ICP-MS Thermo Element2 combined with a UP213 (213 nm, Nd:YAG) laser ablation system at the Max Plank Institute for Chemistry (MPI), Mainz. Synthetic silicate glasses NIST SRM 610, NIST SRM 612, and carbonate reference material MACS3 were used as reference materials. Measurements of 40 elements were made at low and medium mass resolution modes. Five passes of each reference material were made. A pre-ablation pass at 80 µm/second was made along the stalagmite sampling axis at 80% laser output with a spot size of 110 µm prior to ablation for data collection. Abla- tion was conducted in a helium (He) atmosphere, with an argon (Ar) carrier gas flow up line of the plasma torch. Data reduction from counts per second (cps) to parts per million (ppm) was done by calculating the cps intensity relative to the internal standard isotope of 43Ca.

31 32 6. Results

The major results from this thesis are presented as an overview of the sites combined with a summary of papers, followed by a discussion and summation of the most important findings of the project. Dating results for all stalagmites and calcite crust from Alepotrypa Cave are presented in supplementary tables 1, 2, 3 and 4, and age models constructed using StalAge (Scholz and Hoffmann, 2011) for stalagmites GC2, A1, and A6, and supplementary figures 1-3. Modern-day cave environment and drip water data are found in supplementary table 5.

6.1. Constraining the timing of a rapid climate change

6.1.1. Paper I: Early Holocene patterns of rainfall, vegetation and soil conditions, inferred from a southern Caribbean stalagmite Paper I contains the results of the analysis carried out on the GC2 stalagmite, collected from Gasparee Cave, Trinidad. Stable O and C isotope results indicate that Trinidad, with its position in relation to ITCZ movement, is a good site for future studies to constrain the timing and extent of ITCZ related to changes in precipitation amount at the site. δ18O in precipitation is dominated by the amount effect, and wet/dry periods in the GC2 record agree to some extent with those in the Cariaco Basin record (Haug et al., 2001) and in Cuban speleothems (Fensterer et al., 2013) (Fig. 14). By applying spectral analysis to the speleothem stable isotope series it was seen that the site shows a strong periodicity at 1000-1800 years, similar to that seen in many other Holocene climate archives (e.g. Bond et al., 2001; Wanner et al., 2011). Using rampfit analysis (Mudelsee, 2000; Mudelsee, 2010) the onset, duration, and recovery time from the dry conditions was constrained at 8.2 ka to a period of 170 years, occurring between 8.44 – 8.27 ka (±39 a) thousand years before 2000 (Fig. 15) and reflecting the same double peak structure observed in other archives (Alley and Ágústsdóttir, 2005).

33 7500 8000 8500 9000 9500 10000 10500 11000 11500 12000

-33 a) GRIP δ a) -35 18 O ‰ VSMOW -37

-3.5 -39

-2.5 b) -41 O ‰ VPDB

18 -1.5 δ c) Gasparee Cave b) Dos Anas Cave

-4 δ 18 O ‰ VPDB -0.5 c) -2

0 -8 d) -4

0 C ‰ VPDB 13 δ 4 d) Gasparee Cave

e) e) Cariaco Grey scale 200

190

180 0.4 170 f)

0.3 160

0.2 f) Cariaco Ti %

0.1

7500 8000 8500 9000 9500 10000 10500 11000 11500 12000

Years before 2000

Figure 14. Comparison of Caribbean and Greenland archives. (a) GRIP δ18O record (Rasmussen et al., 2006; Vinther et al., 2006), (b) Dos Anas Cave, Cuba, stalagmite δ18O rainfall proxy record (Fensterer et al., 2013), (c) Gasparee Cave, Trinidad stalagmite δ18O rainfall proxy record, (d) Gas- paree Cave, Trinidad stalagmite δ13C rainfall proxy record (e) Cariaco Basin grey scale upwelling (wind strength) record (Hughen et al., 2000) (f) Cariaco Basin runoff record (Haug et al., 2001). Note inverse isotope axes for Gasparee Cave and Dos Anas Cave records. In these records more negative values indicate wetter conditions. Grey boxes indicate timing of the 8.2 ka event, with dating uncertainties (1σ) around 8.0 ka after Rohling and Pälike, (2005) for (a) and (f) and after the original authors for (b) and (c).

34 -5

-4

-3

-2 O ‰ VPDB 18

δ -1

1 -7

-5 δ 13

-3 C ‰ VPDB -1 1 3 5 7600 7800 8000 8200 8400 8600 8800 9000 9200 9400 Years before 2000

Figure 15. δ18O raw data (grey line), adjusted for global ice volume after Guilderson et al. (2001) (black line) and δ13C records. Rampfit analysis shows the rapid recovery from 8.2 ka event (de- layed in the δ13C record). The ramps are fitted using ordinary least squares and a brute-force search technique (Mudelsee, 2000). Standard errors for the ramp parameter estimates are obtained using the moving-block bootstrap (Mudelsee, 2010) with 2000 resamples, which achieves robustness regarding the distributional shape of regression residuals (e.g., non-normality) and also takes into account persistence or autocorrelation. Note inverted isotope scales. 6.2. Moving on from the Caribbean – Novel techniques applied to challenging material

6.2.1. Paper II: Can XRF scanning of speleothems be used as a non- destructive method to identify paleoflood events in caves? Studies of Holocene climate in warm regions continued through the forming of the Nava- rino Environmental Observatory, and an invitation from the Ministry of Greek Culture, the Ephorate of Speleology of Greece, and G. Papathanassopoulos. While speleothem studies at Alepotrypa Cave were being set up, ongoing studies at Kapsia Cave provided the opportunity to test a novel method using the ITRAX µXRF core scanner (Paper II). With its position near a sinkhole, Kapsia cave has been subjected to flooding events (Finné, 2014; Finné et al., 2015). These are visible in the speleothems as detrital rich horizons between laminated porous calcite. Spacing within the sample suggested some regularity in occurrence, and so in order to identify flooding events, stalagmite GK0901 was scanned in thick section along its growth axis. In order to link the detrital horizons to these floods, samples of cave clay were analyzed using the same method to produce an elemental fingerprint. Petrographic thin sections were also used to confirm the presence of detrital horizons, and layer counting was performed between detrital horizons. ITRAX scanning revealed that areas with detrital grains show elevated values of the same elements found in the cave clays, while clean areas of white to dark calcite have much lower concentrations of these elements. Comparisons with the petrographic slides indicate that the ITRAX method was successful in picking up most of the flooding events. However, due to the method used for cutting the stalagmites (water-cooled saw), mate-

35 rial not firmly embedded in the calcite matrix was washed out during the cutting process. This missing material leads to uneven surface conditions and scattered secondary X-rays were emitted. Also, at boundaries between cleaner calcite and detrital rich layers the beam size can lead to layers less than 0.2 mm thick and less than 8 mm in horizontal extent (beam footprint) to being indistinct - which can lead to missed or misidentified flood horizons (Fig. 16). Together these two effects work against each other, with detrital removal causing an overestimation of flood events through the production of scattered secondary x-rays, and the smearing between layers obscuring thin layers, which are otherwise visible in petrographic thin section. The different elemental composition of flood horizons provides potential to correlate individual flood events throughout the cave.

6.3. Alepotrypa Cave – Combining methods to broaden the approach to speleothem studies In order to interpret paleoproxies from Alepotrypa Cave, a look at modern-day conditions is presented to provide background for the interpretations.

6.3.1. Modern-day conditions Alterations made between 1958 and 1970 to the cave structure to accommodate visitors included the digging out of large amounts of mud, displacement of surface calcite crust and surface archeological deposits, bulldozing and enlargement of the cave entrance (Fig. 17), as well as dynamite blasting and jackhammering within the cave to enlarge passageways to a comfortable walking height. Stairways were installed, providing easy access to chambers H and G (Fig. 18). This will have changed the ventilation of the cave from what it was during when the entrance had collapsed, and also when it was inhabited. Studies on modern cave ventilation conditions (Spötl et al., 2005; Mattey et al., 2010) provide an excellent overview of the effects of temperature gradient-driven cave ventilation on the cave environment, drip water chemistry, and speleothem formation. While each cave site is of course unique, Obir Cave presents some well-studied examples which can inform about both modern and past conditions. Obir Cave presents a seasonally controlled cave CO2 patterns with high pCO2 during the summer and low pCO2 in winter, due to enhanced winter ventilation resulting from large temperature differences outside and inside the cave. The modern entrance at Alepotrypa Cave is artificially controlled by means of a large metal door, which limits air movement with the external environment. However, this door is often left open during the summer months while people are moving in and out of the cave during tours, excavation work, and maintenance. This creates an increased potential for movement of air, and the temperature change is noticed in that the area surrounding the entrance is cooler than adjacent areas. By contrast, the cave is less frequently visited during autumn and winter, and so during the season where increased temperature driven ventilation could be expected, the main entrance to the cave is closed. This of course does not exclude the ventilation which occurs through the bedrock system, but as the closed door season also coincides with the time of increased precipitation and rainfall which re-charges the water in the overlying bedrock, air filled space within the bedrock would be reduced, limiting bedrock ventilation compared to the dry summer months.

Measurements of pCO2 in Alepotrypa Cave support this proposed mode of altered ventilation as despite much higher contributions from visitors and researchers during the spring/summer, measured pCO2 values are lower during this time. By contrast, measurements of pCO2 levels in the cave are higher during the winter, likely due to reduced

36 Figure 16. From left 1) Photo of thick section of GK0901 with red boxes marking the positions of thin sections. Layer counting was performed on each thin section. 2) thin sections with green lines indicating clay horizons seen in thick and thin sections, and black lines showing connection of clay horizons in thin section to spikes in Fe count from the XRF analysis. 3) Fe count from XRF analysis. Black arrows indicate peak areas. Areas marked A are peaks interpreted to be overlying larger peaks (see Paper II for details). Letter B indicates peaks with no matching clay horizon in thin section.

37 a)

Figure 17. a) Aerial photograph from 1960 with superimposed cave map. Photo shows terracing and sparse vegetation, and the extent of the slope before it was altered for cave access. b) World- View-2 satellite image taken on 25 September 2011 with a resolution of 2 meters, with superimposed cave map. (Figures by R. Seifried)

38 Figure 18. Cave map showing different chambers, walkways, and lakes (Map by R. Seifried.) ventilation, as when the cave is not in use and the door is sealed (Sup. Table 5). This indicates that the natural expected mode of calcite deposition, which increases in growth rate with lower cave air pCO2 and therefore forced degassing from drip water (Spötl et al., 2005; Mattey et al., 2008), would be biased towards summer deposition (the dry season) rather than winter (wet season) for modern speleothems at Alepotrypa Cave. Humidity measurements were taken at the same sites, and no discernible pattern is seen with the changes. Some variation exists but nothing as clear as the differences inp CO2. Rates of dripping were measured at three sites within the cave on three occasions. Two sites showed faster dripping at the beginning compared to the end of the dry season, while one drip site showed the opposite. Clearly, this is evidence that cave monitoring is most useful when conducted over a long period in order to capture true patterns of variation. Lower pCO2 and lower relative humidity (RH) resulting from enhanced ventilation and negative water balance during drier summer months would increase chances of PCP and raise of modern values of δ13C and δ18O (Fairchild and McMillan, 2007; Lach- niet, 2009). Values of calcite precipitated on glass slides during the summer months today are much less negative than those precipitated during the winter. This large difference is interpreted to represent material affected (PCP) and fast degassing of CO2 due to seasonally low cave pCO2 (Fairchild and McMillan, 2007). 6.3.2. Paper III: Speleothems from Alepotrypa Cave: Towards climate reconstruction A chapter, published in a special volume of materials detailing findings of ongoing excavations at Alepotrypa Cave, provides a detailed description of the project background (Paper III). The chapter gives an overview of Mediterranean climate during the habitation period and in modern times, and introduces the reader to the value of speleothems beyond simple attractive features within caves with a background of speleothems as climate proxies. In combining archeology and speleothem studies, there is an inherent challenge which arises from the fact that humans influence their environment and contribute to a disruption of the “natural” cave environment. In the case of Alepotrypa cave, while the site has preserved many examples of good quality speleothems, the intense human activity within the cave left a discernible fingerprint within the material. From

39 Figure 19. Scans of stalagmites EH1, A6, and A7 showing horizon matching. Area enlarged from A7 is indicated by the white box.

40 Variation in δ18O (‰ PDB) Variation in δ13C (‰ PDB) over time (years before 1950) over time (years before 1950)

1 000 2 000 3 000 4 000 5 000 6 000 1 000 2 000 3 000 4 000 5 000 6 000 Slow growth A1 Slow A1 -11 -5.0 Wetter growth -10

Drier -9 -4.0 -8 -5.5 Slow growth/ Slow growth/ -11 A6 hiatus hiatus A6

-5.0 Wetter -10 -4.5 -9 Drier

-4.0 A2 A2 -11 -5.5 -10 -5.0 -9 Wetter -4.5 -8

-4.0 Drier -7 -12

-11 -5.5 A7 A7

Wetter -10 -5.0 -9 Drier -4.5 -8 -5.5 -7 -11 EH1 -5.0 EH1 Wetter -10 -4.5 -9 Drier

1 000 2 000 3 000 4 000 5 000 6 000 1 000 2 000 3 000 4 000 5 000 6 000 Age (years before 1950) Age (years before 1950)

Figure 20. Stacked plot showing δ18O and δ13C records from A1, A6, (best dated stalagmites), A2, A7, and EH1. Note inverted axis. Records are smoothed to a 50-year resolution to match the coarsest resolution in A1. Dark horizontal lines represent the mean of each stalagmite. Dating sites indicated by small diamonds. Ages are given in years before present (1950).

41 an archeological standpoint, this fingerprint provides information about when people were within the cave, and climate information from exactly this section would be of very high value. From a climate proxy analysis standpoint, the challenge then becomes to disentangle the threads of human and climate information preserved during the habitation period. In Alepotrypa Cave, human presence is clearly marked in several speleothems as dark horizons (Fig. 19). The change in colors is a result of a combination of detrital particles (such as ash from wood, charcoal, and animal dung) as well as dust which circulated within the cave air. While this is a potential proxy for human activity, it complicates the chronology building as an additional source of detrital contamination, which increases uncertainty of the U-Th analysis.

6.3.3. Answering the question of the time of cave closure Paper IV: U-Th dating of calcite on human bones from Alepotrypa Cave, Greece The closure of Alepotrypa Cave has been associated with a tectonic event which occurred in the area around 5.2 ka (Papathanasiou et al., 2000; Papathanasopoulos, 2011). One of the tasks of the project was to investigate if it was possible to date this event using speleothem evidence, and Paper IV was developed to address this. Typological data from cave artifacts has indicated that the cave was inhabited from 8.0–5.2 ka (Papatha- nasiou , 2009), and radiocarbon dates cluster around 5.8 ka with a youngest date on a charcoal fragment dating to 5195 ± 99 cal BP (Oxcal) (P. Karkanas unpublished data). To test this proposed habitation period, dates around dark horizons within the speleothems and of the crust found throughout the chambers were examined. Stalagmite A1 exhibits extremely slow growth and/or a hiatus at 8.2-6.5 ka. This period, which is associated with the development of the S1 sapropel in the Mediterranean Sea is interpreted as having a wetter climate (Bar-Matthews et al., 2000). A6, which grew further from the main habitation area, grew more rapidly between 6-5.5 ka than did A1. Both stalagmites grew very slowly between 5.5-4.5 ka. Recalling the effect of increased

CO2 in the cave air on growth rate, that slower growth and/or corrosion of cave formations is associated with high cave CO2, it could be expected that human activity in the cave would produce slower growth speleothems. Slow growth of the stalagmites can also be a result of changes in the epikarst above the cave, with disturbances and closures of drip water pathways cutting off or reducing the flow of water. These types of disturbances would be expected during tectonic events. Such events have been suggested for changes in nutrient content, electrical conductivity and lake level at Agios Floros fen, Messinia, at 5.7, 5.3, 5.2, and 4.6 ka (Katrantsiotis et al., 2015). These tectonic events occur within the age model error margins of major changes in the growth rate of speleothems A1 and A6, inception of growth in A2, and with occur- rences and boundaries of black layers in A6, EH1, and A7. In the front chamber (B) of Alepotrypa, over 6 m of sediment associated with the inhabitation of the cave has been found. Within these sediments various layers of habitation surface, burials, and rock fall events are interspersed, indicating that major changes of the cave resulting from collapse occurred with regularity during the period of inhabitation. The age of the crust, which grew undisturbed upon dated Neolithic materials, and stalagmites, points to a widespread reoccurrence of speleothem growth throughout Ale- potrypa Cave shortly before 4.3 ka. The lack of disturbance of the crust and artifacts in the cave indicates that at this time the cave was closed to animals with conditions conducive to speleothem growth. It is likely that the abandonment and cave closure occurred

42 simultaneously or close in time. Thus it is reasonable to date the closure of the cave to between 5.2-4.6 ka, in association with tectonic activity, while the abandonment of the site is constrained by a radiocarbon date at 5.2 ka.

6.4. Mid-Holocene Climate in the Peloponnese

6.4.1. Paper V: Stable isotopes and phosphorus patterns in calcite stalagmites from Alepotrypa Cave, Peloponnese, Greece as indicators of Holocene changes in rainfall and vegetation In Paper V stable C and O isotopes from Alepotrypa Cave are presented from five speleothems (Fig. 20), and human influence on the system is investigated by LA-IPC-MS analysis of stalagmite A1 for phosphorus. The record spans from ~6.5 ka to 1.0 ka. The stable oxygen record is interpreted to represent changes in the amount of precipitation, with more negative values corresponding to a greater amount of precipitation, and less negative values corresponding to a lesser amount of precipitation. This is supported by modern relationships between δ18O and rainfall amount, and by previous studies (Finné, 2014). The stable carbon record is interpreted as a record of vegetation and soil biologi- 13 cal productivity. Values of δ C indicate that C3 vegetation is dominant throughout the period of the record, also supported by archeological findings within in the cave. Slow growth in the period defined as the habitation period up until 5.2 ka is interpreted as a reflection of human influence on the cave environment through increased evaporation, input of detrital materials, and higher cave pCO2. During human habitation, P reaches its highest levels above the hiatus layer, likely due to inputs from cave inhabitants and their animals. With a good understanding of the natural level of P (around 110 ppm pre-habitation) and the massive increase after humans move into the cave, we at- tribute the majority of P in the cave to human presence. Following the cave closing and the end of habitation, growth rate increases. Overall, conditions are interpreted as drier from 4.4-2.5 ka, and a period of around 200 years with much less negative δ18O which is interpreted as the 4.2 ka dry event. A similar much less negative value is seen around 3.2 ka. This dry event at 3.2 ka is coincident with major changes in human cultures throughout the Mediterranean region. Values of P continue to fall steadily following the end of habitation until 2.7 ka when there may be increased human activity at the site. At 1.6 ka indications are seen of another dry period, which occurs at the same time as glacial advances in the Alps.

6.4.2. Beyond climate Paper VI: Trace elements as recorders of human activity and environmental indicators at Alepotrypa Cave, Greece Continuing on from the summary of the project given in the Paper III and insights into cave closure in Paper IV, the method of LA-IPC-MS is applied to stalagmites A1 and A6 in concert with petrographic and SEM images from EH1 and A7 (Paper VI). Using the difference between pre (19-8 ka) and post habitation (~4.4-2.4 ka) levels of trace elements compared to the period of habitation in A6 (6.0-5.4 ka), a clear human contribution to the natural cave system is shown. The difference in concentrations of manganese (Mn), aluminum (Al), and iron (Fe) between the black and clear layers associated with human habitation indicates that burning of animal dung was responsible for creating a cave

43 environment which had high amounts of detrital and soot particles in the air, and which allowed microbes and oxides to form thick layers on speleothems growing close to this activity. The change from dark to clear calcite coincides with a drop in the average concentrations of Mn, Fe, and Al to similar concentrations seen in the post-habitation period. After the cave entrance collapses leading to closed cave conditions, trace element levels generally drop but two events are marked by a sustained increased in Al, silica (Si), tita- nium (Ti), Fe and the light rare earth elements rubidium (Rb), yttrium (Y), and lanthanum (La) in A1. These events occur at 3.6 ka and 2.7 ka, and this timing fits with the 3.6 ka Minoan eruption of Thera on Santorini, and an eruption at Somma (Vesuvius) around 2.7 ka. Due to limited colloid transport to stalagmite A6, similar increases in metals are not seen at 3.6 ka. A6 instead shows a response in Fe, Ba, sulfur (S) and uranium (U) which is unrivaled between 3.8 and 3.4 ka, and which falls within previously well-dated estimates of the Minoan eruption. The different drip water paths and mixing conditions provide a more colloid-biased signal to A1, and a solute signal to A6.

44 7. Discussion and Supporting Data

Throughout this thesis a range of methods have been applied in order to explore climate in warm regions and to determine human impact on the cave environment. Ideally, a cave study would be conducted at a site with extensive long term monitoring of those factors which influence the climate proxy signals, and if possible, produce a quantitative record. In reality, proximity to site which enables frequent or constant monitoring studies, and modern-day cave conditions can have a complicating influence on producing an “ideal” study. Beyond a similarity of seasonal rainfall and warm temperatures, the work on the two sections of the project has brought into focus the difficulties in working with sites with altered modern conditions compared to those which were present during the formation of speleothems used for paleoclimate research. In Gasparee Cave, the collapse of the cave roof has opened the cave to the surface environment and this prevents the use of the cave for modern analog studies which would allow for quantitative reconstructions. Also, distance to the site prevented visits for e.g. rainwater collection. Strong regional indications of amount effect control on δ18O in precipitation were key to making the interpretations. Similarly at Alepotrypa Cave, the altering of the cave structure for tourist development means that modern-day conditions match neither the closed cave conditions which are inferred between 5.2 ka to ~1950, nor those which were present during and prior to human occupation of the site. Attempts to correlate modern calcite and rainfall amount were hampered by sporadic sampling opportunities and random factors influencing ventilation, temperature change, and CO2 levels. Despite these stumbling blocks, the aim of providing new records from sparsely studied warm climate regions to help fill the gap of paleoclimate proxy records with good chronologies is addressed with the records from Gasparee Cave and Alepotrypa Cave.

7.1. The Caribbean By looking at the 8.2 ka event in the Gasparee Cave material it was possible to establish a local duration of the southward excursion of the ITCZ, which is expressed as a minima of precipitation through less negative δ18O values. Overall trends to more negative δ18O values are reflected in other nearby records which show increasing rainfall throughout the early Holocene and a “double point” excursion to dry conditions around 8.2 ka. In the complex rainfall patterns of the Caribbean, Gasparee Cave provides a site-specific signal rather than the basin catchment represented by the Cariaco Basin record. The proximity between the two sites allows testing of the Gasparee Cave record against the excellent Cariaco Basin record (Peterson et al., 2000; Haug et al., 2001), and trends between the two tend to have good agreement. To better understand how past atmospheric circulation changes manifested in the Caribbean, site-specific records can provide important nuance

45 to large scale reconstructions. By investigating the duration of the onset and recovery from the event using rampfit analysis (Mudelsee, 2000), we see that the ITCZ responded rapidly to forcing from the input of cold freshwater in the North Atlantic associated with the drainage of Lake Agassiz. The drought-sensitive nature of the deciduous dry tropical forest on the island, along with the shallow soil profile, shows a more gradual recovery as increased wind strengths seen in nearby records seem to have also had an impact on the resilience of the overlying plants and soil. By understanding the duration of these rapid climate change events, such as the 8.2 ka event, we can better predict the way in which future climate changes might manifest.

7.2. Speleothems in the Peloponnese Material from Alepotrypa Cave makes up the majority of the work within this thesis, but as the application and development of new methods for speleothem analysis, particularly non-destructive techniques, is of interest to a wider community we tested the use of µXRF scanning on a detrital-rich speleothem from Kapsia Cave. Results showed that the ITRAX µXRF technique has some promise. However, further work with trace elements was undertaken with more conventional LA-IPC-MS methods.

7.2.1. Human influence on cave environment Human impact on cave environments has been studied more extensively in the past few decades as interest in good conservation and management for sustainable use of tourist caves, especially those containing rock paintings, has increased (Cigna, 1993; Pulido- Bosch et al., 1997; Baker and Genty, 1998; Cañveras et al., 2001; Habib et al., 2008; Russell and MacLean, 2008; Fernandez-Cortes et al., 2011; Baker, 2014). Illumination of the cave space allows purchase for different types of algae, which otherwise do not successfully colonize the cave environment, and the presence of humans also brings an increased input of organic matter and microbes. Increased CO2 in the cave air, as seen in many tourist cave studies, is a direct result of human presence, and in the case of Alepotrypa Cave, it can be assumed that the use of the cave by a population estimated to be at least dozens of people in the settlement significantly increased the cave 2CO levels. The modern example of Canelobre cave (Cuevas-González et al., 2010) in Spain can provide an idea of how humans living in Alepotrypa Cave can have influenced the cave microclimate. With the highest number of visitors during the summer, increases in cave

CO2 can be up to double the annual average concentration (from 493 ppm up to near- ly 1000 ppm). Increased ventilation by convective air circulation is highest during the cooler winter months, when external air temperatures fall below cave air temperatures. Cuevas-Gonzalez et al. (2010) also found that relative humidity within the cave is more stable, even during the dryer summer months, as a result of a stratification of cave air along with a reduced temperature gradient inside and outside the cave which reduces air exchange. Human presence within the cave also increases the cave temperature (Baker and Genty, 1998; Russell and MacLean, 2008; Fernandez-Cortes et al., 2011). With frequent to constant use of Alepotrypa Cave as a habitation site, such an increase in cave temperature would be a reasonable assumption, possibly driving increased ventilation during winter. Studies of human contributions of dust and aerosols to the cave environment (Jeong et al., 2003; Dredge et al., 2013) indicate that even carefully controlled cave environments receive a significant contribution of dust and aerosols from human visits. Inhabi- tation and utilization of cave resources, digging, construction of pits, and combustion

46 a) 200 Mouzaki -14 180 18 -12 Rainfall (mm) δ O SMOW (‰) δ

160 -10 18

140 -8 O SMOW (‰) 120 -6 100 -4 80 60 -2 Rainfall (mm) 40 0 20 2 0 4

2012-09-21 2012-11-10 2012-12-30 2013-02-18 2013-04-09 2013-05-29 2013-07-18 2013-09-06 2013-10-26 2013-12-15 2014-02-03 2014-03-25 b) Methoni

250 30.0

25.0 200

20.0 150

15.0

100 10.0

50 5.0 Monthly avergae temperature 1951-2008 Monthly avergae precipitation 1951-2008 0 0.0 Jan Feb Mar Apr May JuneJuly Aug SepOct Nov Dec

200

150

100

-50

-100 Negative water balance

Calculated water excess Methoni -150

-200 Jan Feb Mar Apr May JuneJuly Aug SepOct Nov Dec

Figure 21. a) Recent δ18O in precipitation and precipitation amount in mm from Mouzaki, Messin- ia. Note inverted scale for δ18O. b) Precipitation and temperature measured at the meteorological station near Methoni. Lower figure shows the negative water balance which occurs in summer, preventing recharge of aquifers. Error bars show one standard deviation. Figure modified after Finné (2014).

47 of biofuels within the cave would have had much greater impacts than today’s tourists. Dredge (2013) states that the preservation of aerosols within speleothems depends on the mechanism of deposition as well as drip water flow rates. While dripping of water onto unconsolidated materials would result in their being washed away, preservation is possible during hiatuses (and very slow growth), particularly when these particles are bound into calcareous horizons. This appears to be the case at Alepotrypa in stalagmites EH1, A6 and A7.

7.2.2. Mid- Holocene conditions at Alepotrypa Cave In order for δ18O in speleothems to provide useful climate proxy data, its relationship to δ18O in local precipitation must be understood. Using deuterium excess (D-excess) Argiriou and Lykoudis (2006) showed that rainfall at Methoni possibly receives a larger proportion of its precipitation from moisture which originated in the Atlantic or Western Mediterranean, compared to e.g. Heraklion, which receives more vapor from the Aegean or Mid-eastern Mediterranean. There is also a compounding of seasonal and temperature dependence of the δ18O values, with winter precipitation in higher amounts (70-80% of the annual), and lower temperatures having a more negative signature. δ18O in precipitation in the coastal Peloponnese has a mean value of between -5.5 ‰ and 6.5 ‰ (Dotsika et al., 2010). The similarity of δ18O in precipitation to δ18O in spring water measured in the Peloponnese suggests that, despite the presence of the Pindus and Taygetos mountains, recharge of aquifers is not significantly dependent on precipitation occurring at much higher elevations (Dotsika et al., 2010). Therefore, δ18O in cave drip water should not have a significant portion of precipitation with altitude effect on δ18O. The best avail- 18 able δ O in precipitation dataset from Methoni shows a weaker amount effect signal than other data stations in the region (data from 1963-1968). However, this is based on only 10 samples representing monthly precipitation averages from that period. Recent sampling carried out at Mouzaki, near Methoni (Fig. 21) shows an amount effect with larger amounts of precipitation agreeing with more negative values of δ18O in precipitation. In using modern measurements from rainfall amount and δ18O taken in Mouzaki, we demonstrate agreement between amount of rainfall and the value of δ18O measured in precipitation. This is also seen in other studies in the Peloponnese (Finné, 2014) and in other studies of speleothems in the Mediterranean region (Bard et al., 2002; Bar-Mat- thews et al., 2003; Verheyden et al., 2008; Jex et al., 2010; Orland et al., 2012; Zanchetta et al., 2014). As the period we examine is not subject to major changes in global ice volume or temperature, and as the source of precipitation has remained the same, we consider influences on δ18O to be dominated by the amount effect. As always, a larger local data set would be welcome, but the evidence presented here and in other speleothem studies from the eastern Mediterranean provide enough confidence of the amount effect to allow for the use of δ18O as a precipitation amount proxy, and suggest that the amount effect has been the major factor controlling δ18O in the speleothems for the last 6500 years. With the modern conditions and other show caves studies as a basis for human impact on caves, it is reasonable to assume that the slow growth at Alepotrypa Cave during the habitation period can be attributed to high levels ofp CO2 and lower RH. The most tan- gible effect that the cave experienced during habitation was a dramatic input of detrital materials and cave conditions which were conducive to microbial communities forming on stalagmite surfaces, especially in those stalagmites found closest to the habitation site. In order to see if these processes have masked or influenced the stable isotope signal, stalagmites A1 and A6 were compared.

48 Variation in δ18O (‰ PDB) over time (years before 1950)

1 000 2 000 3 000 4 000 5 000 6 000 Slow growth

-5.0

-4.5

-4.0

-5.5 A6

Slow growth/hiatus

-5.0

-4.5

-4.0 Kapsia cave -6.0

-5.5

-5.0

-4.5

Soreq Cave

-6.0

-5.5

-5.0

Greenland lake ss1220 3.0

2.0

1.0 NAO Index

0.0

-1.0

-2.0

-3.0

1 000 2 000 3 000 4 000 5 000 6 000 Figure 22. Stacked plot showing Alepotrypa Cave speleothems A1 and A6 δ18O and records from Age (years before 1950) Kapsia Cave (Finné et al, 2014), Soreq Cave (Bar-Matthews et al. 2003) and Greenland lake SS1220 (Ohlsen et al. 2012). Horizontal lines indicate mean value of the record for the period shown, except the Greenland lake record, where the dotted line denotes zero. All records have been inter- polated to annual resolution and smoothed to the coarsest resolution of stalagmite A1 (50 years). Ages are given in years before present (1950).

49 D H

B B

Figure 23. Petrographic thin section showing top of the hiatus and detrital rich layers from the habitation period, area (a) from Fig. 7 in plane polarized light. Letter H indicates identified hiatus in growth, D indicates increased concentrations of detrital grains, and B indicates microbial features associated with phosphate enrichment.

At 5.7 ka, calcite in A6 shifts from dark to clear and at the same time 18δ O values become more negative. In A1, we see a similarly timed shift in δ18O to more negative values and we therefore interpret that the dark coloration of A6 does not mask the δ18O climate signal. The more negative values seen in A1 and A6 at 5.8-5.7 ka indicate that conditions became wetter at this time. Being aware that higher levels of PCP would drive both 18δ O and δ13C to less negative values, we compare the stable O and C profiles to see if human impact was driving PCP before and after the change in conditions at 5.8-5.7 ka. While the stable isotope profiles are similar, as expected in a region where precipitation has a large impact on vegetation productivity, they are not identical, and we cautiously interpret this as a lack of strong PCP influence on the stable isotope signal. Looking further afield to strengthen these interpretations, we examine δ18O in the Soreq cave record (Fig. 22), which at this time also shows a shift to wetter conditions. With the majority of precipitation being controlled by similar systems at these two sites, an agreement in wetter conditions seems reasonable if the speleothems are providing a good climate proxy signal. The positioning of Alepotrypa Cave next to the Ksagounaki settlement on the promontory suggests that human influence on vegetation above the cave was very likely, but similarity between the δ13C and δ18O profiles suggest that the composition of this vegetation was of a similar type throughout the Mid-Holocene. The values of 13δ C in

Alepotrypa Cave stay within the range of that expected for C3 vegetation, which fits

50 with those finds of plant matter associated with the cave inhabitants. The similarities to the δ18O record suggest that the processes which are seen in each of these proxies are related, and this supports the amount effect hypotheses for the interpretation of the 18δ O data. In periods where δ18O and δ13C are not in agreement, positive North Sea Caspian Pattern Index (NCP) conditions could be responsible. During NCP+ conditions, colder air is funneled through the valleys of the Peloponnese, which could lead to increased inci- dence of frost events in the spring while precipitation amounts are largely unchanged. As vegetation at the site is frost-sensitive, it seems likely that temperature could be one explanation for these apparent departures from water availability controlling biologi-

Table 2. Measured composition of elements in the charcoal particle seen in Fig. 24.

Element Wt % σ C 79.5 0.2 O 18.0 0.2 Ca 1.0 0.0 Si 0.6 0.0 Na 0.3 0.0 Al 0.2 0.0

Figure 24. SEM photomicrographs of material from EH1, indicated by yellow rectangle in figure 9. Charcoal particles, likely from nearby burning of animal dung. Spectra taken at white cross in image, results are seen in table 2.

51 Figure 25. SEM map from stalagmite A7, area indicated in Fig. 11. The black layers seen in thick section have varying chemistry. High concentrations of P and Al could be related to the colonization of the stalagmite surface by different microbial communities. cal productivity. This is suggested by δ13C showing less negative values, interpreted as reduced soil and vegetative productivity, while δ18O indicates good water availability for vegetation based on similar values in the record. The replication of a move towards less negative δ18O isotopes is seen at 4.2 ka in the well-dated stalagmites A1 and A6, and within the uncertainties of A2, A7, and EH1. This suggests that the Alepotrypa Cave record shows a robust indication for a rapid dry 4.2 ka event in the coastal Peloponnese. This event, which has been a source of debate in the literature, has not previously been identified in the region (Finné et al., 2011). There is also evidence of a dry 3.2 ka event (Drake, 2012; Wiener, 2013), which occurs during a period of overall drier conditions from 4.5 ka. This is in agreement with lake records from the Mediterranean showing drier values from 4.0 ka and onwards compared to the Early Holocene (Roberts et al., 2008). Around 3.0 ka there appears to be a short move to wetter conditions, though overall drier conditions continue until 2.5 ka, in agreement with dry conditions at Lake Van, Turkey (Wick et al., 2003). Why the 4.2 ka event is “missing” from other proxy records could be related to issues with dating, or a lack of high-resolution records capturing a clear precipitation signal. Comparison of the Alepotrypa Cave speleothems to the SS1220 Greenland lake record (Olsen et al., 2012) indicates some connections between NAO- conditions and wetter conditions at Alepotrypa Cave (Fig. 22) . NAO- conditions are generally associated with milder wetter conditions throughout the Mediterranean, but in the Peloponnese and the eastern Mediterranean, the influence of the NCP is also very important. This becomes apparent in the dry period seen in the Alepotrypa record at 1.6 ka, which occurs at the same time as a cold event identified as having wide expression in the northern hemi-

52 Figure 26. SEM photomicrograph of material from between 53-63 mm dft in A6, indicated by yellow box in Fig. 10. Image shows round calcified structures interpreted to be a colony of microbes, the structure of which has preserved within the speleothem. sphere. The Turkish Nar Gölü lake record indicates that winters were more severe, and precipitation more strongly tied to snowfall at ~1.6 ka, while cold and wet conditions prevailed in the alps (Jones et al., 2006). This implicates teleconnections to the North Atlantic, and more regional effects which are tied to the NCP index (Jones et al., 2006; Ljungqvist, 2010; Wanner et al., 2011; Dean et al., 2013). It is no longer sufficient to simply look to the NAO as the main driver of conditions in the Mediterranean at large, and further work on disentangling the complex influences at longer time scales will be vital to understand if (or how) changes in past human societies relate to climate or other factors. Those strategies which made past societies resilient and successful in the face of climate change, and which can provide important guidance for future climate change adaptation strategies, are best viewed against a background of well dated robust climate data. The use of the caves by humans negatively impacted overall speleothem growth at Alepotrypa Cave, but those specimens which were growing while the cave was in use have provided much more than just climate proxy data. The human impact on speleothem quality in A1 can be characterized through observations in hand section and thin section petrographic analysis. To the unaided eye, the period of 6.3-5.2 ka appears as having a tan to brown coloration. In petrographic thin section, this period is marked by a transition from micritic crystals and higher amounts of detrital particles between crystals to less detrital particles and more long crystals of columnar calcite (Fig. 23). This clear indication of changes in the cave environment guided the choice to continue and use LA-ICP-MS to look more closely at changes in the chemical composition of the speleothems.

53 Figure 27. SEM photomicrograph of pollen/spore encrusted in calcite. Material taken from area indicated by yellow rectangle in EH1, Fig. 9.

In modern show caves, algae and other microbes thrive in environments where only small amounts of light and additional nutrients are provided. The presence of many humans living in Alepotrypa Cave would have provided both of these. By comparing the trace element profiles of the material in the black and clear sections of stalagmite A6, a much higher concentration of metals, particularly those generally associated with oxides (e.g. Mn, Fe, and Al) is apparent in the periods associated with habitation. SEM imaging was used to look for the presence of soot and charcoal particles in the samples (Fig. 24), as it was supposed that the dark coloration could be a result of the intensity of use of chamber E and H. These chambers are distinguished from the rest of the cave by the presence of burnt animal dung on the cave floor, with deposits there measuring 60–150 cm in depth. This burning of dung provided a contribution of detrital material to the air and enhanced nutrient availability in the otherwise nutrient-poor cave system. However, while some charcoal particles are found, the high levels of P, Mn, Al, and Fe identified in LA-ICP-MS and features in SEM images suggest that oxides and phosphates are the likely source of coloration. Elemental maps revealed that layers in A7 contain very high amounts of phosphorus (P) and aluminum (Al) (Fig. 25). Concentrations of P and Al in speleothems can be a result of microbial activity (Jones, 2001; Jones, 2009) which fits with the increased access to nutrients provided by human inhabitation of Alepot- rypa Cave. Microbial films on the surface of stalagmites thrive when people bring dust, spores, and light into the otherwise nutrient poor cave environment. Such conditions occur preferentially during periods of very slow growth (low drip rate) or hiatuses (Fig.

54 23, 26), which fits with the position and discreet nature of the P and Al concentrations in A7. Other finds in EH1 include what appears to be pollen or spores (Fig. 27), likely contributed from the dung and plant matter which was burned. Dating uncertainty in speleothems is closely tied to the detrital thorium contamination and initial uranium concentrations. In the clean calcite sections of speleothems from Alepotrypa cave, age uncertainty is relatively low. Dates from within the black sections, corresponding to the habitation period, are very high in thorium and present a challenge for more closely tying the archeological record to the speleothem chronology. However, by using the dates bracketing black layers it has been possible to gain insight into the change in behavior around chambers E and H close to 5.8 ka. The upper dark layer which separates clean calcite in EH1 and A6 has been dated to around 4.6 ka, and is rich in phosphorus. The hiatus in A1 around 6.5 ka, seen in thin section, is similarly enriched in P. Colonization of the speleothem surface by microbes can occur at times of low drip rates, and can result in increases in P which accumulates on the surface. The input of black material at this surface, and an occurrence of low drip rates, could be related to the tectonic event which closed the cave. If microbial colonization was purely a result of low drip rates, then it seems reasonable that other such horizons would occur in the material even post-habitation, when indications of the driest conditions are seen around 4.2 ka and 3.2 ka, but this is not the case. Using dates of clean calcite growth and the dates on the extensive calcite crust which covers much of the cave floor in chambers A, B and D (detailed in Paper IV), we show that closed cave conditions which favor widespread growth of compact calcite speleothems are in place by this time. In examining the impact of humans at Alepotrypa Cave using trace element LA-ICP- MS data, the signals of several suspected volcanic eruptions were also found. Although some studies have employed sulfur as a tracer (Frisia et al., 2008; Badertscher et al., 2014; Jamieson et al., 2015), it seems that at Alepotrypa Cave stalagmite A1 instead received a large increase in colloidal input at 3.6 ka and 2.7 ka. This is likely due to the position of A1 in the cave in chamber G (Γ), higher up than A6 and overlain with less bedrock. Fis- sures and water pathways in the upper epikarst are larger than those deeper within the bedrock (Williams, 2008) and this can have facilitated the passage of colloid particles to the drip site rather than elements in solution. Taking a broader perspective, these results can contribute to the ongoing debate about the timing of the Santorini eruption (Ham- mer et al., 1987; Pearson et al., 2009; Badertscher et al., 2014; Bietak, 2014; Bruins and van der Plicht, 2014; Cherubini et al., 2014; Manning et al., 2014). Though some would suggest that the timing of the eruption is a topic which has been settled, there is not complete consensus. Disagreement between 14C dates from olive wood and archeological findings make absolute dated archives an important component in determining the timing of this event. While the current uncertainties in the chronology of the Alepotrypa Cave material do not allow for a firm “high” (between 3.7-3.6 ka) or “low” (between 3.6-3.4 ka) chronology, the results show that the material from this site is an excellent candidate to help constrain the timing. While it is most likely that these signals relate to the Santorini and Somma eruptions, given the abundance of colloidal particles in A1, it may be possible to further strengthen the interpretation if the chemical fingerprint of the eruption materials can be identified in the speleothem trace elements.

55 56 8. Final remarks – Perspectives on future research

Within the Holocene human impacts on the global climate have been unprecedented. Where before the natural variations of the global system, Earth’s orbit and the sun gov- erned the conditions, we now face a new type of uncertainty. This uncertainty is higher for those parts of the world which have poor spatial coverage of paleoclimate records, as the model simulations can only provide simulations as good as the data they are based on. To understand how past societies faced the challenges of climate change, it is vital to work towards a detailed understanding of individual climate trends and events and their drivers, regional-to-local expressions as were done at Gasparee Cave, as well as to explore human connections to climate change throughout history. Through the opportunity to test new approaches and work outside the “ideal” cave box, work in the Carib- bean and the Peloponnese is making important contributions to the availability of paleoclimate data. A challenge with working on Alepotrypa Cave is the publication in most related material in the local language. Only a few publications had been made in English despite the extensive work carried out at the site. This has made the contributions of the local team invaluable to the successful interpretation of the results detailed in this thesis. One of the most interesting prospects for continued work on Alepotrypa Cave is the successful marriage of speleothem studies and archeology. A framework of dates which constrain some behavior of people living in the cave is only the beginning, and there is great potential to continue finding new clues in the speleothem data. This thesis does not contain all the data which was produced during the project. More investigation with trace elements to further secure the climate interpretations, as well as statistical testing of elemental associations within the black and clear sections of the speleothems is ongoing. Initial work with the ITRAX µXRF system was continued on speleothem A1, and a comparison to LA-ICP-MS results is forthcoming, and could provide a “quick and dirty” approach to selecting interesting specimens for more costly analysis with LA-IPC-MS. Additionally, the large Pleistocene stalagmite T1 presents an exciting opportunity to extend this record back to 60 ka.

57 58 9. Conclusions

This thesis provides new Holocene records from regions with large uncertainties in the face of future climate change. Following work at Gasparee Cave to understand the mechanisms for a rapid climate change event, a regional shift was made to the Pelopon- nese. Data from Alepotrypa Cave provides new, well dated Mid-Holocene paleorainfall records, which will aid many interpretations of climate and human connections in this archeologically well-studied, highly populated area. The main conclusions in this thesis are: • Speleothems from Gasparee Cave can be used to reconstruct rainfall amount variations which reflect site-specific rainfall amounts tied to the position of the ITCZ and connections to millennial scale climate processes. • In working with an established archeological excavation it has been possible to include scientists from other disciplines in the project. This has greatly enriched the interpretation of the record and provided new angles of investigation. In the quest for more applications for climate data, early involvement and active par- ticipation are key to good dissemination of information and remaining relevant. • Through application of the replication method, the quality of the Alepotrypa Cave climate record is shown. The δ18O precipitation amount proxy provides the first robust, well-dated evidence of a rapid, dry, 4.2 ka dry event, and a dry event within a drier than average period around 3.2 ka. This greatly reduces the uncertainty surrounding the occurrence of these events in the Peloponnese. • A multi-proxy approach to the Alepotrypa Cave record has shown the lingering effects of humans on the cave, with elevated P levels long after cave closure, and increased use of the area above the cave again after 2.7 ka. • The δ18O and δ13C records provide a well dated record of precipitation variation and closely related vegetation and soil productivity. From mismatches in the stable isotopes, there is potential to inform about temperature conditions. • In seeking to understand human impact it was possible to inform about human behavior in the cave. This analysis also led to the unexpected potential identification of two nearby volcanic eruptions:; the Minoan eruption of Thera (Santorini) at around 3.6 ka and the eruption of Somma (Vesuvius) at 2.7 ka. This PhD work began as an effort to improve coverage of Holocene paleoclimate data in two regions vulnerable to changes in precipitation, which it has delivered. In taking a broad approach to the methods available in speleothem analysis, this study has gone beyond its original scope to inform about ways in which speleothem research has value outside of its established place as a provider of paleoclimate data. Research at Alepotrypa Cave began in the 1970s and has provided much enlightening information about the people who lived at the site. By applying U-Th dating and looking at element contribution to speleothem calcite, it has been possible to see how people affected their living

59 environment over time, and when large changes occurred. This provides a new angle from which to view human activity at the settlement. The climate series provides not only an important record for the Alepotrypa cave settlement interpretation, but also a wider regional basis for understanding the changes in rich archeological setting of the Peloponnese.

60 10. Acknowledgements

Funding for the project has been provided by the Swedish Research Council, grant number 621-2012-4344 (K.H.), and by Navarino Environmental Observatory. Analytical costs have been partially covered by the generous support of the Bolin Centre for Climate Re- search, and with contributions from the Mannerfelt’s, Ahlmann’s and Lagrelius’ funds. Field work was supported by the Swedish Society for Anthropology and Geography, and The Geographical Society of Stockholm (Geografiska Förbundet). Collaboration with the University of the West Indies, St. Augustine, Trinidad with permissions from the Chaguaramas Development Authority facilitated work in Gasparee Cave, Trinidad & Tobago. Work in Alepotrypa Cave, Greece, was possible through extensive collaboration with the Ephorate of Paleoanthropology and Speleology of Greece, and the Greek Min- istry of Culture. I would especially like to thank the Alepotrypa Cave research team, under the leadership of G. Papathanassopoulos, Anastasia Papathanasiou, and Panagiotis Karkanas for reaching out to the Navarino Environmental Observatory and supporting a rewarding cross-disciplinary partnership. A challenge with working on Alepotrypa Cave has been that only a few publications are available in English despite the extensive work carried out at the site. This has made the contributions of the local team, especially A. Papathanasiou and P. Karkanas, invaluable to the successful interpretation of the results detailed in this thesis. Cave visits and collection of water samples at Mouzaki were made possible by NEO station managers Giorgos Maneas and Nikos Kalivitis. Additional information was provided by Bill Parkinson of the Chicago Field Museum, American co-director of the Diros Project. Maps of Alepotrypa Cave and aerial photo figures in the thesis were made by Rebecca Seifried, also of the Diros Project and Chicago Field Museum. Comments and suggestions which improved this kappa were made by Steffen Holzkämper and Peter Jansson, and the process of getting it to print was made possible by a very patient Helle Skånes, with formatting work by Hugo Ahlenius at Nordpil and proofreading by my good friend and fellow Canadian Teslin Seale. Thanks to the awesome team at Stockholm University Library who handled the printing process and spikblad. To my wonderful, fabulous, amazing, and fantastic and patient advisor, Karin Holmgren. Thank you for supporting me throughout my undergraduate, Masters, and PhD work with tireless amounts of manuscript editing and guidance. I never realized that staying after a lecture to ask a few questions about the potential for climate research and speleothems would lead down this path, but I am so very glad that it did! I am deeply grateful for the

61 honest and professional working environment you make possible. Your encouragement to experiment, improve, test, and try was central to a creative and rewarding process. To never divide efforts between good science and good working relationships makes for the best partnerships, and working with you has set a standard I hope I can continue with for the rest of my career. Your unwavering professionalism and support meant I never had to worry about the small things. You were always in my corner, and I knew you were root- ing for me to succeed the whole time. I hope that your future colleagues, wherever they are, realize their good fortune to be working with someone who is an excellent scientist and a remarkable, deeply caring, loyal person. Thanks to Paul Shaw (and Lynn!), savage scientist and my academic grandfather, who introduced me to Trinidad, caving, soca, and the benefits of having a blue office. Your hospitality was boundless, as was your patience and support. I hope that you don’t mind if we visit more often! Hanna Sundqvist, whose absence at the department has been keenly felt by me this last year. I know you’re excelling in your new career but I selfishly wish you had stayed on until I was finished. Your good advice and friendship were impossible to replace. You’re the best fieldwork mate anyone could ask for, thank you for all your help and support! A great number of people have helped with the preparation and analysis of the samples, starting with two local stone cutting companies in Areopolis and Athens, and Dan in the geo workshop at IGV. Additional sampling and prep was carried out by Dawn Cederberg, Laura McGlynn and studentpraktik assistant extraordinaire Michael Maszk. Initial statistical consulting for Paper VI was generously provided by Jan Plue. Many others who contributed are co-authors on the papers in this thesis, and it is through their generous donation of lab time and resources that these studies were made possible. Augusto Mangini made it produced the first set of TIMS dates on the Gasparee Cave material, and that has grown into the rest of this work. Christoph Spötl first opened his stable isotope lab to me in 2010 and has been a source of encouragement as well as a dedicated co-author with a keen eye for improving manuscripts ever since. Sampling help, micromill malfunction fixes, and analysis of stable isotope samples was conducted by the amazing Manuela Wimmer. Manfred Mudelsee and Paul J. Krusic have helped steer the project through the sometimes treacherous waters of statistics with great dedi- cation. Dirk Hoffmann has carried samples through two countries to two different labs, patiently answered every question, and supervised many hours of drying down the fractions supplemented with engaging conversations about sampling procedures to get the chronology done. Denis Scholz recently became involved and through him it was possible to collaborate with Klaus Peter Jochum and Brigitte Stoll. Their work on the trace elements portion of the project opened up many new possibilities, and I hope we will continue to make new discoveries. Thanks in particular to Martin Finné, fellow Greek carbonate botherer, who began sharing an office with me while I was finishing writ- ing up under a self-imposed deadline of doom. We had some great discussions and I appreciate your help with forming order in chaos, and for all the fun ITRAX work we started up years ago. Those whose knowledge has contributed indirectly to the suc- cess of the project include Andrea Borsato and Silvia Frisia, who generously hosted my visit to Newcastle, NSW in 2014, and showed me the basics of petrographic analysis of speleothems. Radovan Krejci (ACES) and Prof. Brian Jones (U of Alberta) assisted with SEM image interpretations. Thanks to Anders Moberg who stepped in as co-supervisor at the last minute. Lindsey Higgins created many location maps and the side-view cave

62 map. Field work support was provided by Paul Shaw, Fredrik Ljung, Hanna Sundqvist, Giorgos Maneas, P. (Takis) Karkanas, and Martin Finné, with guest appearances by Karin Holmgren and Putte. Thanks to Håkan Grudd and Laura McGlynn, formerly of the NG dendrolaboratory, for all their tireless contributions of time and effort to the ongoing work on these speleothems using ITRAX and Coo Recorder, which has not made it into this thesis. To the administrative and support staff at the Department of Physical Geography, including but not limited to, Susanna Blåndmann, Carina Henriksson, Maija-Liisa Is- dal, Monika Stolarska, Malin Stenberg de Serves, Maria Damberg, and Sabina Pracic, who have always risen to the occasion when things go awry and kept things running smoothly the rest of the time - we’d all be lost without you! Thanks Sven Karlsson, Johan Skantz, and Bengt Brotén, who have helped set up the speleothem lab space and make all the modifications we’ve asked for (however odd). Big thanks to all my past instructors at NG and IGV, especially those who undertook field courses with me and tried to answer all the questions I peppered them with. NG has been a great place to work, in a large part due to all the other PhD’s (past and present), Post-Docs, and everyone else at NG who have taken the time out to fika and chat, or just to answer my questions. Thanks to all of you who show up to work and make the day better with a generous spirit. The list is far too long to write out, but you know who you are! A special thank you to the tireless PhD council, and those of you who take on the extra effort to organize events for the rest of us to enjoy! To my Bolin Centre for Climate Research RA5 and RA1 leaders, Malin Kylander and Qiong Zhang, and Agatha de Boer and Rodrigo Caballero, thank you for your support which made it possible for me to travel and work with new analytical methods! Malin and Qiong, thank you both for many interesting discussions, your time and assistance, and all your encouragement over the years. Thank you also to everyone involved in setting up the Bolin Linking Program, which enabled me to have the wonderful mentor- ship of Annica Ekman, whose sage advice and good energy were precisely what a half- finished PhD student needed. The Bolin Centre has been a fabulous resource, and I am grateful to have been able to participate. Thank you to all of those who included me in all manner of seminars, lectures, dinners, and events, and thank you to Bolin Centre co- director Alasdair Skelton, whose engagement in outreach work, and inclusive, positive, and forward-thinking spirit inspires many around him. My thanks and appreciation to all of you who have helped me along the way!

And to more personal comments: To the Interdisciplinary Fika Foundation and Tiramisu Fridays groups – In a world gone mad you’ve been the shining beacon of sanity at the little round table. Rollcall! Ali Hind, with exceptional knowledge of quality action movies, JCVD trivia, and Ger- man power metal (preferably pirate or barbarian themed). Natasha Caldwell, with mind- blowing personal tales of celebrity breadings gone horribly wrong tempered with in- tersectional insights. Laura McGlynn, with shuggelty pegs, all the pies, and annually resolved world views. Lindsey Higgins, aka Dr. Batman, bartender, sandwich master, and eyebrow guru and map goddess. Evan James Gowan aka The Wild Party, superpotato, who is teaching us all how to Follow Your Bliss while explaining Japan. James Lea, aka Hot Dog, who always forgets the T in G&T, is a terrible influence whenever the opportunity presents itself, and is a MATLAB wizard too! Ewa Rocha, Alexander Koutsouris, Norris Lam, let there be cake (and drinks)! I’m so glad I met you all! I miss you guys already, thanks for getting me through the last sprint to the finish.

63 To my sisters of the First Church of Suck it Up - Dawn Cederberg, who is still the coolest person I know, my wingman, and partner in Star Wars re-enactments. Natasha Caldwell, the amazon who serves as the inner circle voice of reason and kindness. Wendy Chan, dumplings master, kidney puncher, and gum disease warrior. Monica Marie Davis, geneticist with the home experiment bend and owner of the face I love to make scrunch in disapproval. Thanks for listening, laughing, recharging the batteries, and for all the support when things were not going according to plan. Tequila, cheetos, CAH, Expend- ables, fondue, Magic Mike XXL, thrifting, FTS, laugh till it hurts, fika, hugs, tears, walk it off, fistbumps, Amen. Last but not least, thank you to all my family on both sides of the ocean for your support. To my Mom and Dad, thank you for driving all over North America on summer trips to see geological and geographical wonders, pushing me to try harder, and for always supporting me, and encouraging me to go abroad and see the world. Most of all thank you for my sister and brothers. Drina, who had the little sister who wanted to be everywhere she was (because my big sister is awesome), thanks for always being there! Hugs and high fives to Neal, Christine, Ryan, Sue, Brooke, and Rory in Canada, and to Sven and Elisabeth in Pålsboda, as well as both branches of Clan Ljung. To my mother- in-law, Christina Majlöf, thank you for taking me in to your home and making me feel like family, for all the cozy Sunday dinners, and for raising such a wonderful and kind man for me to marry. And to Fredrik Ljung, my husband. Thank you for literally following me into dark- ness in scary places. For being there, always, without fail, and leading by example. You showed me over 17 years that love really is unconditionally kind, unbreakably strong, unwaveringly honest and loyal, and endlessly supportive, no matter what. I wouldn’t change a single second. I love you.

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73 74 12. Supplementary material

StalAge model GC2 12500

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Supplementary Figure 1. Age model for GC2 stalagmite made using the StalAge (v. 1.0) algorithm, showing error bars of individual 230Th dates and 95% model confidence intervals (Scholz and Hoff- mann, 2011). Ages shown are in years before 2000. Black boxes indicate TIMS-dated and grey boxes indicate MC-ICPMS-dated samples. Ages with large error bars include material from a larger (1cm) sample area.

75 21000

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Years before 1950 before Years 8598 1105 6000

3126 5805 5625 4249 1879 3762 1182 1274 1173 3301 1000 1845 2047 0 20 40 60 80 100 120 140 160 Distance from top in mm

Supplementary Figure 2. Age model for A1 made using the StalAge (v. 1.0) algorithm, showing error bars of individual 230Th dates and 95% model confidence intervals (Scholz and Hoffmann, 2011) with areas of linear adjustments marked by grey shading.

14000

12000

10000

8000 7400

6000 5608 5556 5707

4367 Years before 1950 before Years 4000 3611 3064

2000

0 0 10 20 30 40 50 60 70

Distance from top in mm

Supplementary Figure 3. Age model for A6 made using the StalAge (v. 1.0) algorithm, showing error bars of individual 230Th dates and 95% model confidence intervals (Scholz and Hoffmann, 2011) with areas of linear smoothing adjustments marked by grey shading. Vertical dotted line indicates end of material and hiatus above clean white calcite which was not analyzed for stable isotopes, but used as a dating constraint.

76 Supplementary Table 1. TIMS dates from stalagmite GC2. a) e 9.37 9.27 8.64 8.25 8.86 8.11 8.24 7.95 7.83 7.98 8.33 7.97 ( k re ct ed a g o r b2k C ) 0.46 0.62 0.22 0.10 0.49 0.15 0.16 0.51 0.15 0.29 0.30 0.12 a ± k ( ) e 9.39 9.28 8.65 8.26 8.86 8.12 8.24 7.95 7.84 7.99 8.34 7.98 a k re ct ed a g ( o r C d e t 9.39 9.37 8.66 8.27 8.91 8.12 8.28 7.98 7.84 7.99 8.34 7.99 c ) e e a k a g ( ncor r U 7.4 6.4 4.2 3.6 4.5 2.8 4.1 7.3 2.8 2.8 4.2 2.6 o.) or erg e lb r ab s i d e ( , H e e s c n 73.9 84.6 76.8 79.2 79.7 74.2 80.8 64.4 74.1 78.9 80.8 75.8 r.) ) i e o o r o c / ( k o ( f S d U o emy 0.01 o.) a d 0.038 0.028 0.013 0.045 0.015 0.012 0.041 0.018 0.017 c 0.0069 0.0079 ± A ab s ( ) 0.68 g h erg e id lb 0.813 0.441 0.531 0.847 0.803 0.666 0.555 0.533 0.512 / T 0.4853 0.7149 g 23 0 ( p e H h t a t 0.12 o.) 0.077 0.035 0.026 0.031 0.015 0.053 e d or 0.0031 0.0084 0.0011 r ab s r m e ( . erf o a d e p .d. .d. i d ) n n h u g es 0.19 T / 1.064 0.232 0.081 0.202 1.043 0.118 ri n 0.7267 0.4671 0.0884 23 2 a g n g T

hn i q ( e , T h e c 23 0

S t Ca v M o.) I or 0.0011 0.0006 0.0011 0.0012 0.0013 0.0011 0.0011 T are e 0.00079 0.00078 0.00091 0.00085 0.00079 r ab s e ( Gas p s an d si ti on s an d R1 ) g U mp o / , D o 0.5603 0.5546 0.6113 0.6367 0.5263 0.5425 e GC2, 23 8 µ g r y 0.30213 0.39439 0.39055 0.45603 0.42743 0.39342 c i t

o ( i c p si t o t 50 mg sampl e 15 82 40 alag m ) 267 222 210 183 170 210 107 140 140 2 is o R ep o 30 -

s, s t m 190 - 100 - 100 - ri u m dft (m Data o e su l t h l e r 00 mg an d 4 si s 5184 5185 5208 5041 5051 4946 5039 5052 4930 5040 4947 Ta b ple s ple s y ID a nd t 4930w e al m sa m sa m g g u e t ana l amp l d S alysis o n alysis y ran i n o 250 m Ages given in thousand years before 2000. given in thousand years before Ages 400 m A TIM S B U

77 Supplementary Table 2. TIMS dates from stalagmite GC2.

d t e 2k c a) b e ( k a g C orr e 8.40 8.31 8.31 11.71 11.91 8.40 10.97 10.74 9.19 8.94 9.88 11.67 15.16 ± 05 05 04 10 11 08 11 11 08 08 06 08 42 0 . 0 . 0 . 0 . 0 . 0 . 0 . 0 . 0 . 0 . 0 . 0 . 0 .

d t e c e a) a g ( k 72 92 98 75 68 17 C orr e 41 32 33 41 21 95 89 8 . 8 . 8 . 11 . 11 . 8 . 10 . 10 . 9 . 8 . 9 . 11 . 15 . s ± t u i 0.0019 0.0018 0.0016 0.002 0.0021 0.0021 0.0021 0.002 0.0022 0.0019 0.0018 0.0018 0.0017 de t r e ) t h U atio i n 23 8 ai n / ty r h i U ti v 23 4 ay c ( c a c e . 1.0713 1.0776 1.0768 1.0715 1.068 1.0735 1.0722 1.0707 1.077 1.0767 1.0717 1.0728 1.0826 U d ag e e 23 8 n f i t h ± a i s T Sp

, r iu m o 0.0004 0.0004 0.0004 0.0008 0.0008 0.0007 0.001 0.001 0.0007 0.0007 0.0005 0.0006 0.0007 r e e ) o s h g U qu ili b r atio ), w 23 8 T . / ar e Bu ty r l U i u T h 234 ) 23 8 ti v

r 23 0 EH , se c o ( a c 230 - l 0.0799 0.0794 0.0793 g 0.1096 0.1115 0.0798 0.1031 0.1009 0.0874 0.0849 0.093 0.1091 0.1478 ti ( l f o - . 1 N I - r d mi n y ra a y C E u 0 1 - e ± 1 d vi t - ] ( t i ) ti a c 0.9 1.4 1.9 1.7 1 3.4 2.2 2.1 3.6 6.4 5.2 4.2 0.1 10 23 4 nd as s ] a ] Tri n - l h T , T h 23 0 me d atio l s 23 2 0.4 a v e / ( / 23 2 e o r h / ty r f g 23 0 8 ± T i 1.55125 x r C a a [l T h e 23 0 ti v f 0 . h [ 23 0 ee p o [ T a c d r o 130.6 217.3 301.6 167.5 86.8 263 175.2 187.6 301.5 536.7 585.9 497.9 14.4 U, an d a ti r e /1000 ) 230 u 23 4 ed qu e r r s p i u a s y ra s a a n f o nd ± vi t 1 G - me a m e ti r c h , e U s y e 6 a c - 0.007 0.003 0.003 0.008 0.012 0.004 0.008 0.007 0.005 0.002 0.003 0.002 0.214 23 4 h C 2 y t h d o n T S t ( 10 G b ti d + 23 2 i / T ) te U g h i o s at e 23 0 / T l CP M c - i p 23 8 g I m

d 2.826 x 23 2 , g ( n n m C - h ta l i a i T s 1 - e l t r i M c o a = 1.002 0.525 0.432 0.704 1.008 0.299 0.59 0.562 0.352 0.145 0.265 0.213 26.262 e 23 0 n y

t c r i o s t v i nd , a d p f o a ti ac ti g 1 ± . a ] - n n r U t o s a n 1.6 1.3 1.4 1.7 1.3 1.6 1.8 1.9 2.1 1.4 3.2 1.4 6.8 y 6 e - 23 8 us i l s o tam i s ul t / ) d i n p

h e g 10 o T U / at e m c m g l s r 23 0 h 23 8 u [ T ( n i s a s i

n 535.5 470.4 537.1 351.9 256.9 322.1 327.7 341.9 397.2 299.7 547 318 838 y alc u 23 0 g l

o o r c 2s of the m e a d 9.1577 x 0 e e ta l r e t h n i e a s t r 1 5 ar e s a r e

w b r S a s t s nd n o n dft (mm) 169 173 180 366 341 194 323 311 258 223 277 352 370 f d a o

o n o M rr ta n o

ti s e a ti e s c l m n ID e r s i o u e i r re CP- 1 2 3 5 6 7 8 9 10 11 y tic a l I AB1 AB2 AB3 l alc u o - - - y L - L - L - L - L - L - L - L - L - L - a c c ay c de g 2 C - a l c e e e n 2 U 2 U 2 U C 2 C 2 C 2 C 2 C C 2 C 2 C 2 C 2 C 2 a mp l n g g h S Uran A M G G G G G G G G G G G G G T A A D e Ages given in thousand years before 2000. before given in thousand years Ages A

78 Supplementary Table 3. MC-ICP-MS dates from Alepotrypa Cave (CENIEH) ± 0.36 0.23 0.48 0.24 0.45 1.39 1.67 0.10 0.06 age (ka) Corrected results 4.21 4.31 4.17 1.04 5.74 18.59 1.11 3.52 4.51 ± 0.0017 0.0017 0.0018 0.0020 0.0021 0.0024 0.0023 0.0021 0.0021 U) 238 U/ 234 ( activity ratio activity 1.1094 1.1080 1.1495 1.1085 1.0994 1.0859 1.1295 1.1141 1.1098 ± U decay chain in detritus the chain decay U 0.00047 0.00057 0.00038 0.00031 0.00078 0.00151 0.00098 0.00046 0.00055 238 is the age. is the U) 238 Th/ 230 ), where T where ), ( activity ratio activity Measured ratios Measured 0.04954 0.04790 0.05330 0.01591 0.06533 0.19389 0.04521 0.03769 0.04591 U. ± 238 -(l230 - l234) T 0.05 0.11 0.03 0.05 0.07 0.04 0.02 0.21 1.46 for -1 a )](1 - e Th] -10 234 232 - l Th] activity ratio ratio activity Th] Th ages Th/ 230 232 230 /(l 230 [ activity ratio activity 5.45 8.58 4.28 2.66 5.92 5.67 1.08 16.86 106.97 Th/ 230 230 ± /1000)[l U, and 1.55125 x 10 x 1.55125 and U, 0.011 0.007 0.022 0.005 0.007 0.024 0.017 0.004 0.001 234 measured for -1 U a Th 234 -6 Th activity ratio of 0.8 ± 0.4 and assuming secular equilibrium of of equilibrium secular assuming and 0.4 ± 0.8 of ratio activity Th 232 (ng/g) 232 + (d 3.098 1.752 6.040 1.770 2.130 7.192 5.832 0.570 0.137 U/ -l230 T 238 Th, 2.826 x 10 x 2.826 Th, ± = 1 - e 230 activity 0.44 0.40 0.56 0.29 0.19 0.22 0.13 0.25 0.32 for -1 U] a -6 238 U Th/ 238 230 (ng/g) Th contamination is indicated by the measured [ by measured the is indicated contamination Th 230 111.51 102.67 158.77 96.63 63.18 68.84 45.52 83.37 104.25 dft mm crust crust crust 3 117 154 4 130 250 Sample ID Uranium thorium and isotopic compositions and MC-ICP- MS analysis results of calcite crust on bone and speleothems, Alepotrypa Cave, Greece Spain Burgos, CENIEH, at performed technique MC-ICPMS by samples mg 200 on Analysis Z595 #1 Z595 Z595 #2 Z595 D968 #1 D968 A1-T A1-M A1-B Age calculation based on [ on based Age calculation 10 x 9.1577 are constants Decay detrital of degree The detrital using a calculated were Age corrections level. 95% confidence at are uncertainties Analytical 1950 before given years in are Ages thousand A2-T A2-M A2-B

79 Supplementary Table 4. MC-ICP-MS dates from Alepotrypa Cave (Max Planck) 0.22 ± 0.07 0.14 0.04 0.03 0.05 0.06 0.06 0.05 0.04 0.15 0.17 0.09 0.09 0.08 0.17 6.86 0.19 1.03 0.65 0.23 Corrected results (ka) age 1.71 1.21 1.81 3.08 1.11 3.63 1.78 1.12 4.38 1.98 5.62 3.06 5.57 3.24 5.72 3.70 7.42 4.18 9.75 5.56 8.53 ± 0.0017 0.0026 0.0019 0.0016 0.0018 0.0016 0.0020 0.0019 0.0017 0.0020 0.0021 0.0022 0.0018 0.0020 0.0026 0.0020 0.0021 0.0024 0.0021 0.0025 0.0035 U) 238 U/ 234 activity ratio activity 1.1094 ( 1.1095 1.1063 1.1043 1.1102 1.0989 1.1036 1.1113 1.0950 1.0919 1.1073 1.1007 1.1011 1.0902 1.0900 1.1008 1.0890 1.1047 1.1005 1.1008 1.0955 ± 0.00025 0.00038 0.00036 0.00031 0.00021 0.00044 0.00024 0.00041 0.00046 0.00052 0.00027 0.00056 0.00064 0.00064 0.00060 0.00085 0.00123 0.00056 0.00132 0.00081 0.00138 U) 238 Th/ 230 activity ratio activity Measured ratios Measured ( 0.02233 0.01396 0.01921 0.03409 0.01222 0.03671 0.01955 0.01296 0.04408 0.05804 0.02122 0.03426 0.03402 0.05596 0.05732 0.04024 0.18642 0.04568 0.11335 0.06750 0.08615 ± 0.30 0.92 0.08 0.54 2.33 0.20 0.34 1.10 0.19 0.34 0.13 0.41 0.45 0.52 0.22 0.01 0.13 0.05 0.05 0.37 0.04 Th] 232 Th ages Th/ 230 230 activity ratio activity [ 10.16 46.59 9.71 27.01 167.02 14.65 10.39 96.07 25.65 17.06 8.37 21.79 39.35 42.82 10.57 1.22 10.07 4.45 4.20 20.48 3.99 ± 0.002 0.001 0.010 0.001 0.001 0.004 0.003 0.002 0.003 0.012 0.008 0.002 0.003 0.003 0.008 0.246 0.009 0.021 0.015 0.004 0.012 Th (ng/g) 0.262 0.217 2.439 0.163 0.103 0.682 0.407 0.217 0.380 1.357 1.112 0.344 0.558 0.470 0.776 55.331 1.277 5.030 3.693 0.545 3.405 232 ± 0.21 0.54 0.92 0.39 0.57 0.52 0.33 0.66 0.48 0.55 0.36 0.43 0.31 0.48 0.28 0.54 0.37 0.26 0.28 0.21 0.76 U 62.35 172.22 (ng/g) 227.31 117.86 153.37 167.12 106.85 154.98 150.21 130.45 88.89 128.45 72.03 114.94 66.67 118.26 92.06 64.63 75.21 42.38 198.94 238 13 20 10 dft mm 5 21 25 8 34 45 37 68 43 74 52 89 58 102 65 112 124 2 Uranium thorium and isotopic compositions and MC-ICP- MS analysis results, speleothems, Alepotrypa Cave, Greece technique MC-ICPMS by samples mg 100 and 150, on 200, Analysis Germany. Leipzig, Anthropology, Evolutionary for Institute Planck Max at performed A1-13 A6-2 Sample ID A1-8 A6-3 A1-11 A1-4 A6-4 A1-19 A1-14* A6-5 A1-5 A6-6 A1-9 A6-7 A1-1 A6-8 A1-3 A6-9 A1-21 Ages are given in thousand years before 1950 A1-22 A6-1

80 Supplementary Table 4, continued. s 9 9 6 4 t 6 0 0 9 . . . . u l ± ± 0 0 0 0 s e r d e t c ) 0 4 7 7 a 0 6 5 9 o rr e . . . . ge k ( a C 0 2 4 1 002 3 002 2 002 1 001 9 . . . . ± 0 0 0 0 s u o t ti ) a U r

de tr i y 23 8 t i / he t v U

ti n 160 7 157 8 161 5 110 3 i . . . . c

23 4 a ( 1 1 1 1 n i a h c

. e t . a de ca y e

g 0003 2 0003 4 0003 8 0003 5 U a . . . . ± 0 0 0 0 23 8 ccu r os he t a

ti of t

s a i o

o ) r m ti T u U

n d i a r e r e h

23 8 y u r t he r i s h/ v w a T , ti equ ili b 0144 5 0301 6 0491 1 0390 1 )

. . . . c r 23 0 T ( a M e 0 0 0 0 a l nd 232 T . u l 234 ) c

a U - e s o

2 6 3 1 23 8

230 l g ti 0 1 4 0 ( . . . . - a r e ± 0 0 0 0 fo r

- 238 U 1 y mi n

- r 1 a o

( o 0 ] h] ss u ti ) 1 f - a T a s 0 r ac tivi t 23 4

l 1 23 2

] nd y - x

h a t lu e

i T h/ 4 2 a 4 v 23 0 . T 0 0 7 5 l 23 2 0 ( ti v 8 6

/ / . . c n 23 0 ± h

[ a 0 13 . 46 . 1 55125 o T 23 0 . 8 l . 1 [ ti 0 23 0 a r nd of t a o n , ed [ 1000 ) r ti / U 03 1 01 1 00 4 04 4 d u a . . . . e r s r

± 0 0 0 0 23 4 nc e a u

y e o a s e fo r m m

, c , 1 - U d a he ac tivi t

e t 6

23 4 - s h y d g) 0 T ( h b

81 5 1

T + 18 1 40 6 60 5 23 2

x . . . ss u / ed T . 7 / (ng 1 0 10 . 23 2 l a U e l 23 0 ca t v 826 - 23 8 . m

e e l l 2

d - a nd i ,

i 195 0 e t e

h 1 s

e i T

= m r

y o 23 0 5 6 8 6 c den de tr i

i t o n f

5 8 7 5 ﬁ ti a ti v . . . .

a for b e a c 0 ± 0 0 0 g

o n ] 1 s n - c i

U r a s

d. A ss u mi n a 6 u a - 23 8 e e t / r 0 95 % h

1 ed u

t o n T 5 9 t 3 9 s x c a a

3 8 4 9 g) nd y l a 23 0 e h a u [ e r U

T c a

u s s 1577 130 . 23 0 / (ng 198 . 188 . 149 . o n m 23 8 .

ca l e

t l 9 h o

a e ti o t t ed r e n s i r e n a mm a i

w b

rt a ss n n s t 8 de tr i e a e n 2 d ft 6 3 3 o n v o n a of i ti t ti m un c s g a D

l I ee

e u r o n r c e ca l pl e c

a ti o rr e

y m c ca l s de g 1 2 3 l

- - - a e ca y a mp l e e g 7- T S e g g n H H H a he * E S A E E A A A D T A

81 Supplementary Table 5. Dates and values of cave conditions measured at Alepotrypa Cave.

–

δD vs VSMOW (‰) δ O vs VSMOW (‰)

δ C ‰ VPDB δ O ‰ VPDB