Muséum national d’Histoire naturelle

Master Erasmus Mundus en Quaternaire et Préhistoire

Contextualizing faunal dispersals and early cave hominid bearing occupations in SE Asia during MIS5: chronologic and palaeoclimatic approaches on speleothems and fossil tooth

Hua TU

Tuteur/s :

Christophe Falguères François Sémah

Année académique 2011/2012

Content

1. Introduction .......................................................................... 1

1.1. Early modern human dispersal to Southeast Asia...........................................1

1.2. Human and fauna migration and landscape change........................................4

2. Background of the region and the sites............................... 6

2.1 Gunung Sewu region in Java ...........................................................................6

2.2 The site of Gunung Dawung ............................................................................7

2.2.1 Introduction of the Punung sites ...........................................................7

2.2.2 Stratigraphy and previous chronological studies ................................11

2.2.3 Samples from Gunung Dawung..........................................................12

2.3 The site of Song Terus ...................................................................................13

2.3.1 Introduction of Song Terus .................................................................13

2.3.2 Stratigraphy and previous chronological studies ................................15

2.3.3 Occupation floors in Upper Terus layer..............................................18

2.3.4 Samples from Upper Terus layer ........................................................22

3. Dating methods and experiments ...................................... 25

3.1 A review of Quaternary dating methods ........................................................25

3.2 U-series disequilibrium (230Th/234U) dating...................................................27

3.2.1 Principle of 230Th/234U dating .............................................................27

3.2.2 Assumptions and reliability.................................................................30

3.2.3 Different measuring techniques ..........................................................32

3.2.4 Procedure for conventional alpha spectrometry .................................33

3.2.5 Procedure for MC-ICPMS ..................................................................39

3.3 Combined ESR/ U-series dating on tooth......................................................40

3.3.1 Introduction of ESR dating .................................................................40

3.3.1.1 Basic principle of ESR.............................................................40

3.3.1.2 Paleodose determination ..........................................................42

3.3.1.3 Annual dose assessment...........................................................43

3.3.1.4 The challenge of ESR dating of fossil teeth.............................44

3.3.2 Combined ESR/U-series dating of fossil tooth...................................45

3.3.2.1 Principle of combined ESR/U-series dating of fossil tooth .....45

3.3.2.2 Procedure for combined ESR/U-series analysis ......................47

3.3.2.3 US-ESR age calculation...........................................................49

4. Climatic reconstruction by stalamite δ18O record ........... 50

4.1 Introduction and theory of stalamite δ18O record ..........................................50

4.2 Modern climatic pattern of Indonesia ............................................................53

4.3 Material and Method of stalagmite δ18O analysis..........................................54

5. Results and discussion ........................................................ 56

5.1 The age of Gunung Dawung ..........................................................................56

5.1.1 U-series age of Gunung Dawung........................................................56

5.1.2 Combined ESR/U-series age of Gunung Dawung..............................57

5.1.2.1 Equivalent doses, DE................................................................57

5.1.2.2 U-Th data .................................................................................58

5.1.2.3 Annual dose rate.......................................................................58

5.1.2.4 Combined ESR/U-series age....................................................60

5.1.2.5 The age of Punung fauna and its implication...........................63

5.2 U-series age of occupation floors in upper Terus layer of Song Terus ..........64

5.3 Interpretation of δ18O record from Song Terus ..............................................67

6. Conclusion ........................................................................... 74

Reference ................................................................................. 76

Acknowledgment

I would like to thank Christophe Falguères who provided the guidance in dating

and the access to the geochronological and geochemical laboratories in Gif sur Yvette.

And my deepest gratitude also goes to François Sémah, who designed the subject of my

master thesis, and gave unceasing direction to the whole process of thesis writing.

The achievement of experiments is a result of teamwork. Dr. Qingfeng Shao has

contributed a lot in sampling on the stalagmites and in the analysis the MC-ICPMS

samples. Norbert Frank and Eric Douville provided the assess to MC-ICPMS analysis

in Laboratoire des Sciences du Climat et de l’Environnement (LSCE), Dominique

Genty and Dominique Blamart analyzed the stable isotope in LSCE. Simon Puaud

performed the XRD analyses on the stalagmites. Mailyse Richard helped in

pretreatment and gamma spectrometric analysis of the dental sample. I would like to

thank all of the people above for their help.

I wish to thank Jean-Jacques Bahain for his patience in correcting the draft of this

thesis and those valuable discussions with him. I am grateful for Xavier Gallet,

Mohammed Ruly Fauzi and Sofwan Noerowidi for their patient explanations of the

sites. I am sincerely indebted to my friend Kat Manalo who corrected part of the thesis

draft.

I also want to thank Shafika Falguères, David Pleurdeau, Pierre Voinchet for their

help during my master in Paris. And thanks are due to Erasmus Mundus Master

Program for providing two years of financial support.

I want to give my special gratitude to Prof. Shen Guanjun for his guidance during

these years.

Abstract

Song Terus and Gunung Dawung caves are two key sites for the understanding of

the human settlement in SE Asia during last interglacial stage (MIS 5).

In this study, a tooth and some surrounding calcite crystals from a fissure of

Dawung rockshelter were dated by combined ESR/U-series dating and alpha

spectrometric U-series dating methods respectively. The combined ESR/U-series age

of the tooth enamel (162 ± 17 ka) is considered to be overestimated because of the poor

estimation of sediment gamma dose rate. On the other hand, the minimum age provided

by the U-series age of the calcite (~126ka) coincides with the previously published

luminescence age, and indicates that the immigration of Punung fauna in Java should

be just before the Last Interglacial optimum.

In addition, two stalagmites of Song Terus cave (ST06 and ST05) were collected

from two human occupation floors in the upper Terus layer and dated by MC-ICPMS

and alpha spectrometric U-series dating methods. Based on the statistic consistency of

the 15 U-series data, the crystallization of these stalagmites is dated back to 91 ~ 84 ka

(ST06) and 91 ~ 82 ka (ST05) respectively. δ18O records determined on the same

stalagmites were compared with the Chinese-cave based records in millennium scales.

ST06 record is perfectly coherent with the BD22 one, at around 89.5~ 87 ka and

corresponding to the GIS 22 warm period; ST05 record likely corresponds to the

beginning of following GS 22 cold period, about 86.5~ 85.5 ka. The chronology

coincidence verifies and restricts the ages yielded from U-series data, and suggests that

humid condition still continued in Java during the MIS5b stadial. The stalagmite

growth and human occupation in Song Terus Cave happened from the GIS 22 warm

period to the following GS 22 cold period, but with a short time interval at the cooling

transition from GIS22 to GS 22.

Résumé Song Terus et Gunung Dawung sont deux sites-clé dans l’étude du peuplement de

l’Asie du Sud-Est durant le stade isotopique 5. Dans ce mémoire, une dent et des spéléothèmes provenant d’une fissure de l’Abri Dawung ont été daté par les méthodes combinées ESR et U-Th et U-Th par spectrométrie alpha respectivement. L’âge ESR/U-Th de la dent semble avoir été surestimé, dû à une dose gamma annuelle faible. Cependant, L’âge minimum proposé par la calcite (~126ka) est en accord avec l’âge obtenu par OSL/TL et indique que la faune Punung serait arrivée avant le dernier maximum interglaciaire .

Deux stalagmites prélevées dans des niveaux d’occupation humaine dans les niveaux Terus de la grotte de Song Terus ont été datées par U-Th (ICP-MS et spectrométrie alpha). A partir des données obtenues, ces stalagmites ont été datés de 91~ 84 ka (ST06) et 91 ~ 82 ka (ST05).

Les données δ18O obtenues sur ces deux stalagmites ont été comparées avec celles provenant de grottes chinoises, à l’échelle du millénaire. ST06 est cohérente avec les données BD22 vers 89,5~ 87 ka, correspondant à la période chaude du GIS 22. ST05 correspondrait au début de la période froide du GS 22 (86,5~ 85,5 ka). Ces données suggèrent que durant le stade 5b, le climat était toujours humide à Java. Le développement de la stalagmite, ainsi que l’occupation humaine de Song Terus se seraient déroulés à partir de la période chaude du GIS 22 jusqu’à la période froide suivante du GS 22, mais de façon brève à la transition GIS 22-GS 22.

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1. Introduction

1.1. Early modern human dispersal to Southeast Asia

Java Island has long history of Homo occupation since early Pleistocene, but the

timing of Homo sapiens emergence is still ambiguous because of the insufficiency of

discoveries and studies in and out of this region. However, we understand the true story

of Human origins better and better as the more and more discoveries of human

occupation, especially those oldest ones.

Modern Homo sapiens is believed to have emerged in East Africa as early as

195~165 ka BP evidenced by the sites of Omo-kibish and Herto (White et al., 2003;

McDougall et al., 2005). Their earliest traces out of Africa were documented at Skhul

and Qafzeh in Levant during ~120-90 ka BP. (Stringer et al., 1989; Grun and Stringer,

1991), indicating a northern route from Levant to Eurasia. But some other evidences

imply a southern route which across the mouth of Red Sea, as artefacts dated to Last

Interglacial were found in an emerged reef terrace on the Red Sea coast (125 ka by

U-series dating, Walter et al., 2000), and at Jebel Faya in east Arabia (127 to 95 ka by

OSL, Petraglia et al., 2010; Armitage et al., 2011). Although, the route of modern

human’s first step out of Africa is still in debate (Petraglia et al., 2010; Oppenheimer,

2012), but the time of that is sure to be no later than Last Interglacial. After that, modern

human records were disappeared and probably replaced by Neanderthals in West

Eurasia, until their reappearance at ~50 ka, which was considered to be another exit

from Africa, and gave the spread from there to Western Europe (Bar-Yosef, 2007; Shea,

2008).

The tropical coastline of circum-Indian Ocean should have played an important

role in human dispersal, but few significantly old fossils of Homo sapiens were

recorded in Indian subcontinent. Only some cultural remains related to this species,

have presented in southern India as early as the Younger Toba Eruption (YTE) at ~74 ka.

For instance, some technically continuing lithics were found below and upon the

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Younger Toba Tuff in Jwalapuram (Petraglia et al. 2007).

The situation is similar in mainland Southeast Asia, which few Homo sapiens

fossils were found earlier than YTE. Majority sites were dated to late upper Pleistocene

and Holocene. With some Exceptions such as, two lithic assemblages from Kota

Tampan in Lenggong Valley On Malay peninsula, which are dated to the YTE event

and 70 ka BP (by OSL) respectively (reviewed in Oppenheimer, 2003; Hamid, 2008;).

At the end of one dispersal arc, the evidence of modern human arrival in Australia

was latter than those in South Asia and mainland Southeast Asia. Timing of human

dispersal to Sahul Shelf has been restrained to at least 48 ka BP., probably 50-60 ka BP.,

according to a series of sites in front of and inside Australia, such as, Jerimalai in East

Timor (>42 cal. ka BP.; O’connor, 2007); Nauwalabila and Malakunanja sites in

Northern Territory (50-60 ka BP. by Luminescence and Radiocarbon dating; Roberts et

al., 1990; Bird et al., 2002); Devil’s Lair cave in the extreme southwest of Western

Australia (48 ka BP. by OSL and ESR; Turney et al., 2001); Lake Mungo in western

New South Wales (62 – 76 ka BP. by multi-dating methods; Thorne et al., 1999).

Based on these records, some researchers suggested a just-pre-YTE southern exit

of modern human from Africa, and with rapid migration round the Indian Ocean coast

to Australia (Oppenheimer, et al. 2009; 2012). This is also supported by majority of the

records in insular Southeast Asia, which were dated from OIS-4/3 (67-40 ka), such as,

Tabon Cave, Palawan in the Philippines (~16.5-47 ka by directly U-series dating on

human fossils; Detroit et al. 2004); Niah, Borneo in Malaysia (ca. 46 ka to ca. 34 ka by

14C dating; Barker et al. 2007); and also Callao Cave, Luzon in the Philippines which

yielded a metatarsal provisionally attributed to a small-bodied H. sapiens (~67 ka by

U-series dating on bones; Mijares et al., 2010).

Contrarily, some modern human remains in southern China and Java have been

found almost contemporary to those in Levant during Eemian interglacial. Shen et al.

(2002) applied stratigraphic studies and U-series dating on the discovery site of the

Liujiang Man site in Southern China, and gave three possibilities for the age of the

AHM skull. > 68 ka, the minimum estimation, ~111-139 ka with strongly

recommendation and >153 ka with lower probability. The conservative date of 68 ka

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has been widely accepted, but the others were cautiously treated because of not only the

uncertain provenance of the skull, but also the rareness of parallel regional support.

This has been changed since some modern human fossils were found in Zhiren Cave in

the neighboring province, the age of these well-located fossils should be >100 ka,

constrained by U-series ages of some flowstone layers (Liu et al. 2010). Considering

this new and more substantial date, the age of ~111-139 ka for Liujiang Man seems

more acceptable, although still controversial (Oppenheimer, 2012).

In eastern Java, a well described faunal association, designated as Punung fauna,

was dated back to the equivalent period. Three sites in Punung area were found bearing

Punung faunal assemblage. Two of them (Punung I and II) have yielded six human

teeth, and the only extant one was sorted to Homo sapiens (Storm et al., 2005). The

third site (Gunung Dawung) was dated to 128 to 118 ka, by U-series and luminescence

(Westaway et al., 2007). This age coincides with its paleontological interpreting as an

immigrant indicating a presence of a tropical rainforest (Badoux, 1959; De Vos, 1983;

Storm et al. 2005; Storm and de Vos, 2006).

Recent excavations in the same region yielded archaeological remains dating back

to 300 ka in the Song Terus cave. The anthropic remains (artifacts, human modified

bones and burnt stones) show evidence of human occupation floors in upper Terus layer,

reflecting ever-wet conditions, marked by the development of mushroom stalagmites

on the cave floors (Fauzi, 2008; Sémah et al. 2004; Ansyori, 2010). Preliminary dating

has attributed these layers to MIS5 (120 and 85 ka, Sémah et al, 2007), probably the

earliest cave occupation in SE Asia. The paleontological analyses to the animal remains

in these layers have revealed the close resemblance of Terus assemblage with the

Punung fauna (Ansyori, 2010).

Both of the sites are suggesting an MIS 5 appearance of modern human in SE Asia,

which is contemporary to those in Middle East and Southern China, and showing a

novel scenario for modern human origin. It is indispensably to restrict the age of these

human remains, in order to not only know the exact time of their emerging but also

understand their behavior during the dramatic environmental change period of MIS 5.

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1.2. Human and fauna migration and landscape change

The island of Java is considered to be have a rich fossil biodiversity. Its

mammalian biostratigraphy is divided into seven faunal stages identified on the basis of

changes in faunal content at “type” sites, stratigraphic relations and numerical age

estimates. These stages comprise Satir, Ci Saat, Trinil, Kedungbrubus, Ngandong,

Punung, and Wajak faunas, arranged from oldest to youngest (Theunissen et al., 1990;

Van den Bergh et al., 2001).

The Punung breccias contain no extinct mammals but record the first appearance

on Java of a fully modern faunal suite. The presence of some species like Pongo and

Hylobates (gibbon and siamang), indicates a tropical rainforest at that time (Badoux,

1959; Storm et al. 2005; Storm and de Vos, 2006; Westaway, 2007).

The first numeric age of Punung fauna is situated in a period of frequent climate

oscillations and landscape changes, which in turn consequently raise an apparent

contradiction between “(i) the ever-wet conditions which resulted into the development

of the rain forest, a favourable habitat for these animals and (ii) the obviously ‘isolated’

conditions of Java at the time (periods such as MIS 5.e underwent high sea-level which

reinforced the isolated conditions), which prevented these mammals from crossing the

sea straits.” (Sémah and Sémah, 2012)

Migrations require both a land bridge and suitable habitat across that land bridge.

The landscape changes mainly depend on the climatic cycles (glacial/ interglacial;

stadial/ interstadial), appearing as repetitive expansion and fragmentation of the

rainforest, also as emerging and disappearance of land bridges caused by sea level

eustatic changes. In coarse scales, the changes in temperature, vegetation and sea level

are generally synchronous, during majority phase of the glacial, the land bridge was

open, but the rainforest has fragmented and reduced, restricting to locally humid

patches among an open landscape. While during the main phase of interglacial, the

ever-wet condition is optima for rainforest development, but the land bridge has been

submerged. Both of them were impossible for a migration of rainforest species into

Java.

5

These periods are assimilated to “red light” according to the “traffic light model”

which allowed for dispersals to occur during the time lag (green light) between climatic

change and its effects (vegetation and geography) allowing dispersal in a certain

direction during this short time lag (Vrba, 1995; Van der Made, 2011).

In more precise scales, all the changes are progressive processes, which leave

some temporal window for the migration of animals between the continents/ islands. In

the case of Java island in the MIS 6/5 transition, a “green light” probably could have

existed if some rainforests had developed before the land bridges have been submerged

completely. The corridor should have open also during the slight cold even sub stages

included into MIS 5, during which the land bridge has emerged again, and the

vegetation hasn’t been destroyed severely (Lambeck et al., 2002, Sémah and Sémah,

2012).

The previous age of Punung fauna (128~118 ka) give a ambiguous background for

the faunal migration, since it is greatly overlaps the duration of full Last Interglacial

which was estimated to be from 128 ka to 121 ka (Stirling et al., 1998) or from 129 ka to

122 ka (Zhao et al., 2001) in Australia. Hindered by the high sea level in this optima

period, the only possible opportunities for the Punung Faunal to enter Java is just before

or just after this period, meaning early MIS5e or MIS5d, and this is what we need to

confirm in this study.

U-series dating (MC-ICP-MS and Alpha Spectrometry) and combined

ESR/U-series dating are chose to verify the occasion of the immigration of Punung

fauna (plausibly with humans) into Java, and to yielded the precise age of cave

occupation in Song Terus which seems to be the earliest cave occupation in Southeast

Asia. Furthermore, a tentative analysis of stable isotopic composition (δ18O) is

performed on two stalagmites from Song Terus, trying to gather more climatic

information about the period of human occupation in this site.

The background of the sites and dating materials are introduced in Chapter 2,

followed by the introduction of dating methods in Chapter 3. The theory and procedure

of stable isotopic analysis are explained briefly in Chapter 4. All the results are

presented and discussed at Chapter 5, and concluded at Chapter 6.

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2. Background of the region and the sites

2.1 Gunung Sewu region in Java

Gunung Sewu (thousand mountains in Javanese) is a karstic region in east Java,

about 80 km west to east and 30 km from north to south. It stretches from the Kali Oyo

River south of Yogyakarta to the Pacitan area, and facing the Indian Ocean at the south

(Fig. 2.1). In this region, there are possibly 40,000 limestone conical hills, whose

heights range from 80 m to 500 m above the sea level. Almost each of the hills contains

karstic cavities, and a great many of which were used as shelters during prehistoric

times (Gallet, 2004; Sémah et al., 2004).

Fig. 2.1 Up: the locations of Gunung Sewu in Java (Westaway et al., 2007); Down:

the Gunung Sewu region (after Budiman, 2008).

The Gunung Sewu region consists of mainly shallow marine Miocene

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sedimentation, documented by reef limestones, stratified limestones and clastic

deposits. The evolution of the landscape in the area has been driven by successive

episodes of coral limestone volcano-tectonic uplift (Lehmann, 1936, Sémah et al.,

2004). After the last main uplift, the Miocene limestones underwent deep karstification,

which was estimated to middle Pleistocene (Lehmann, 1936; Djubiantono et al., 1992).

This estimation was confirmed by the U-series ages of some speleothems found in this

region, for instance, ~245 ka from Braholo Cave, ~326 ka from Guwo Tabuhan and

~443 ka from Gunung Dawung ( Sémah et al. 2004; Westaway et al., 2007).

The Punung area, located at the east of Gunung Sewu, has long been an attractive

region for the archaeologists, because of it richness in Neolithic and earlier finds. This

study focuses on two sites within this area, Song Terus and Gunung Dawung.

2.2 The site of Gunung Dawung

2.2.1 Introduction of the Punung sites

Punung sites

The Punung fauna was found in three typical cave breccias in the limestones of

Gunung Sewu. Punung I and Punung II were first reported when von Koenigswald and

Tweedie were surveying the region of Pacitan and Punung in 1930s. von Koengiswald

excavated Punung I site in 1936, and collected fossils from Punung II in 1938, but

failed to record the original localities of the sites. These collections were then mixed

together without recording their provenances (Badoux, 1959; Storm et al. 2005).

In 2003, the original localities have been relocated by a joint Indonesian-Dutch

team. Punung I was found near the site of Song Agung (S 08°08′30.3″, E 111° 01′

58.3″), and Punung II was located at the entrance to Tabuhan Cave (S 08° 07′ 33.2″, E

110° 58′ 58.5″), which has since been largely obscured by construction of a walkway.

Momentously, a similar fossiliferous breccia, Punung III, was found near Tabuhan

Cave at Gunung Dawung (S 08° 07′ 33.5″, E 110° 59′ 15.1″) (Fig. 2.2; Storm et al.,

2005; Storm and de Vos, 2006; de Vos, 2007).

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The similarity and simultaneity of the Punung sites were concluded from different

points: 1) they are remnants of former caves; 2) the sedimentary properties of these

breccia deposits are well weathered and composed predominantly of moderately sorted,

unconsolidated, angular limestone and calcite clasts, with a 20% sandy-silt matrix; 3)

the consistency of faunal species represented in all three Punung breccias (see Table

2.1). Thus the faunal remains from the three breccias were considered to be broadly

contemporaneous and representative of a single entity (von Koenigswald, 1934, 1935;

Badoux, 1959; Storm, 2001, Westaway et al., 2007). Since there is no direct

stratigraphic association between the breccia and datable deposits in Punung I, and

Punung II has been largely obscured by construction of a walkway, Gunung Dawung is

the only site offers potential to date the typical Punung assemblage (Westaway et al.,

2007).

Fig. 2.2 Left: Locations of Punung III (Gunung Dawung), Gua Tabuhan and Song

Terus in Punung area. Right: An enlarged illustration of Gunung Dawung. (Westaway

et al., 2007)

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Table 2.1 List of Punung Fauna (Westaway et al. 2007)

1 Recovered from Punung I and II by von Koenigswald (1934, 1935). Names revised from Badoux (1959)

by de Vos (1983, 1985) or Storm et al. (2005). 2 Recovered from Punung III by Storm et al. (2005) and in 2004-2005. 3 According to van den Bergh (1999), the Elephas M3 fragment described originally by Badoux (1959) is

too small to ascertain its attribution to E. maximus with certainty. 4 Identified as Homo erectus by von Koenigswald (1939) and Homo sapiens by Storm et al. (2005), but

the provenance and identification of this hominid material has yet to be confirmed.

Punung fauna and Hominid fossils

In Gunung Dawung, fossils were found both in situ and washed out into the field

directly next to the breccia. These fossils clearly indicate a tropical rainforest

environment, evidenced by the presence of orangutan (Pongo pygmaeus) teeth. The

discovery of other mammals, such as the siamang (Hylobates syndactylus) and the sun

bear (Helarctos malayanus) indicate a similar environment. This faunal assemblage

represents the same fauna as those from Punung I and II (Table 2.1). Notably, these

rainforest mammals are also known from Vietnam, Borneo, and Sumatra,

demonstrating a connection between mainland Southeast Asia and Sumatra, Borneo,

10

and Java, as orangutans, siamangs, and sun bears are not known to cross water barriers

(Storm et al., 2005).

In the collection of von Koenigswald from 1930s, five human teeth (two I2s, an

upper and lower C, and possibly an upper M) were recorded in the work of Badoux

(1959). Storm et al. (2005) failed to re-find these five teeth, but an additional human left

P3 (PU198; Fig. 2.3). This P3 has been gnawed by porcupines, which was common for

other Punung fossils. The crown is completely preserved and shows some wear. Storm

et al. (2005) placed this premolar in the range of H. sapiens, based on a series of

morphometric comparisons and especially the inference that H. sapiens had more

probability to survive in the closed rainforest than H. erectus.

Fig. 2.3 Lateral view of the left human P3 (PU-198) from the Punung fauna; B)

occlusal view of the left human P3 (PU-198) from the Punung fauna (Storm et al. 2005)

The importance of Punung fauna is embodied in following aspects. Firstly, It

represents the most significant faunal change in Java during the last 1.5 million years.

Comparing to the earlier faunal stages, it contains no extinct mammals, and it

documents the first known appearance on Java of several extant Southeast Asian

species, including asian elephant, sun bear and siamang. Secondary, the Punung fauna

is the only Javanese faunal assemblage yielded mammals representing a tropical

rainforest environment. Thirdly, it stems from a breccia. The older faunal remains

(Trinil, Kedungbrubus and Ngandong) from Java, associated with the remains of Homo

erectus, all come from river or lake deposits. While those younger faunas (Wajak,

Hoekgrot, Kecil and Jimbe) are clearly associated with Homo sapiens and are probably

the result of human burial practices (Storm, 1995; Storm et al., 2005). Additionally, the

replacement of H. erectus by H. sapiens may have occurred, coinciding with transition

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of habitat and animal inhabitant.

2.2.2 Stratigraphy and previous chronological studies

Gunung Dawung

Gunung Dawung is located at 355 m above mean sea level on the north side of a

karst cone near the Ndawe River (Fig. 2.1). Gunung Dawung situated in the saddle

between two large cones which should be previously the north and south cave wall of a

collapsed cave. This cave should be measured about 130×75 m as indicated by the

remnant dripstone features on both sides of cones. Punung III breccia is contained

within a small rockshelter (3.5 m long, 1.1 m deep and 1.5 m high) in the southern wall

of the now collapsed cave (Westaway et al. 2007).

Stratigraphy and chronology

The sediment inside the Dawung rockshelter could be discriminated as following

sequence, from bottom to top: clay with weathered limestone clasts; a 50-cm-thick

“lower flowstone”; an 80-cm-thick “middle flowstone” of pure calcite; a 105-cm-thick

cave breccia containing faunal remains; and a 22-cm-thick “upper flowstone”. “The

latter is horizontally oriented in the upper layers but has contorted lower layers, which

suggests precipitation by water flowing directly over the angular breccia. On the west

side of the site, only remnants of the upper flowstone and the breccia adhere to the

rockshelter wall. On the east side, however, these are covered by a protective jumble of

large, soluted limestone blocks. Disoriented drip features on the blocks indicate that

they fell as part of the process of cave collapse.” (Fig. 2.4; Westaway et al. 2007)

Westaway et al. (2007) collected samples from all the three flowstone layers, and

yielded U-series ages of 492 ± 38 ka, 424 ± 19 ka and 118 ± 3 ka (2σ), respectively.

They also dated the breccia directly by luminescence methods, a mean age of the TL

and OSL ages is 128 ± 15 ka (1σ). Considering the minimum age provided by the upper

flowstone, the Punung breccia were dated back to an age range of 158 to 115 ka at the

95% confidence interval. This coincide with the presence of rainforest-depend species,

but give different possibilities of the time of their immigration, as it includes a

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dramatically climatic change periods from late MIS 6 to MIS 5d.

Fig. 2.4 Stratigraphy at Punung III (Dawung rockshelter) showing position of the

samples collected for luminescence dating (L) and uranium-series dating (circled

numbers). The plan view of the rock shelter is shown inset.

2.2.3 Samples from Gunung Dawung

In the Dawung rockshelter, we found teeth and bones in some fissures.The

porcupines collected these remains in these small fissures inside the limestone bedrocks,

and gnawed almost all of the tooth root and bones, leaving only tooth crowns and some

bone fragments. Then during a period of high sedimentation, these fissures should have

been filled by clays and sands, which are still partly left now. But, these fissures were

easily washed out as in the climate of Indonesia. Finally, it was during a humid period,

when the karst was full of water and with high degree crystallization, that the remains

were wrapped by the growing calcite crystals. There probably wasn’t a big lag between

the accumulation of teeth and the formation of calcites, according to the fresh surface of

13

the tooth fragment.

Trying to examine the age of this faunal assemblage, we collected a piece of

rhinoceros tooth fragment (BD-2, see Fig. 2.5), containing both of dentine and enamel

which are good material of ESR dating. Some calcites cemented to the teeth were

collected also (BD-1, see Fig. 2.5), by performing U-series dating, these pure and well

crystallized samples would yield a minimum age for the tooth sample (Fig. 2.5).

Fig. 2.5 Left: fragment of a rhinoceros tooth, designated as BD-2; Right: Calcite

crystals cementing to the bones and teeth, designated BD-1.

2.3 The site of Song Terus

2.3.1 Introduction of Song Terus

Song Terus cave was formed in one of the limestone karstic hills in Gunung Sewu

Area (Fig. 2.2). It is located at Weru village, Pacitan, East Java. This cave is an

elongated tunnel measuring 100m long and c.20m wide, lying at c. 335m above sea

level. The tunnel has an east-west orientation, with mouths at both sides (Fig. 2.6).

14

Fig. 2.6 Up: Topographic view of Song Terus (after Sémah et al., 2002 in Gallet,

2004); Down: Floor plan of the excavation units (after Sémah et al., 2002 in Tiauzon,

2011)

The Early archaeological investigation of Song Terus was conducted by R.P

Soejono and Basoeki in the 1950s (van Heekeren, 1972), led to the discovery of some

Neolithic artifacts and animal remains. Intensive excavations were performed by a joint

French- Indonesian research team since the 1990s. Two test pits (KI and KII) in the

inner part of the cave and a square about 45m² near the entrance were excavated (Fig.

2.6), yielded a long cultural sequence from Middle Pleistocene to Holocene.

15

2.3.2 Stratigraphy and previous chronological studies

Stratigraphy

The test pits of KI and KII have reached 15m and 8 m of depth respectively,

providing an overview of the stratigraphy. , As illustrated in Fig. 2.7, the sediment of KI

can be roughly divided into two parts: a sequence deposited under stream influence

from >4m down to the base; and an upper sequence representing a typical cave deposit

including the uppermost 4 m ( Sémah et al. 2004).

According to Sémah et al. (2004), the base of the sequence consists of massive

brown clay interbedded with fluvial sand lenses and occasionally thin weathered

volcanic ash layers. These fluvial layers have undergone intense weathering, which

dissolve most of the limestone elements and formed thick ferruginous concretions.

Such deposit is attributed to remnants an ancient river terraces, being trapped and

preserved inside the cave.

The uppermost 4 meters includes three phases of cave deposition. The first was a

silty brown layer with in-situ limestone blocks. They are often interbeded with volcanic

ash lenses up to 15cm thick that were probably deposited by the wind. The second

phase saw a resurgence of karstic dissolution activity with dark clay interrupted by

white carbonate laminations or centimetric hard calcareous layers. The uppermost part

is less than 2 m thick, the presence of large limestone blocks, and its increasing density

from the pit to the squares near the entrance show their relationship with some severe

earthquakes.

Archaeological records and chronology

The whole sequence has yielded culture remains from different periods, which

were discriminated into three main archaeological phases, Terus layer, Tabuhan layer

and Keplek layer, from old to young. Each of them is related to specific sedimentary

filling and archaeological discovery, which will described as following.

16

Fig. 2.7 Stratigraphic profile of KI test pit unit (after Sémah et al., 2004 in Tiauzon,

2011)

1) Terus layer

Terus layer is the lowest part of the section, named after the cave. In pit KI, it

comprise of the stratigraphic units of IV, III, II and I, means the sedimentological levels

of RL, BO1, BO2, BO3, BO4, BO5, BO6 and L3, more than 10 meters thick. In pit KII,

it is composed of it includes levels R, Q1, Q2, Q3, Q4, Q5, and Q6, ~ 4.5m thick (Gallet,

2004). This section is ended by a thick and dense dark grey layer of volcanic ashes,

17

level J, representing the last fluvial action in the cave and considered as the boundary

between the Terus and Tabuhan layers.

In this lithic and fossil bearing layer, combined ESR/ U-series dating were

performed on two animal teeth and yielded the age of 254±38 ka at 448 depth of KII

and 341±51 ka at 820cm deep in KI (Hameau et al., 2007). The uppermost of this layer

were preliminarily dated to 120-80 ka, yielded from two stalagmites. The upper Terus

layer is attractive in this study because of the rich and diverse remains, like artifacts,

bone assemblage, burnt limestone and stalagmites. The details will be discuss later in

2.3.3

2) Tabuhan layer

This layer was dated back to 39-18ka, by U-series dating performed on bones.

These apparent ages are contemporary to those yielded from the lowermost anthropic

layers in the Guwo Tabuhan cave, around 300m far away ( Sémah et al., 2004).

Lithic industries were relatively rare in this layer, probably suggesting a short term

human occupation. Both pollen record and large mammals show open environments

and a dry climate. (Kusno, 2009; Sémah et al., 2004). This dry and open environmental

condition triggered windblown activity that brought substantial amount of volcanic

deposit into the cave (Sémah et al., 2004). In the uppermost Tabuhan level, the presence

of some carbonated banks and laminations and the pollen spectrum suggest a transition

from an open environment to a rainforest environment which should relate to the

Pleistocene/ Holocene boundary.

3) Keplek layer

The uppermost 1.5 meters, above the carbonate lamination, was dated back to c.10,

000 and 5000 BP by radiaocarbon dating. The archaeological record attributed to the

Keplek layer is dated to 11,600 ~ 5,000 ka. Holocene human activity in the cave

documents diverse subsistence strategies, toolkits, ornaments and mortuary practices

(Ansyori, 2006, Fadjar, 2006, Kusno, 2006, Ingico, 2010). Additionally, a human

skeleton was found in this layer, which may relate to burial activity according to recent

study (Détroit, 2002; Budiman, 2008).

18

2.3.3 Occupation floors in Upper Terus layer

Occupation floors:

The uppermost Terus layer, at a depth of 400-500cm below the surface in KI, and

at the depth of 400-450 cm (below D.P.) in squares, produced a rich faunal assemblage

associated with stone tools (also stalagmites and burnt stones in the squares).

In the upper Terus layer of L8, L9, and M9-11, the findings comprise of 82

stalagmites, 38 pieces of burnt limestone, 365 pieces of fresh chert artifacts, 410

specimens of animal remains, and also lots of little burnt limestone, artifacts and

microfaunal remains collected from sieving (Fauzi, 2008; Ansyori, 2010).

In order to have an overview of all the remains from the squares, a joint cross

section was made, consisting of the stratigraphy of L8, L9, M10 and M11 (Fig. 2.8).

The vertical and horizontal positions of the remains from these squares are projected to

this cross section, while the east wall of L9 (L9/10) is removed when projecting, and

the findings from M9 is projected to the north wall of L9 (K/L9). The distributions of

these numbered remains (only 170 identified animal specimens) are plotted in Fig. 2.9,

Fig. 2.10, Fig. 2.11 and Fig. 2.12, respectively.

The distribution of the fresh chert artifacts is fairly even (Fig. 2.9; Fauzi, 2008).

While the burnt limestone are concentrated in two layers at ZDU 400-600 cm and ZDU

469-502 cm, leaving a sterile phase at ZDU 469-468 cm (Fig. 2.10; Fauzi, 2008).

Analysis on the bone assemblage by Ansyori (2010) also confirmed the existence

of two different sub-culture-levels in upper Terus layer. He defined the layers as Level

A and Level B, according to the different preservation of the bone assemblage (Fig.

2.11). Level B preserved high percentage of rounded and iron-oxide coated bones,

which have been heavily affected by fluvial dynamics. While in the Level A, high

concentration of fresh bones is present. His further analyses showed possible evidence

of anthropic breakage of animal remains in Level A, densely concentrated in M11, and

more scattered in M9. Anthropic impacts on animal bones have been observed in the

presence of cutmarks on a Cervidae distal radius. Human modification on bones also

has been observed in Level B, but it is ambiguous as the remains are rounded and

19

Fig. 2.8 A continuous cross section of L8, L9, M9, M10 and M11. (Modified from Fauzi, 2008)

20

Fig. 2.9 Vertical distribution of fresh chert artifacts in Terus layer (after Fauzi, 2008).

Fig. 2.10 Vertical distribution of burnt limestones in Terus layer (after Fauzi, 2008).

Fig. 2.11 Archaeostratigraphical preposition for the Terus assemblage (Ansyori, 2010)

21

coated with iron-oxide.

The stalagmites are also distributed in two different layers, coinciding with the

cultural remains distribution (Fig. 2.12). Fauzi (2008) sorted the stalagmites into two

categories, Category I is gave to the stalagmites with other materials cemented on the

basis, such as chert, sand, andesite gravel, limestone gravel; meanwhile Category II

without any evidence of that cementation. We could infer that at least those stalagmites

of Category I (64 in all of 82), grew in situ on the cave floors, which at the time were

very rich in Fe-coated pebbles. And finally, these stalagmites with “mushroom” shapes

fell to the floors, because of gravity.

Fig. 2.12 Vertical distribution of stalagmites in category I and II in upper Terus layer.

The dashed line is close to the limit of findings. The red arrows point to the sample of

ST 05 (left) and ST06 (right). (after Fauzi, 2008)

Above all, the imbalance distributions of bone assemblage, burnt limestone and

stalagmites suggest two human occupation floors during extremely humid periods.

Relationship between the occupation floors and Punung Fauna (human):

The taxonomical classification to the Terus assemblage has shown the high faunal

diversity in both Level A and B, and 17 taxa were identified. The presence of S.

syndactylus, Muntiacus muntjak, Echinosorex sp, and Hystrix sp. correspond to the

species that presence in the Punung fauna collection. Furthermore, the presented

species of Sympalagus syndactylus (siamang), Pithecheir parvus (monkey rat), and

Leopoldamys sabanus (long-tailed giant rat) are known as the marker of forested

22

environment. Thus, the upper Terus assemblage could be linked to the Punung fauna.

Tiauzon (2011) analyzed 966 lithic artifacts from the Terus layer in the pits of KI

and KII, and offered compelling evidence regarding the technological continuity of

stone tool production from the lower levels dated to 341 ± 51 ka up to the upper Terus

layer dated to MIS 5, based on the unchanging exploitation of locally available chert

material, technological stasis of the flaking strategy and the tool forms. Thus there is no

evidence for an obviously technological change between the lower and upper Terus

layers.

2.3.4 Samples from Upper Terus layer

Two stalagmites were chosen for U-series dating and isotopic analysis (Fig. 2.12).

ST05 (ST.05.M9 5264 13IG3) come from M10 (coordinate:10, 185, 430; dimensions:

24×12×7, in cm), it is a Category I stalagmite belong to the upper occupation floor.

ST06 (ST.06.M10 14088 13JM4) come from M9 (coordinate: 27, 160, 483; dimensions:

35×28×11, in cm), it is a Category II stalagmite belong to the lower occupation floor.

The stalagmites were cut along the axis, and sampling was performed at the

sagittal section. On each stalagmite, a series of dating samples were taken by an electric

saw; and another series of powder samples were taken equidistantly (1 cm) along the

growth axis, for analysis the stable isotopic composition.

In ST05, 9 samples (ST05-1 to ST05-9) were taken for MC-ICPMS U-series

dating, 1 sample (ST05a) for alpha spectrometric U-series dating, and 12 samples

(ST05-01i to ST05-12i) for isotopic analysis. In ST06, 5 samples (ST06-1, 2, 3, 4, 7)

were taken for MC-ICPMS U-series dating, and 25 samples (ST06-01i to ST06-25i) for

isotopic analysis.

23

Fig. 2.13 Sagittal section of ST05. Big red points mark the positions of dating

samples, and little black point mark the positions of isotopic samples.

24

Fig. 2.14 Sagittal section of ST06. Big red points mark the positions of dating

samples, and little black point mark the positions of isotopic samples.

25

3. Dating methods and experiments

3.1 A review of Quaternary dating methods

The first attempts to try to date the past, could be traced to as early as 17th century,

when biblical thinking placed the creation of the world around 6000 years ago. After

that, more attempts have been made to date this event in more “scientific” ways. As an

example, the Nineteenth Century scientist John Joly yielded an age of 100 million years

by calculating the quantity of sodium salt in the world’s oceans, as well as the amount

added every year from rock erosion. However, it seems impossible for the

pre-Twentieth Century scientists to have any bases for determining the passage of

geological time. (Walker, 2005)

Since (or some earlier than) the early years of the twentieth century, lots of relative

dating methods have been developed, and some of them are still employed, such as

layered sediment (e.g. varves), dendrochronology, palaeomagnetism and

biostratigraphy. Relative dating can determine the sequential order in which a series of

events occurred, but we would refer to absolute dating if we want to know when they

have occurred exactly.

In the middle of 20th century, the decay of certain radioactive nuclides has been

used as a basis for dating. It was the pioneering work of Willard Libby that led to the

development of radiocarbon dating, and to the establishment of the world’s first 14C

dating laboratory in 1948 (Goodrum, 2004). 14C dating now is the most widely used

radiometric dating technique in Quaternary science, especially after the development of

AMS 14C, which has decreased the sample mass and measuring time needed, and

increased the precision, more importantly expanded the limiting age up to about 10

half-lives (T1/2=5,730 yr).

After radiocarbon, uranium-series (U-series) dating has probably been another

most widely employed radiometric dating technique. 230Th/ 234U dating (See details in

section 3.2) could be used to date the materials like speleothems, travertine and corals,

yielding the time span since they have been formatted. It has been a very important

technique in researches as landscape evolution, archeology and human evolution within

half a million years.

In the sites which lack suitable materials, or beyond the range of radiocarbon and

U-series dating, it is also possible to obtain ages through 40K-40Ar, and its variant

26

40Ar/39Ar, dating systems which are based on the decay scheme of the 40K isotope

(t1/2=1,250 Ma), if volcanic minerals are available. The K-Ar method requires two

separate measurements in 40K and 39Ar, which has limited the precision of the samples

younger than 100,000 yrs. This could be obviated in 40Ar/39Ar method, which

transforms nature 39K into 39Ar by artificial neutron activation. Since the nature ratio of 39K/40K is a constant in the nature, 40K could be known by measuring 39Ar. As single

element is measured simply using mass spectrometer, 40Ar/39Ar dating has reached a

greater level of analytical precision, means that much younger samples (~10,000 yrs)

can be dated. (Walker, 2005) 40K/40Ar (40Ar/39Ar) would be limited as it is not so common to find volcanic ash

in some regions like East Asia during the Middle/Early Pleistocene. But taking the

advantages of the development of ultra-sensitive accelerator mass spectrometry (AMS),

it is possible to obtain the burial age of quartz by measuring the in-situ cosmogenic

nuclides such as 10Be, 26Al and 21Ne, named as 10Be-26Al burial dating (and its variation, 10Be-26Al-21Ne burial dating). When the quartz is exposed to the secondary cosmic rays,

these isotopes will be produced inside at a fixed ratio. If the quartz being buried

suddenly, decay of 10Be and 26Al decay make their ratio decreasing exponentially

(apparent half life ~1.48 Ma), and form the chronometer of burial dating. This new

developed method has the theoretic dating range from ~ 0.3 to 5 Ma (Granger and

Muzikar, 2001), and has been applied in some Middle and early Pleistocene

archaeological sites, such as Zhoukoudian and la Noira (Shen et al. 2009; 2012)

In addition to these isotopic techniques, there are another group of important

dating methods, Radiation Exposure Dating (RED), which obtain ages by measuring

the cumulative effect of nuclear radiation on the crystal structure of minerals or fossils.

Three of them correspond to the same principle: a time-dependent accumulation of

electrons and holes in the crystal lattice of minerals, which are collectively referred to

as techniques of Trapped Charge Dating (Grün, 2001). Thermo-luminescence (TL) and

Optically Stimulated Luminesence (OSL) are related techniques. The former date the

age when materials like ceramics and burnt flints were last heated over 500℃, and the

latter date the age when minerals like quartz and feldspars were last exposed to the

sunlight before being buried in the sediment. Both events could release the trapped

electrons, and reset the “clock” to zero. Luminesence techniques can date objects up to

50,000 years old. They can be useful for dating early sites and those that do not contain

material suitable for radiocarbon or other dating methods. Compared with TL and OSL,

27

ESR (and combined ESR/U-series dating, see details in Section 3.3) has a greater

applicable time range. ESR dating on quartz could date the sediment as early as ~2Ma,

and some recent combined ESR/U-series dating studies have show its prospect in the

sites as old as 1.2 to 1.8 Ma (Han, 2012; Duval et al., 2012).

Another RED method is Fission Track Dating which is based on the degree of

radiation-induced damage reflected in the number of ‘damage tracks’ or ‘trails’ in

irradiated crystal structures and glass caused by fission events produced from the

spontaneous decay of uranium-238. FT dating is suited for determining

low-temperature thermal events using common accessory minerals over a very wide

geological range (typically 0.1 Ma to 2000 Ma, vary from materials and Uranium

concentrations).

The sites of Song Terus and Gunung Dawung are located in the karst region of

Gunung Sewu, where speleothems are easily found. In the sediment layers we are

interest in, we find some stalagmites (from Song Terus), calcite cementation and animal

teeth (from Dawung). According to the previous studies (stratigraphy, preliminary

chronology and prehistorical remains), these samples should belong to the period of

MIS5. Hence, U-series dating should be the foremost method to date these carbonate

samples, and combined ESR/U-series dating on the teeth would provide an strong

evidence for verifying the U-series age in Dawung. This two dating methods will be

elaborated in following sections.

3.2 U-series disequilibrium (230Th/234U) dating

3.2.1 Principle of 230Th/234U dating

This technique is based on three naturally occurring decay chains starting from 238U, 232Th and 235U, which decay to stable forms of lead (206Pb, 208Pb and 207Pb, respectively;

see table 3.1). In the uranium decay chains, the 230Th/234U, 231Pa/235U, 234U/238U

daughter/parent combinations are used in Quaternary dating. As 238U is far more

abundant than 235U in nature, (the activity ratio of 238U/235U is around 21.7:1), the

analysis of the 235U decay chain is correspondingly more difficult, which has limited the

application of 231Pa/235U. However, the 238U-234U-230Th-232Th system has been utilized

widely as an absolute chronometer with applications in paleoclimatology.

28

Tabl

e 3.

1. T

he c

hain

dec

ay p

athw

ays

and

half

-liv

es o

f 23

8 U, 23

5 U a

nd 23

2 Th.

207 Pb

st

able

21

1 Bi

2.1

6m

207 T

l 4.

79m

227 T

h 18

.5d

223 R

a 11

.1d

219 R

n 3.

92s

215 Po

1.

83×

10-3

s

211 P

b 36

.1m

231 Pa

3.

25×

104 a

227 A

c 21

.77a

235 U

se

ries

235 U

7.

13×

108 a

231 T

h 25

.5h

212 Po

3

.0×

10-7

s

208 Pb

st

able

212 B

i 60

.5m

208 T

l 3.

1m

228 T

h 1.

91a

224 R

a 3.

64d

220 R

n 54

.5s

216 Po

0.

158s

212 Pb

10

.6h

2

28A

c

6.13

h

232

Th

ser

ies

232 T

h 1.

40×

1010

a

228 R

a 5

.75a

210 Po

13

8.4d

206 Pb

st

able

210 B

i 51

d

214 Po

1.

6×10

-4s

210 Pb

22

.3a

214 B

i

19.7

m

234 U

2.

45×

105 a

230 T

h 7.

54×

104 a

226 R

a 16

22a

222 R

n 3.

285d

218 Po

3.

05m

214 Pb

26

.8m

234 Pa

1.

18m

238 U

4.

47×

109 a

23

4 Th

24.1

d

238 U

s

erie

s

U

Pa

Th

Ac

Ra

Fr

Rn

At

Po Bi

Pb Tl

↓mea

ns α

dec

ay, a

nd ↗

mea

ns β

deca

y

29

To introduce basic terms used in radioactive dating, half life (T1/2) of a radioactive

isotope is defined as the time needed for the decay of half of the number of atoms in a

batch of the isotope. While the decay constant is defined as

1/ 2

ln 2

T (1)

Then decay rate of given number of atoms is given by the equation: dN

Ndt

(2)

Integration of this equation yields the atoms left,

0 * tN N e (3)

Where N0 is the size of an initial population of radioactive atoms at time t = 0.

In a chain of parent-daughter isotopes, if an intermediate nuclide (Ni), has its

parent nuclide (Ni-1) and daughter nuclide (Ni+1), its decay rate could be presented as:

1 1i

i i i i

dNN N

dt (4)

As the half-life of 238U is significantly longer than any of its daughter isotopes,

which means that the number of parent atoms remains essentially constant for several

half-lives of the daughters. If a uranium mineral is left undisturbed (in a close system)

long enough, the activity of each of the daughter isotopes will come to be equal to that

of the parent isotope, called secular equilibrium. In this status, we have:

1 1 2 2 3 3 n nN N N N (5)

However, if the system is not closed and daughter isotopes can escape, then there

will be a break in the decay chain and a state of disequilibrium will exist. Once the

system becomes closed again, the isotope migrations will stop, and the system will

return to equilibrium conditions slowly. This is this process that forms the basis for

estimating age, so called the uranium-series disequilibrium dating.

Particularly, 230Th/234U dating is based on the principle that as uranium is soluble,

whereas the daughter products (such as 230Th) are not. In the case of secondary

carbonate (such as speleothems), CO2 dissolved in nature water will react with the

carbonate in the soil or bedrock, as following equation: 2+ -

3 2 2 3CaCO +CO +H O Ca +2HCO

U6+ in the aqueous solution is present as the uranyl ion (UO22+), which forms

soluble complex anions. After transported to caves, the water evaporates and CO2

degas, then Ca2+ precipitate into calcite or aragonite, the dissolved uranium will be

30

taken up and be incorporated into the carbonate. But thorium is easily to be hydrolyzed

and form insoluble hydroxide in nearly neutral water, which has been absorbed by clast

in the water and deposited in during the transportation. Thus it is considered that there

will be little or no uptake of thorium in the pure carbonate samples. When the system

closed, the 230Th growing back towards equilibrium with its parent 234U could describe

as,

234 230230 2342340

230 234

( )t tTh U e e

(6)

Where t = time; λ230 = decay constant of 230Th; λ234 = decay constant of 234U;

Taking the 238U into account, the 230Th/234U age can be obtained by (Schwarcz,

1989a):

230 230 234

230 238 238( )230

234 234 234230 234

(1 ) (1 ) ( ) (1 )t tTh U Ue e

U U U

(7)

Where the isotopic ratios of 230Th/234U and 234U/238U can be obtained by α spectrometry

or different kinds of Mass spectrometry, which will be explained in section 3.2.3.

3.2.2 Assumptions and reliability

As mentioned before, the 230Th/234U dating is based on two important

assumptions:

First, there was any nuclides exchange between the sample and its environment

after its formation, meaning that the parent to daughter ratio changes only because of

the radioactive decay process. It has been confirmed that speleothems, travertine and

corals samples which are dense and without weathering could form a closed system for

the isotopes, while most of the materials like bones, teeth and shells have complex

history of uranium uptake, made their 230Th/234U age not reliable (Shen, 1996).

Second, there was any initial 230Th in the sample at the time of crystal formation,

hence the measured 230Th was produced by the decay of 234U only. However, it is not

always the case in natural condition. Carbonate materials are easy to be contaminated

by “dirt” (such as aeolian dust, water-transported silts and clays, or some organic

matters) that already contains daughter nuclides. Such contamination can lead to

U-series ages that are older than the true age.

Thus, in order to gain accurate ages, the sample should be selected carefully before

31

analyzing. It is easy and effective to break the sample into little grains and examine one

by one, to eliminate the ones with obvious “dirt”. After this, majority of initial 230Th

will be excluded from the measuring.

Besides, the effects of detrital contamination can be corrected by measuring the

activity of 232Th that is present in the sample but which plays no part in the decay chain

of uranium. This isotope is present in detritus, but not in pure calcite, and hence the 232Th/230Th ratio can be used to correct for initial 230Th. Generally, if the activity ratio of 232Th/230Th is bigger than 20, the effect of initial 230Th could be ignored (at the

precision level of alpha spectrometry), unless it should be calibrated using the

isochronal technique, in which multiple-sample leaching analyses are undertaken and

the activity ratios of the different isotopes in each of the samples are plotted against

each other (Schwarcz and Latham, 1989). This will show the extent to which detrital

contamination has influenced the 230Th/234U and 234U/238U ratios, the isotopic ratios

from which ages are calculated (Fig. 3.1). These ratios will be corrected before inserted

into the normal age equation to calculate the age.

Fig. 3.1 Variation of 234U/238U and 230Th/234U activity ratios with time in a closed

system where there is no initial 230Th present. The near vertical lines are lines of contant

age (isochrons), while the near horizontal lines show changes in nuclide activity with

time for different initial 234U/238U activity ratios (after Heijnis, 1995 in Walker 2005)

32

3.2.3 Different measuring techniques

As a conventional technique for measuring U-series nuclides, α spectrometry has

been used since the middle-1950s. Alpha particle is a positive particle consisting of two

protons and two neutrons (identical to Helium nucleus, 4 22 He ); it could be produced by

alpha decay. Isotopes could be detected and distinguished by α spectrometer according

to the characteristic energy levels of the alpha particles they emit, and showed as

different peaks in the energy spectrum.

In order to yield data with statistic significance, 1~10 μg of 238U in the sample

(usually, representing > 10 grams of sample mass), several days of measurement are

necessary. According to chemical and instrumental conditions, the precision could

reach to around ± 3% (1σ), means that the real age divergence would be covered up by

the statistic fluctuation after 5 half-lives (when the activity ratio of daughter to parent

will reach to 97% of that in the equilibrium states ). Thus the up limit of 230Th/234U

dating is ~350 ka. As it is economically to build and to maintain, this conventional

method are still used in some young samples, when the sample is sufficient and the

error range is acceptable (~± 10% for the samples within ~200ka), or in ESR dating

which use the isotopic ratios in dental samples as one of the parameters.

Alpha spectrometer is relatively inefficient as it only measures the abundances of

atoms that actually decay during the measurement period. In contrast, mass

spectrometry offers the opportunity of counting every atom in the sample, also with

approximately an order of magnitude improvement in sensitivity and in precision.

Simultaneously, the dating limit has been extended to somewhat over 500,000 years.

Thermo Ionization Mass Spectrometer (TIMS) was the first mass spectrometer

used in U-series dating in the late-1980s (Edwards et al., 1987a, b; Edwards, 1988), it is

capable of making very precise measurements of isotope ratios of elements that can be

ionized thermally. Compare to Alpha spectrometry, it greatly reduced the required

sample size (to 10~100 ng of U or Th) and measuring time (in hours instead of days),

and provided high precision (± 1-4 ‰). This method has generally replaced the

conventional alpha spectrometry, although it also has some limitations, particularly

those associated with 232Th filament blanks and lower ionization efficiency for high Th

loads, also labor intensive chemical procedures (Shen et al. 2002).

Inductively Coupled plasma Mass Spectrometer (ICP-MS) could achieve nearly

complete ionization of all elements using an ICP source, and provide broadly

33

comparable analytical capability with TIMS, and advantageous for analyses with very

large thorium loads. In the case of Multi-collector ICP-MS (MC-ICP-MS), it could

reach to a precision of better than ± 1‰, with faster measuring speed and simplified

chemistry, but using instruments much more expensive.

Quadrupole ICP-MS is another widely used technique for trace and isotopic

analyses. Although the analytical precision hardly reach to better than ~0.5 %, but with

the advantages of fast measuring (up to 50 U-Th dates per day), and simplified

chemistry, it provides an extremely rapid and low-cost U-series dating technique

(Douville et al. 2010).

Considering all the resources available comprehensively, we chose the high

precision technique of MC-ICP-MS (Thermo-Finnigan Neptune, Laboratoire des

Sciences du Climat et de L’Environnement, GIF sur Yvette, procedures see section

3.2.5), to establish a detail chronological framework for the stalagmites, by taking a

series of samples intensively. We also use conventional alpha spectrometry (in

Geochronological laboratory of Departement de Prehistoire, Muséum National

d’Histoire Naturelle, procedures see section 3.2.4) to yield ages for the other calcite

samples and isotopic ratios for ESR dating with less precision.

3.2.4 Procedure for conventional alpha spectrometry

Sample preparation:

In this study, both calcite samples (ST05a and BD-1) and dental samples

(BD-2dentine and BD-2enamal) were analyzed by alpha spectrometry. Calcite samples

were prepared as following:

a. The calcite was broke into grains by dental drill and pliers.

b. Each grain was examined in order to remove visible dirty material.

c. The grains were washed by dilute HCl, and then by water in an ultrasonic

cleaner.

d. Step a and b were repeated until the sample was visually pure.

For dental samples, the dentine and enamel were separated and cleaned by dental

drill, making sure that no contamination from each other. Then they were cleaned

ultrasonically, and ground to ~ 200 μm.

Chemical protocol:

34

Before measuring by alpha spectrometer, a chemical protocol should be performed

to separate and purify U and Th, in order to improve the resolution of the U and Th

spectra. Because of the uncertainty of chemical recoveries in alpha analysis, precise

elemental concentrations are determined by isotopic dilution methods. This method is

based on the determination of the isotopic composition of an element in a mixture of a

known quantity of a tracer with an unknown quantity of the normal element (Goldstein

and Stirling, 2003). The spike is a solution containing known concentration of the

elements being analyzed, whose isotopic composition has been enriched in one of the

isotopes of these elements. The spikes for alpha spectrometry used in this work are 232U

and 228Th. The half-lives of these two isotopes are 70 and 1.9 years respectively and the

concentration of the tracer used in this work was 8.223 dpm / ml, and was calibrated in

LSCE, Gif sur Yvette, and by Qingfeng Shao sequentially.

The AG 1×8 anion resin was used to separate U and Th from aqueous solution and

U-TEVA resin (extractant diamyl amylphosphonate – DAAP) to eliminate Fe, (PO4)3-

and other interfering ions. The procedure of the chemical separation will be described

briefly in following paragraphs, and illustrated in Fig. 3.2; this protocol was designed

by Bischoff et al. (1988) and Shen (1985), and then developed by Shao Qingfeng in

IPH.

a. Dissolution of the samples

The samples were heated at 500 ℃ for 2~3 hour in a Muffle furnace, then

dissolved in the 8N HNO3. According to the mass and U concentration, certain volume

of 232U and 228Th spike was added. The sample solution is allowed sit overnight on

hotplate to make sure complete spike-ample equilibration. Some of the samples were

filtered, if irresolvable residue is visible.

b. Co-precipitation of Fe(OH) 3

Add 15 mg Fe3+, and heat the solution for ten minutes. Adding NH4OH to the

solution until the pH is about 7, when red brown precipitation has been made. U and Th

was co-precipitated in the Fe(OH)3, which then was collected by centrifugation, and

dissolved by hot 2N HCl. After that, the solution was evaporated to dryness, and then

dissolved in 8 N HCl. This step has removed majority of unknown ions from the

solution, which is more important for calcite samples. Additionally, during the process

of making precipitation, it is necessary to pause at PH=2 to judge the concentration of

(PO4)3- in the solution.

c. Separation of U and Th using anion exchange resins

35

Fig. 3.2 Chemical procedures for U and Th separation in calcite and dental

samples. Steps with asterisks (*) are optional steps according to the conditions of

different samples.

36

The anion exchange resin AG 1×8 (100-200 mesh chloride form) was used to

separate U and Th, based on the different absorption properties of these two elements.

In HCl solution, U forms strong anionic complexes of the uranyl ion (UO2Cl3) - and

(UO2Cl4)2-, which can be increasingly absorbed on to strongly basic anion resin with

increasing strength of HCl (see Fig. 3.3). The distribution coefficient (Kd) of U rises to

about 103 in 8 - 10 N HCl (Lally, 1992), while Th is hardly to be absorbed in any

strength of HCl. The sample solution in 8 N HCl (2-5 mL) was then loaded to the anion

exchange column, then rinse the column with 4 cv 8 N HCl. Both of the effluent and

washing solution are collected as Th solution. The column was then rinsed with 4 cv 0.1

N HCl to elute the absorbed U.

Fig. 3.3 U (IV) distribution coefficients in anion-exchange resin column under the

different concentration of hydrochloric and nitric acid system (Qin et al., 1984)

d. Purification of U using U-TEVA resins

To eliminate unwanted interferences (e.g. Fe 3+) in the spectrum of U isotopes,

UTEVA resin (Uranium and TEtraValents Actinides) was used to purify U (Horwitz et

al., 1992). The extractant of UTEVA resin (Dipentyl pentylphosphonate) forms nitrate

complexes of U(VI) and also Th(IV), Np(V) and Pu(IV). The distribution efficients of

these elements increase as the strength of HNO3 (or HCl) (see Fig. 3.4). In contrast,

37

most of other elements are not retained on the resins in high concentration of HNO3

condition. The U solution was evaporated and re-dissolved in 3 N HNO3, then loaded to

the UTEVA resins column. Additional 4 cv of 3N HNO3 was added to rinse the column.

Lastly, 5 cv of 0.1N HCl was added to elute U.

Fig. 3.4 Nitric acid (left) and hydrochloric acid (right) dependencies of k’

(capacity factor) for selected ions on U-TEVA resin (T=23-25°C, 50-100μm particle

size resin) (Horwitz et al., 1992)

e. Purification of Th using anion exchange resins

In order to eliminate calcium ions and phosphate anions from the Th solution,

anion resin column has been used again. As in the condition of 5-10 N HNO3, Th forms

stable nitrate complex of the form Th (NO3)62-, which could be well retained on anion

resins (Lally, 1992). The Th collected from step c was firstly co-precipitated with

FePO4 by the addition of ammonium to sample solution until pH-value approaching 2.

After centrifugation, the FePO4 precipitation was separated and dissolved in 7 N HNO3,

then passed over an AG 1×8 resins resin. After that, the column was rinsed by 4 cv 7 N

HNO3 to wash out the traces of calcium and phosphate. Lately, Th is eluted with 4 cv 8

N HCl.

f. Preparation of U and Th sources

38

According to the different pH conditions of U and Th extraction by TTA

(thenoyltrifluoroacetone) (see Fig. 3.5), the U and Th solutions from step d and e were

evaporated, and dissolved in 2 ml of distilled water and 0.1N HNO3 respectively.

Additionally, bromthymol blue, EDTA (ethylenediamine tetra-acetic acid), HAc-

NH4Ac (buffer) were added into the U solution. Then 1ml of TTA in benzene was been

added to U and Th solutions respectively, to extract the elements. After stirring and

centrifugation, the TTA solutions was taken and dropped onto a hot stainless steel

planchet. Finally, these planchets were heated at 450℃ in the Muffle furnace for 30 min,

in order to destroy the TTA.

Fig. 3.5 The metal ion extract percentage of TTA solution under different pH

values (Hagemann, 1950)

Measurement by alpha spectrometer

The planchets were measured in an alpha spectrometer for days, and the isotopes

of interest were presented as peaks in alpha spectra (see Fig. 3.6). The counts of 238U, 234U, 232U, 232Th, 230Th, 228Th and 224Rn were integrated over a roughly 40 channels,

while B-228Th (daughter of spike 232U) over 10 channels. The age calculation was

performed by a Matlab program developed by Qingfeng Shao.

39

Fig. 3.6 Uranium (Upper) and Thorium (Lower) isotope spectra of BD-1

3.2.5 Procedure for MC-ICPMS

The procedure for MC-ICPMS is somewhat easier than that for alpha spectrometry,

but needed to be performed in ultra-clean conditions. The sample preparation was

similar with that for alpha spectrometry, but less mass of sample was used. The samples

were powdered, dissolved, and spiked with a mixed 233U, 236U and 229Th.

A rapid and simplified chemical separation technique for U and Th using UTEVA

resin has been developed by Douville et al. (2010) and used in this study. The main

steps are presented as following:

U-238 U-234 U-232 Th-228

Th-228 Ra 224 Th-230 Th-232

40

a. Preparing UTEVA resin columns;

b. Cleaning and charging the resin with 3 N HNO3;

c. Loading sample solutions in 3 N HNO3 on resin column;

d. Rinsing the columns with 3 N HNO3;

e. Eluting Th with 3 N HCl;

f. Eluting U with 1 N HCl.

The UTEVA column resin highly retains U (VI) and Th (IV) if the resin is charged

with >3 N HNO3 (Horwitz et al., 1992), while most other major elements (earth alkalis)

are not retained under those conditions. So they were removed in step c and d. In the

following step, Th was eluted by changing 3 N HNO3 to 3 N HCl, since under such

conditions the retention coefficient of Th in HCl is less than that of U, which therefore

allows separation. Finally, U was eluted by changing the HCl normality from 3 N to 1 N.

Resulting solutions were evaporated to dryness and then dissolved in a 3 ml nitric

solution for analysis.

14 samples from the two stalagmites (ST06- 1, 2, 3, 4, 7 and ST05-1 ~ 9 ) were

analyzed by MC-ICPMS, the chemical analysis were in Laboratoire des Sciences du

Climat et de L’Environnement, GIF sur Yvette.

3.3 Combined ESR/ U-series dating on tooth

3.3.1 Introduction of ESR dating

3.3.1.1 Basic principle of ESR

ESR (Electron Spin Resonance), also called EPR (Electron Paramagnetic

Resonance), is an analytical method to study minerals with unpaired electrons, yielding

meaningful structural and dynamical information on atoms and molecules. When a

mineral is just formatted or reset, all electrons are at ground state. If exposed in some

natural occurring ionizing radiations (mainly α, β and γ-rays) emitted by the radioactive

decay of the elements (like U, Th and K), the atoms of insulating mineral are ionized,

making some electrons eject from the atoms. These electrons are then transferred to a

higher energy state, leaving positively charged holes near the ground state. After a short

41

time of diffusion in the crystal lattice, most of the ejected electrons will recombine with

the holes, except those which have been trapped in some defect sites (e.g. lattice defects,

interstitial atoms etc.). Ordinary the electrons in the mineral are paired by opposite

spins (self-rotation), but the trapped electrons are unpaired, and they will form

magnetic singularities in the crystal lattice named paramagnetic centers. Additionally,

ionizing radiation can split the bonds of molecules, and forms some free radicals

behaving like paramagnetic centers (Callens et al., 1998).

Paramagnetic centers and free radicals can be detected by an ESR spectrometer,

based on the following principle. If placed in a magnetic field, the trapped electrons

will act as magnets, and the directions of their magnetic moments will be the same with

or opposite to the direction of the magnetic field. Thus all the unpaired electrons will be

grouped into two populations with different energy levels (Zeeman splitting). The

difference between the energy levels could be changed along with the magnetic field. If

the sample is radiated by a constant microwave at the same time, the resonance of

electrons spin will happen when the frequency of microwave matches the energy

difference. Energy of microwave will be absorbed by electrons’ transition from the

lower energy state to the higher. The degree of absorption of microwave is expressed as

ESR intensity, which is proportional to the abundance of trapped charges and in turn to

the accumulated radiation in the sample during its geological history.

ESR dating

Trapped electrons and paramagnetic centers accumulate over the time of exposure

to radiation, providing a “clock” for determining the time elapsed since the formation

of the mineral or since the last release of the trapped charges by heating or light

exposure. This accumulated dose, called paleodose or Equivalent dose (DE), is a

function to the exposure time and dose rate:

0

( )T

ED d t dt (8)

where T is the ESR age, meaning the time elapsed since the sample’s formation or

last zeroing event.

If dose rate d is constant, the T can be expressed as:

42

EDT

d (9)

This dating method is based on the following assumptions (Grün, 1989),

1) The inherited ESR intensity must be equal to zero or zeroed by heating or light

exposure, when the dated event occurred;

2) The signal intensity increases proportionally with the radiation dose;

3) The mean-life of the trapped charges is at least ten times larger than the age of

the sample.

Theoretically, ESR dating is suitable for variety of materials like carbonate

(speleothems, travertine, coral, shells etc.), phosphate (tooth, apatite), silicate (quartz,

silex, feldspar etc.) and sulfate (gypsum), spanning the whole quaternary period. But

most of its archaeological applications were carried on quartz and tooth, and only a few

of them were dated back to the early Pleistocene (reviewed by Han, 2011).

3.3.1.2 Paleodose determination

Normally, the paleodose is determined by additive dose method. The samples are

divided into several aliquots, and then irradiated (except one for measuring natural ESR

signal) by different doses. These added doses produce more paramagnetic centers, thus

the ESR intensities increase with the given doses. If we plot the ESR intensities of all

the aliquots against the laboratory doses, and use a fitting function to model the

response curve, the DE value could be extrapolated. As illustrated in Fig. 3.7, the

intercept of X axis, where the ESR intensity equals zero, determines the DE value.

43

Fig. 3.7 Additive dose method for equivalent dose determination (from Shao, 2011)

3.3.1.3 Annual dose assessment

The annual dose corresponds to the sum of the dose rate from α, β and γ rays

emitted by radioactive nuclides (mainly of U, Th, and K) inside the sample and in the

surrounding sediments, and also of the cosmic ray which have penetrated the covering

sediment. Because of the different penetration capabilities of α, β and γ-rays, their

effects on the enamel samples are presented as Fig. 3.8. The α-dose mainly came from

the radiation source (U) inside the enamel, β-dose was produced by the radiation source

(U) in the dentine and cement, as well as enamel itself, and the γ-dose was mainly

contributed by radioactive nuclides (U, Th and K) in the sediments within the range of

about 30 cm around the tooth.

Fig. 3.8 Radiation effect to the tooth samples (after Rink, 1997 in Han, 2012)

44

Thus the Alpha dose in the enamel and beta dose in the dental tissues could be

determined by U-series analysis by alpha spectrometry (see section 3.2). Gamma dose

rate could be measured in laboratory and on the field, for homogeneous deposition and

complex deposition respectively.

Radon-222 is the gaseous daughter in the 238U decay chain; it is easy to escape

from the non-closed system during the equilibrium. Thus radon loss needs to be

corrected during the age calculating. It can be determined by gamma and alpha data of

different tissues of the tooth (Bahain et al., 1992), described as equation (10).

222 230 222 238 234 238 230 234/ ( / ) /( / ) /( / )Rn Th Rn U U U Th U (10)

where the ratio 222Rn/238U is from the gamma spectrometric data, the ratios of

234U/238U and 230Th/234U are from alpha spectrometric data.

Water content is another factor need to be considered, as water in the sediments

absorbs part of the radiation, making the dose rate in wet sediment smaller than in dry

sediment. Thus if this factor is ignored, the age will be underestimated.

Cosmic rays (mainly, neutrons, electrons and muons) reach the earth surface and

partially (mainly muons) penetrate the covering sediments, resulting to a small part of

contribution to the annual dose. If the depth is higher than 1.5 m, its contribution could

be roughly calculated with the following equation (Prescott and Hutton, 1988):

( 0.07 ( ) 0.0005 ( )^2)cosmicD 0.21 d de (11)

where Dcosmic – cosmic dose; d – burial depth of the sample ; ρ – the density of

the sediments.

This function is suitable for the sites at sea level and with high geomagnetic

latitudes ≥ 55º. Prescott and Hutton (1994) provided a suit of method which could

extend the application of equation (11) into any other latitude and altitude.

3.3.1.4 The challenge of ESR dating of fossil teeth

Mammalian tooth consist of enamel, dentine and cement (not always present),

which contain organic part and inorganic matters (hydroxyapatite) in different

proportions. Fossil teeth are important dating materials as they yield ages direct on the

45

archaeological remains, and enamel is most preferable for ESR dating, because of its

highest mineralization degree and stability. But the application of this method is

challenged by the complex uranium uptake history of the dental tissues, which

complicates the accurate determination of dose rate.

Several models were proposed to analogy the uranium uptake history in an

theoretical way. The Early Uptake (EU) model (Bischoff and Rosenbauer, 1981)

assumes that the uranium was took up soon after the burial of the tooth, and after that it

could be considered as a close system. While the Linear Uptake (LU) model (Ikeya,

1982) assumes that the tooth continually took up uranium with a constant rate.

Usually, the authors publish ages based on both of the models in the same sample,

and imply that the real age probably lies somewhere between the EU and LU age

estimates (Grün and Stringer, 1991). But Pike and Pettitt (2003) compared 103

published U-series dates on bones calculated by EU and LU models with the

independent age constraints. Neither of them gives a reasonable accurate date at a

chance of more than 50%. Shao (2011) analyzed 290 published ESR age estimates

calculated by these models, and suggested that the difference between the ESR EU age

and LU age apparently changes with the real age, especially for the samples older than

200 ka. Considering this, a new approaches of modeling the uranium uptake in bones

and teeth were proposed proposed by Grün et al. (1988), called combined ESR/U-series

dating method (US-ESR model), which is applied in this study.

3.3.2 Combined ESR/U-series dating of fossil tooth

3.3.2.1 Principle of combined ESR/U-series dating of fossil tooth

The combination of ESR and U-series method is an improved model to reconstruct

the uranium uptake history (Grün et al., 1988), which could be expressed by a p-value

diffusion equation:

1( ) ( / ) pt mU U t T (12)

46

where U(0) = 0: U-free in the teeth of living organisms; U(T) = Um: the U

concentration observed today; U(t) = U-concentration at time t; T = age of the tooth; p =

diffusion parameter or uptake parameter (p≥-1).

The U-series/ESR model is based on the assumption that there was no uranium

loss during the burial history, thus the present day values are the maximum U-content

over the burial period. The u-content change over time along different p-value is

illustrated in Fig. 3.9, where the EU and LU models are special cases of

U-accumulation (p = -1 and 0, respectively). If p-value > 0, it means that the U-uptake

rate increases over time, while -1< p-value <0, means an early uptake which is between

EU and LU.

Fig. 3.9 U-uptake patterns according to the ESR-US model (after Grün et al., 1988 in

Shao, 2011)

The 230Th/234U and 234U/238U ratios yielded from alpha spectrometry are used to

establish the relationship between the p-value and its apparent U-series age, and the

dose received by the sample at any given time can be calculated by considering the p/t

relationship (Fig. 3.10).

47

Fig. 3.10 Function of p vs t for measured 234U/238U and 230Th/234U ratios (up) and

plot of DE vs t. Arrowed line gives the estimation of the US-ESR age from the measured

DE (down). (Han, 2011)

3.3.2.2 Procedure for combined ESR/U-series analysis

Fig. 3.1.1 shows the general strategy for performing combined ESR/U-series

dating of tooth enamel. It consists of field sampling, laboratory analysis, data treatment

and age calculations.

Field work

It is preferentially to choose the teeth of the Equid, Bovid, Cervid, and

Rhinocerose taxa, which can provide a piece of flat and thick (> 100 μm) enamel with

mass > 1g as dating samples. Some surrounding sediment (within 30 cm) should be

collected for determining the gamma and beta dose by gamma spectrometer in the

48

laboratory. If the burial condition is too complicated to find representative sediments, it

is necessary to measure the in-situ dose rate by thermo-luminescence dosimeters or

portable γ-ray spectrometry. Additionally, the burial depth of the tooth sample should

be recorded in order to evaluate the cosmic dose rate.

Laboratory analyses

For tooth, the different tissues will be separated and cleaned by a dental drill. The

enamel will be polished to about 10 micros of thickness from each face, and then

ground to make 10 aliquots for artificial irradiation and later for ESR signal

measurements. The enamel, dentine and cement (if exists) will be analyzed by γ-ray

spectrometry to test their contents of U, Th and K, and then by alpha spectrometry for

U-series isotopic ratios (procedures see section 3.2.4).

Fig. 3.11 Strategy of combined ESR/U-series dating of tooth enamel (after Bahain et al.,

2002, in Shao, 2011)

For sediments, water content will be measured by comparing the weight before

49

and after drying. Then they will be measured by a γ-ray spectrometry to test their

contents of U, Th and K.

3.3.2.3 US-ESR age calculation

The combined ESR/U-series model age of fossil tooth is carried on an “ESRUSAGE”

program developed on Matlab R2009 by Shao (2012). There are 28 parameters need to

be input for the age calculation, some of them are standard values (see table 3.2).

Table 3.2 Parameters for combined ESR/U-series model age calculation (Han, 2011)

50

4. Climatic reconstruction by stalamite δ18O record

4.1 Introduction and theory of stalamite δ18O record

Human activities are deeply related to the climate change in different scales. The

history of human evolution was marked by adaptation to the climate change and its

resulting landscape and geographic evolution. Thus reconstruction of the history of

climate change is an important way to understand human activity in adaptation and

migration. Usually, owing to the application of high resolution mass spectrometry in

U-series dating, it is possible to determine stable isotope composition in stalagmitic

calcite with very high resolution. δ18O record from stalagmites has been widely

accepted as a indicator of temperature and/or precipitation (Yuan et al., 2004; Wang et

al., 2001; 2008).

A tentative analysis of stable isotopic change of O and C was performed on the

two Song Terus stalagmites, in the aim to yield some climatic information about the

period of humans occupied in the cave.

Carbon has three natural isotopes, 12C and 13C are stable and common in the nature

(98.93% and 1.07%), 14C is radioactive and trace. Naturally occurring oxygen is

composed of three stable isotopes, 16O, 17O, and 18O with natural abundance of

99.759%, 0.037% and 0.204% respectively. The stable isotope composition is

expressed as delta values (δ), which is expressed in parts per thousand (‰) differences

from a standard. For instance, stable isotope composition of carbon and oxygen is: 13

12

13

12

13( )

1 *1000( )

( )C

sampleC

CstandardC

C ‰ (13)

18

16

18

16

18( )

1 *1000( )

( )O

sampleO

OstandardO

O ‰ (14)

where the ratios with suffix of “standard” mean the value from a world accepted standard sample or value, like PDB and VPDB, whose δ value is considered as 0.

The isotopes of an element have almost the same chemical characteristics, but, due

51

to different free energies for atoms of different atomic weights, they have slightly

different properties during chemical or physical processes such as diffusion and

vaporization, which could result into the so called “mass-dependent isotope

fractionation”. There are two main types of fractionations: equilibrium isotope

exchange reaction and kinetic fractionation. The former is an equilibrium process in

which the forward and backward reaction rates of any particular isotope are identical,

meaning the ratios of the different isotopes in each compound are constant for a

particular temperature. The latter is related to an irreversible process, whose forward

and backward reaction rates are not identical and isotope reactions may be

unidirectional. The evaporation of water from the ocean is mostly kinetic fractionation,

while the rain formation in the cloud is mostly equilibrium.

18O has two neutrons more than 16O, hence water H218O is heavier than H2

16O, the

lighter molecule has an easier time to break up the bonds, and is enriched in the vapor

phase. So during the evaporation process, 16O enriches in the vapor and the 18O

concentration increases in the residual water, while in a condensing process, 18O

preferentially enters into the water, and causes a decreased concentration in the

residual vapor. When a bank of vapor is evaporated from the sea, its 18O concentration

is lower than that of the sea water. As the clouds move toward the pole, this value will

continues to decrease after every rainfall, and finally reaches its lowest value until it

forms snowfall in the pole. Thus the δ18O in the precipitation is higher in the tropics

and subtropics, and lower in the pole (ice shell). Based on the same mechanism, the

δ18O values of precipitation also decrease at increasing altitude, latitude and distance

to the coast (Dansgaard, 1964; Fritz and Fontes, 1980; Eriksson, 1983; Rozanski et al.,

1992). Furthermore, according to the “amount effect”, the δ18O values of precipitation

are correlated to the rainfall change, meaning that δ18O values decrease if the rainfall

amount increases. And it is the reason of the “seasonal effect” which is observed as

higher δ18O values during the winter than during summer (Dansgaard, 1964).

Stalagmites are formed by continuous carbonate precipitation at the same

dropping point. The dropping water in caves mostly originates from meteoric water.

Being acidified by CO2 in the soil, it dissolves the carbonate bedrocks when percolating

52

down to underlying caves. After entering into the cave, it releases the CO2 and

precipitates CaCO3 because of the relatively lower partial pressure in the cave. The

δ18O values of the seepage water and the dissolved carbonate are dominated by the

water molecules themselves, they are not significantly influenced by bedrock δ18O

values and are generally dominated by the meteoric precipitation isotopic signature

(Harmon, 1979).

If the calcite is precipitated under isotopic equilibrium conditions, the δ18O

variation can directly reflect changes in δ18O values of meteoric water and cave

temperature (considered to be the mean temperature of the year or years, as caves are

relatively closed) (Dansgaard, 1964; Siegenthaler and Oeschger, 1980). The isotopic

equilibrium needs slowly degassing process and no evaporation during the calcite

precipitation, so the fractionation of 16O and 18O between liquid phase and solid phase

is only a function of temperature. However, the existence of kinetic processes

(deposition of calcite out of isotopic equilibrium) or vadose processes (evaporation of

water at or near the land surface) could change the δ18O values in speleothems and

thereby mask primary environmental signals (Dorale and Liu, 2008).

Therefore, checking the fidelity of stalagmite δ18O variation in reflecting the

climatic change is a precedence work of climate reconstruction. Hendy (1971)

proposed two criteria to distinguish the kinetic effect from an equilibrium

fractionation on stalagmites: first, δ18O values along a single growth layer should

remain constant in an equilibrium condition; second, there is no strong correlation

between δ13C and δ18O in the same stalagmite. The author considered that the process

happeneing at the center and along the flank of the stalagmite should be the same, and

the occurrence of isotopic equilibrium will lead to the same isotopic composition in

the same layer; however a kinetic process will result into a systematic isotope

increasing toward the edge of the stalagmite. The second testing way is based on the

assumption that speleothems 13C are not linked to climate, as its primary sources are

soil CO2, atmospheric CO2 and bedrocks, Hence correlation between δ13C and δ18O is

unlikely to be caused by isotopic equilibrium process.

Until now, Hendy Test criteria has been widely accepted and applied as a standard

53

of checking whether the calcite was deposited under isotopic equilibrium condition

(for instance, Wang et al, 2001; 2008; Genty et al., 2003; 2005).

Dorale et al. (2008) queried the validation of Hendy Test that, 1) fitting the first

criterion of Hendy Test is not theoretically necessary for an isotopic equilibrium just in

the center of the stalagmite, and practically it is not easy to sample on just a single layer;

2) the second criterion of Hendy Test is not a prerequisite to isotopic equilibrium for all

the cases, because the assumption that speleothems 13C are not linked to climate is flaw.

As a main source of speleothems 13C, soil CO2 is related to the type of vegetation,

which is deeply influenced by climate. Furthermore, the authors proposed a Replication

Test which evaluates the likelihood of calcite deposition under isotopic equilibrium

conditions by the demonstration of similar isotopic profiles among two or more

speleothems, because it is highly unlikely that kinetic/ vadose-zone processes affection

on spatially separated speleothems would result to same isotopic variation tendency.

This testing criterion has been used in several studies, such as Dorale et al. (1998),

Dorale and Liu (2008), Lewis et al. (2011).

4.2 Modern climatic pattern of Indonesia

The region of interest in this study has been introduced in chapter 4, and the

modern climatic pattern of Indonesia will be summarized briefly in this section, in

order to understand the significant of δ18O records in this region.

In Indonesian archipelago, the annual mean temperature is ~28°C in the coastal

plains, ~26℃ in islands and the mountain areas, and ~23℃ in the higher mountain

region, and the relative humidity ranges between 70 and 90 %.

Rainfall is the most predominant variable of Indonesia’s climate and it is

correlated to the monsoon blowing from southeast from June to September, and from

northwest from December to March. Two monsoon seasons results into different effects

as the Indonesian archipelago is located between two large continents. The dry season

(June to September) is influenced by northwestward dry air masses from Australia

54

desert, while the rainy season is caused by southeastward humid air masses drived by

the high pressure system over the Asian mainland. The rainfall pattern is also influence

by topographic conditions, as humid air masses have limited transport distance and are

easily trapped in the mountain areas. Thus, in general, the western and northern

Indonesia undergoes more precipitation, and the rainfalls in western Sumatra and Java

are more than 2,000 mm per year. But the islands close to Australia are much drier, with

precipitation less than 1,000 mm per year.

4.3 Material and Method of stalagmite δ18O analysis

Description of Samples

Two stalagmites (ST05 and ST06, see Fig 2.13 and Fig 2.14 ) were collected from

two stalagmite-concentrated sub-layers in the upper Terus layer of Song Terus Cave,

which should represent two ancient human occupated floors. These stalagmites are

partly described in Chapter 2. Their chronology is provided by MC-ICPMS U-series

dating which is explained in Chapter 3.

The stalagmites were sectioned vertically along their growth axes, and both

showing clearly annual layers which could be result of rainy and dry season cycling.

Counting these annual layers could provide auxiliary information for the ages of the

stalagmites, but it is not available in this study, because of some objective reasons. No

growth hiatus is observed in both stalagmites, meaning uninterrupted growth history.

ST05 has homogenous appearance with alternating white and light gray calcite layers.

ST06 is generally gray in the basal half, and gradually turn to much deeper in color and

less spongy in the upper part which shows a change of deposition conditions.

Procedures of stalagmite stable isotope analysis

The samples were polished in IPH to provide a smooth surface for sampling.

Using a dental drill, a series of powder samples was collected by drilling on the surface

along the growth axes. The drill was washed by diluted HCl between two sampling to

55

prevent contamination. As a tentative work, the resolution is 1 sample per centimeter,

12 sample from ST05 and 26 samples from ST06 were taken. The sampling were

performed in IPH and Laboratoire des Sciences du Climat et de l’Environnement

(LSCE, CEA-SACLAY, France).

Calcite δ18O were analyzed with a VG-OPTIMA mass spectrometer in LSCE after

orthophosphoric acid reaction at 90°C (Genty et al., 2003). The data are expressed in

the conventional delta notation relative to the V-PDB for oxygen and carbon. The

analytical error is ± 0.08 ‰ for δ18O and ± 0.05 ‰ for δ13C.

56

5. Results and discussion

5.1 The age of Gunung Dawung

One rhinoceros tooth fragment collected from a fissure in the Dawung rockshelter

was analyzed by combined ESR/U-series dating, hopefully to yield an age representing

the antiquity of Punung fauna. Meanwhile, some calcite crystals cemented to the teeth

were collected from the fissure, and was analyzed by alpha spectrometric U-series

dating, which would yield a minimum age for the tooth sample as mentioned in chapter

2, the calcite should have formed quickly after the fossils accumulation, the age

between tooth and the calcite should be close.

5.1.1 U-series age of Gunung Dawung

The U-series dating result of the calcite by alpha spectrometry is listed in Table 5.1.

An age of ~ 126 1412 ka has been yielded for the calcite sample from the fissure in the

Dawung rockshelter. According to the high ratio of 230Th /232Th (compare to the

standard of 20), this sample could be considered as pure enough to neglect the

contaminant 230Th. This age contains relatively big error range which should be

resulted by its extremely low uranium concentration (~0.13 ppm).

Table 5.1 alpha spectrometric 230Th/234U dating result for calcite sample from Dawung

Sample U(ppm) 230Th/232Th 234U/238U 230Th/234U age(ka) plus minus

BD-1 0.13±0.01 285.38 1.0068±0.0429 0.6865±0.0329 126.4 14.2 12.1

All isotopic ratios shown are in radioactivity. All errors are ± 1σ.

57

5.1.2 Combined ESR/U-series age of Gunung Dawung

5.1.2.1 Equivalent doses, DE

For the enamel sample of BD-2, the ESR signal measurement has been repeated

for 5 times in different days. The data of the first measurement is obviously deviated

from the mean values, maybe relating to the instability of the spectrometer. Thus only

the other four sets of data were used to calculate the paleodose, using the following

fitting function,

( ( ))(1 )Csen x Dey Isat e

where y is ESR intensity at a laboratory dose, Isat is saturation intensity, and Csen

is sensitivity coefficient and De is equivalent dose.

The data of ESR signal measurements is listed in Table 5.2, and the growth curve

is plotted in Fig. 5.1. An equivalent dose of 186.99 ± 7.59 Gy with regression

coefficient of 0.99853 was obtained.

Table 5.2 the data of ESR signal measurement of BD-2 enamel

Aliquot weightTube

Height Artificial

dose Measure

1 Measure

2 Measure

3 Measure

4 Measure

5 1 46.3 4.5 0 429 480 500 496 479 2 46.5 4.5 40 506 552 578 580 550 3 46.4 4.5 60 558 597 632 606 583 4 46.4 4.5 100 687 734 742 711 704 5 46.3 4.5 160 799 896 879 840 836 6 46.3 4.5 250 940 1120 1114 1079 1066 7 46.4 4.5 400 1192 1419 1461 1406 1415 8 46.5 4.5 630 1754 1942 2019 1989 1966 9 46.5 4.5 1000 2444 2692 2864 2742 2727 10 46.3 4.5 1600 3459 3818 4004 3859 3797 pf 7026 7869 8731 7753 6427 pd 6829 7691 8771 8041 7841

58

Fig. 5.1 Single Saturation Exponential fitting result of BD-2

5.1.2.2 U-Th data

The dentine and enamel of BD-2 (BD-2d and BD-2e, respectively) were analyzed

by alpha spectrometry, in order to determine the uranium content and ratios of 234U/238U

and 230Th/234U, and the results are listed in Table 5.3. The ratios of 230Th/232Th are high

enough (>20), and no correction of contaminant 230Th is necessary.

Table 5.3 Alpha spectrometric U-Th data for BD-2

Sample U(ppm) 230Th/232Th 234U/238U 230Th/234U

BD-2d 67.76±1.10 36.96 1.1303±0.0169 0.7772±0.0188

BD-2e 2.27±0.09 333.91 1.0931±0.0403 0.5946±0.0354 All isotopic ratios shown are in radioactivity. All errors are ± 1σ.

5.1.2.3 Annual dose rate

Gamma and beta dose rates generated from the sediment (dγ, dβs2) are calculated

from the gamma data of sediment surrounding the tooth. Two sediment samples (8.5g

and 17.1g) were measured in laboratory by gamma spectrometer. As listed in Table 5.5,

both of them has extremely low Th content (no significant data), showing an

59

underestimation of the dose rate from sediment. This could result from the unbalanced

uranium concentration in the sediment, as the U content of the calcite cementation (0.13

ppm) is much lower than the tooth samples (2 ~ 67ppm) and bones, also lower than the

breccia (2.3 ppm; Westaway et al. 2007). The sample taken for measuring couldn’t

represent the heterogeneous sediment in the sites, thus we use the data of the breccia

measured by Westaway et al. (2007), which could be more representative for the whole

sediment in the fissure. The results of gamma spectrometric data and dose rates from

sediment are listed in Table 5.4.

Table 5.4. Gamma spectrometric data and dose rates from sediment

element Measure 1 Measure 2 Westaway et al. (2007) data

U (ppm) 1.31±0.14 1.12±0.20 2.27±0.15

Th (ppm) 0 0 1.03±0.05

K (%) 0.044±0.009 0.01±0.02 0.05±0.005

dγ+cosa (mGy/ka) 298±25 270±29 442±25

dβs2 (mGy/ka) 15±2 11±2 26±3 a dγ+cos is the sum of external gamma dose rate and cosmic dose rate, dose rate used here is 153 mGy/ka,

and water content is 8 ± 4 according to Westaway et al. (2007).

The dose rates generated from the enamel and dentine depend on not only the

uranium concentration but also on the pattern of U-uptake. Using the methods

introduced in section 3.3, we tried to calculate the internal dose produced with in the

enamel (dint), and beta dose produced by the dentine (dβs1). Based on the data presented

above and also in Table 5.5, the results of dint =418 ± 107 mGy/ka, and dβs1 =268 ± 69

mGy/ka were yielded.

Table 5.5 Other parameters used to calculate the annual dose rates.

Total thickness (μm) 1754.0±175.4

Removed side 1 (μm) 228.9±22.9

Removed side 2 (μm) 154.4±15.4 Enamel

Density (g/cm3) 2.95±0

Enamel (%) 3±1

Dentine (%) 7±5 water content

Sediment (%) 8±4

Dentine 0.3975 222Rn/230Th Enamel 1

60

5.1.2.4 Combined ESR/U-series age

The combined ESR/U-series age is calculated in the “ESRUSAGE” program on

Matlab R2009 (Shao, 2012), the calculation results are showed in Fig 5.2.

The p-value of dentine is -0.96, suggesting that its history of U-uptake is

extremely close to an Early Uptake model (see Fig 5.2). Considering the burial history

of the tooth that: 1) after being moved to the fissure, it was burial in the clay and sandy

sediment containing limestone blocks during a high sedimentation period; 2) these

sediment was then washed out; 3) finally, the tooth was covered again by calcite

crystals grew during a period of high kastic activity. There is some probability that the

U-uptake history and burial history of the tooth are correspondence in this way: the

majority of uranium uptake happened at the beginning during a very short time (a

vertical part in the curve), which could be linked to the period of sediment burial and

kastic activity. After that, the U-uptake continued in a very low speed which probably

corresponds to the period of being blocked within the calcite cementations.

The combined ESR/U-series age yielded is 162 ± 17 ka within ±1σ, this age is

older than TL/OSL age of the breccia (128 ± 15 ka, Westaway et al., 2007), but they are

still coincident within the error range of ±2σ. The age of the tooth should have been

somewhat overestimated, as the rainforest habitants in Punung fauna suggest a warm

and humid condition for their immigration, rather than a severe dry condition in MIS 6.

The annual dose rates and their percentages to the total dose are listed in Table 5.6.

As the external β dose are mainly (90%) produced by the dentine, 60% of total dose was

contributed by dentine (β dose) and enamel (internal dose). But notably, external

gamma dose and cosmic dose are account for 25% and 13% respectively, which means

the age is very sensitive to the dose rate from the sediment and cosmic ray. In this study,

the sediment surrounding the tooth is not homogenous, and the sediment sample

measured in the laboratory is only partly representative, resulting to an underestimation

of sediment dose rate. Then a set of data measured from the breccia is used to calculate

the external gamma dose, but the final age seems still overestimated. Cosmic dose

could be another factor response for the age potential error. Because of the thin depth of

61

covering, the influence of cosmic dose to the age is remarkable. Besides, the peculiar

shape of the bedrock around the fissure in the rockshelter also complicated the

estimation of cosmic dose rate. Therefore, an in-situ measurement of gamma dose in

the sediment and re-examination of the cosmic dose rate would yield a more accurate

age in future works.

Table 5.6 Annual dose rates of BD-1 Internal dose External β dose External γ dose Cosmic dose Total dose

mGy/ka 418± 107 294±72 289±45 153± 20 1154±130% 36 26 25 13

62

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63

5.1.2.5 The age of Punung fauna and its implication

Gunung Dawung is the only typical site of Punung fauna with convenient dating

potential. A series of mass spectrometric U-series dating and luminescence dating have

been performed to the site and yielded an integrated age range from 118 ± 3 ka to 128 ±

15 ka for the fossil-bearing breccia (Westaway et al., 2007). This age overlaps with the

full interglacial period, which conflicts to time of Punung fauna immigration.

In this study, a tooth fragment and its calcite cementation from a fissure in the

same rockshelter of Dawung were dated. By performing combined ESR/U-series

dating on the tooth sample, an age of 162 ± 17 ka is yielded. Although this age should

be an overestimation for the tooth, but it still coincide with the luminescence age (128 ±

15 ka) in the range of ±2σ. Moreover, the calcite cementation is dated back to ~126 ka

by conventional alpha spectrometric U-series dating. This age is perfectly coinciding

with the previous luminescence age.

According to the U-uptake history of the dentine of BD-2, the majority of

U-uptake happened in a very short period, which could be linked to the time before

being cemented by the calcite, meaning that the time lag between the fossilization of the

tooth and the formation of the calcite should be short. The age of the calcite provides a

minimal but very close estimation of the Punung fauna. As this minimal age conform to

the onset of full Last Interglacial, which is considered to be around 128~130 ka in

different continents (Zhao et al., 2001; Tzedakis et al., 2002; Yuan et al., 2004; Jiang et

al., 2005), we suppose that the Punung fauna should have entered Java before the

optimal interglacial.

The present depth of Java sea is around 10 to 80 meters, the closest distance from

Java to Sumatra is ~30 km, even consider Sangiang and Ular islands as step stones, the

closest distance is around 10 km, it’s impossible for some typical Punung faunal species

(like orangutans, siamangs, and sun bears) to pass through the water during a period of

sea level as high as present. Thus for a pre-optimal-interglacial immigration, the age of

Punung fauna is also limited by the time of landbridge submergence in Last Interglacial.

According to Stirling et al. (1998), the relative sea-levels were at ~ 3 m above the

64

present level along the entire Western Australian coastline at ~128 ka; Omura et al.

(2004) dated a series of fossil corals collected from coral reef terraces and tidal notches

in the Philippines, and suggested that the sea level near Palawan was 6.8 m higher than

present at 126.5 ± 2.1 ka, and near Panglao island it was ~12m higher than present at

117 ~ 123 ka. These studies provide a consistent age limit for the Punung fauna arrival

(before 126~128 ka).

It is important to reconstruct the landscape of Java before ~ 128 ka, since existence

of a rainforest corridor is substantial for the Punung fauna immigration. Unfortunately,

the Javanese rainforest development of the early MIS 5e is not well documented. A

weak evidence come from a lacustrine sequence from the Bandung intermontane basin

in West Java, it suggests that the humid condition has started as early as 126ka, which is

the basal limit of this sequence yielded from isochronal corrected U-series ages (Van

der Kaars and Dam 1995; 1997). A more continuous record from the Banda Sea

provides a longer (180 ka) regional vegetation, fire and climate history of the Banda

Sea area, but its chronological framework was largely adjusted from another benthic

δ18O record, which is less dependable to be took into account of this discussion (Van

der Kaars et al., 2000).

5.2 U-series age of occupation floors in upper Terus layer of Song Terus

5 samples from ST06 and 9 samples from ST05 stalagmites were dated using

MC-ICPMS in LSCL in Gif sur Yvette, and 1sample from ST05 was analyzed by alpha

spectrometry. All the dating results are listed in Table 5.7 and 5.8. All the samples taken

for dating are very pure and with ratios of 230Th/ 232Th higher than ~100, which mean

the contaminant 230Th should be neglected. The MC-ICPMS ages have error ranges

from 0.3% to 1%, much more precise than the alpha spectrometric age (~5%).

The samples for mass spectrometry are designated along their distances to the

basis, and supposed to yield two series of descent ages, but the actual results are

somewhat disordered. Samples of ST06-1, 2, 3, 4, 7 are dated back to 91 ka, 81 ka, 87

65

ka, 84 ka and 85 ka respectively. ST06-2 was sampled below the sample of ST06-3, 4, 7,

but yielded an age obviously younger, which is an abnormity. There is another reverse

between ST06-4 and -7, but the ages still agree with each other within the error range.

So generally, the stalagmite of ST06 is dated back to around 91 to 84 ka.

Majority of the ages gathered from ST05 are fall into the range of 91 ~82 ka,

except ST05-3 and ST05-4, which yielded some quite different ages (187 ka and 103 ka

respectively). In order to check these results and their consistency, an additional control

was made by sampling between them. This sample is then analyzed by alpha

spectrometry, and yields an age of 81 ± 4 ka, which conforms to the other samples

rather than ST05-3 and -4. Thus, the stalagmite of ST05 should have grew at a period

during 91 ~81 ka.

In order to find the source of age disarray in the both stalagmites, the existence of

laboratory bias should be considered. Three additional data should be taken into

account here, these data were gathered from the preliminary dating of this two

stalagmites by alpha spectrometry in IPH. A sample was taken from the middle of ST06

(see the gap in Fig. 5.14), it is located between ST06-3 and ST06-4, and dated back to

~120 ka; two samples were acquired at the bottom of ST05, below ST05-1, and was

dated back to 86 ka and 80 ka (Sémah et al., 2007). All the MC-ICPMS ages were yield

from the same laboratory of LSCL using same protocol, materials and mass

spectrometer, while all the alpha spectrometric samples were analyzed in IPH, using the

same spike and alpha spectrometer. But both of the methods have yielded one or two

ages which are significantly discordant, and the rest ages are generally fall into a

relatively short time range although with some disorder. Thus, there is no evidence of

laboratory bias or method bias.

One probably reason of the age fluctuation could be the existence of aragonite in

the stalagmites. Aragonite is a meta-stable polymorph of calcium carbonate, which will

slowly converts to calcite at normal surface temperatures and pressures and faster when

heated to about 400° in dry air. Stalagmites composed of aragonite usually have high

uranium content because aragonite has bigger capacity for uranium uptake than calcite,

and some uranium loss will happen when it converts into calcite. This problem

66

Table 5.7 230Th/234U dating results by MC-ICPMS

distance Mass[mg] 238U[ppm] 234U/238U 234U/238U_0 230Th/238U 230Th/232Th Age[ka]

ST06-1 1.5 1563.59 1.12 1.1398±0.0011 1.1810±0.0015 0.6557±0.0021 98.93 91.4±0.5

ST06-2 5.5 2421.89 1.33 1.1406±0.0010 1.1768±0.0012 0.6050±0.0018 287.49 80.9±0.4

ST06-3 8.5 1598.15 1.14 1.1407±0.0013 1.1799±0.0016 0.6349±0.0030 152.45 86.9±0.6

ST06-4 15.5 440.38 1.16 1.1412±0.0026 1.1792±0.0032 0.6224±0.0023 204.11 84.3±0.6

ST06-7 21.5 1824.32 1.21 1.1428±0.0008 1.1818±0.0011 0.6291±0.0028 94.46 85.5±0.6

ST05-1 0 301.53 2.99 1.1168±0.0012 1.1504±0.0016 0.6319±0.0015 2052.60 89.4±0.4

ST05-2 1.0 497.29 3.50 1.1183±0.0010 1.1517±0.0012 0.6259±0.0025 10986.67 87.99±0.5

ST05-3 3.5 590.39 3.61 1.1127±0.0009 1.1422±0.0012 0.5962±0.0012 4845.07 82.43±0.3

ST05-4 4.5 92.45 3.64 1.1177±0.0015 1.1996±0.0025 0.9374±0.0034 2866.72 186.8±1.8

ST05-5 6.5 759.30 2.40 1.1116±0.0009 1.1493±0.0011 0.6882±0.0016 1539.94 103.1±0.4

ST05-6 10.0 825.63 3.53 1.1086±0.0009 1.1391±0.0011 0.6187±0.0044 4510.04 87.6±0.9

ST05-7 12.5 381.19 4.54 1.1066±0.0005 1.1352±0.0006 0.6005±0.0012 2596.66 84.4±0.2

ST05-8 14.5 494.86 3.58 1.1055±0.0007 1.1363±0.0009 0.6304±0.0022 4196.88 90.6±0.5

ST05-9 17.0 393.99 3.65 1.1030±0.0007 1.1324±0.0009 0.6203±0.0014 9352.38 88.7±0.3 All isotopic ratios shown are in radioactivity. All errors are ± 2σ.

Table 5.8 230Th/234U dating result by alpha spectrometry

sample U(ppm) 230Th/232Th 234U/238U 230Th/234U age(ka) plus minus

ST05a 3.48 345 1.1026±0.0200 0.5285±0.0156 80.9 3.8 3.6 All isotopic ratios shown are in radioactivity. All errors are ± 1σ.

67

complicates the chronological studies on corals and aragonite-bearing speleothems

(Tompson et al., 2003; Frank et al., 2006; Ortega et al., 2005; Yang et al., 2008).The

stalagmites form Song Terus have high U concentration comparing to normal

speleothems, which make us think over the possibility of aragonite existence in them.

Although preliminary X-ray Diffraction on several samples of the stalagmites didn’t

show the evidence of aragonite (according to Simon Puaud, personal communication),

but it couldn’t eliminate the occurrence of aragonite converting during the history.

These two stalagmites were collected from two human occupation floors in the

upper Terus layer, although the apparent ages were disturbed and enlarged the time span,

they are generally dated back to 91~ 84 ka (the lower floor) and 91 ~81 ka (the upper

floor) respectively, according to statistical consistency. These ages indicate that human

occupations in the upper Terus layer of Song Terus cave have happened approximately

from late MIS 5c to early MIS 5a.

5.3 Interpretation of δ18O record from Song Terus

For analyzing the stable isotopic composition, 12 and 24 samples were taken from

ST05 and ST06 Song Terus stalagmites respectively. Isotopic measurements were

performed using a VG OPTIMA mass spectrometer in LSCE, Gif-sur Yvette.

The δ18O and δ13C results are presented in Table 5.9. The analytical error is ±0.08

‰ for δ18O and ±0.05 ‰ for δ13C.

Isotopic equilibrium discussion

Isotopic equilibrium during the calcite deposition is the prerequisite of using the

speleothems isotopic record as a proxy of climatic change. Hendy Test is a traditional

criterion to check the occurrence of isotopic equilibrium by the following two ways: 1)

the study of stable isotope variations along single growth layers; 2) the study of δ18O

and δ13C correlations (Hendy, 1971). Because of objective reason, the first way is not

available in this work, and only the second way was applied.

68

Table 5.9 Stable Isotope results of ST05 and ST06 Song Terus stalagmites.

sample position

(cm/base)

δ18O

(‰, PDB)

δ13C

(‰, PDB)sample

position

(cm/base)

δ18O

(‰, PDB)

δ13C

(‰, PDB)

ST05-01i 0 -6.43 -11.40 ST06-07i 7 -5.94 -9.75

ST05-02i 1 -5.90 -10.43 ST06-08i 8 -6.07 -9.84

ST05-03i 2 -5.86 -10.34 ST06-09i 9 -5.65 -9.26

ST05-04i 3 -5.57 -10.00 ST06-10i 10 -5.92 -9.80

ST05-05i 4 -5.80 -10.45 ST06-11i 11 -5.54 -9.01

ST05-06i 5 -5.82 -10.49 ST06-12i 12 -5.33 -8.11

ST05-07i 6 -5.89 -10.60 ST06-13i 13 -5.83 -9.25

ST05-08i 7 -6.02 -10.72 ST06-14i 14 -6.03 -9.48

ST05-09i 8 -5.90 -10.30 ST06-15i 15 -5.39 -8.52

ST05-10i 9 -5.83 -10.17 ST06-16i 16 -5.84 -9.00

ST05-11i 10 -5.83 -10.43 ST06-17i 17 -5.91 -9.18

ST05-12i 11 -5.98 -10.67 ST06-18i 18 -6.13 -9.53

ST06-19i 19 -5.84 -9.17

ST06-01i 1 -5.30 -7.41 ST06-20i 20 -5.63 -8.31

ST06-02i 2 -5.50 -8.16 ST06-21i 21 -5.98 -9.18

ST06-03i 3 -5.72 -8.72 ST06-22i 22 -5.91 -8.62

ST06-04i 4 -5.32 -8.09 ST06-23i 23 -5.62 -8.72

ST06-05i 5 -5.83 -9.19 ST06-24i 24 -5.41 -8.05

ST06-06i 6 -5.60 -8.87 ST06-25i 25 -4.90 -6.75

Fig 5.3 and Fig 5.4 show the correlation of δ18O and δ13C in ST05 and ST06. Both

of them indicate high δ18O - δ13C correlation (r2=0.89 and 0.82, respectively), meaning

coeval δ18O - δ13C changes. As discussed in Chapter 4, it could be a result of kinetic

fractionation during the calcite deposition (Hendy, 1971), but also could be a sign of

simultaneous change in precipitation and vegetation which is reflected by δ18O and

δ13C respectively (Dorale and Liu, 2008). An advanced way to approach the real

situation is performing the Replication Test, by comparing the studied records with the

other records with have ascertained climatic significances.

69

y = 1.6297x - 0.8846R2 = 0.8881

-13

-12

-11

-10

-9

-8

-7 -6 -5 -4δ18O

δ13C

Fig. 5.　 3 δ13C-δ18O correlation of the ST05 calcite

y = 2.2902x + 4.2264R2 = 0.8194

-11

-10

-9

-8

-7

-6

-5

-7 -6 -5 -4δ18O

δ13C

Fig. 5.4 δ13C-δ18O correlation of the ST06 calcite

Interpretation of δ18O variation

The δ18O values of ST05 calcite range from -6.43 ‰ to -5.57 ‰, with a mean

value of -5.90‰. As plotted in Fig. 5.5, there is a shape positive shift in the first 3

centimeters, with amplitude of 0.86‰; then it goes back to -5.80‰, and keeps stable

within 0.2‰.

70

-7.0

-6.5

-6.0

-5.5

-5.00246810

position(cm)

δ18O(‰

, PDB)

Fig. 5.5 Plot of δ18O values against their positions in ST05.

The positions are the distances to the base, e.g. 0cm =bottom.

In ST06, the δ18O values range from -6.13‰ to -4.90‰, with a mean value of

-5.69‰. As showed in Fig. 5.6, in majority period, the δ18O value is oscillating between

-6.13‰ and -5.30‰, shows a gradually decreasing at the beginning and two short

increasing periods in the middle, after another decreasing to the minimal values, it

begins to continuously increasing up to -4.90‰ at the end. The amplitude of the last

shift is 1.25‰.

-6.5

-6.0

-5.5

-5.0

-4.5024681012141618202224

positionbase (cm)

δ18O(‰

, PDB)

Fig. 5.5 Plot of δ18O values against their positions in ST06. The positions are the distances to the base, e.g. 0cm =bottom.

71

Owing to the application of Mass spectrometric U-series dating and annual layer

counting, it is possible to make global comparison between stalagmite isotopic records

in very precise scales. The Chinese-cave-based record has been one of widely used

references for comparison within the recent two glacial cycles, with the clearly

identified millennial-scale strong summer monsoon events (Chinese interstadial, CIS)

(Wang et al., 2001; Kelly et al., 2006; Cheng et al., 2006; Wang et al., 2008). These

events correspond to the warm Dansgaard-Oeschger (DO) events or Greenland

interstadials (GIS) which were initially numbered in the GRIP records (Johnesen et al.,

1992; Dansgaard et al., 1993) and are also identified in NGRIP ice core (North

Greenland Ice Core Project members, 2004).

The δ18O variations recorded in stalagmites from southern Indonesia are related to

the change of precipitation or the Australian-Indonesian Summer Monsoon (AISM),

which brings the main part of precipitation in this area. This has been confirmed by the

records from both recent and ancient periods.

Watanabe et al. (2010) analyzed the isotopic composition of a stalagmite collected

in Ciawitali Cave, West Java. A comparison between the temporal variation of δ18O and

δ13C values and the temporal variation in annual precipitation amounts that occurred

since the 1950s at Cikidang station near the cave shows significant negative correlation.

This pioneer work provides a direct evidence for the usefulness of speleothems isotopic

composition with correlated δ18O and δ13C values (which could be a demonstration for

Song Terus records) in reflecting the precipitation change in this region. Another

stalagmite record from Liang Luar cave in Flores yielded a temporally consistent

relationship between hydrological changes in the AISM and East Asian Monsoon

(EAM) in orbital or millennium scales throughout GIS4/3 warm intervals (Lewis et al.,

2011).

Also considering the absolute ages and time span obtained for ST05 and ST06

stalagmites, the Chinese-cave-based record was chosen for δ18O records comparison, in

order to check the climatic coherence between two monsoon areas during around 90~80

ka, and reveals the likelihood of calcite deposition under isotopic equilibrium

conditions for ST05 and ST06 as well.

72

ST06 and ST05 are apparently dated back to around 91 ~ 84 ka and 91 ~81 ka

respectively, but according to their original stratigraphy, ST05 is most likely to start

growing after the burial of ST06, meaning the ST05 is younger than ST06, and there is

no temporal overlap. Thus as references of this study, two stalagmites records which

covers the related age range were selected from the long isotopic record published by

Wang et al. (2008). These stalagmites were collected from the Sanbao Cave in central

China, designated as SB25-1 and SB22.

After exhaustive examination of the isotopic variation of Sanbao samples during

the 95~80 ka period, we have tentatively adjusted the Song Terus records into the

Sanbao chronology (Fig. 5.6). A DO warm event (GIS22 or CIS 22) and its following

cold stadial (GS22) are recorded in the Sanbao record around 90 ka(Fig 5.7). Based on

the data of BD-22, the onset of warming (δ18O values negatively increasing) is around

91.0 ka, followed by a ~1.56 ‰ of δ18O values continuous decreasing. After a little

increasing, it starts to decrease again at ~89.5ka, and undergoes two short increasing

periods before reaching the minimum value at ~87.7 ka, the amplitude is ~0.52‰. Then

a sharp increasing of ~1.95‰ happens, and doesn’t turn to gradually deceasing before

~86.9 ka. The variation tendency and amplitude of ST06 is exactly coherent to the

BD22 curve at around 89.5~ 87 ka, and ST05 is more likely correspond to about 86.5~

85.5 ka. The evident cold tendency at the end of ST06 and the beginning of ST05

should be linked to the extremities of the cold period during 87.7~86.9ka in BD22

records.

Thus the comparison shows a preliminary coherence between stalagmites isotopic

records in AISM area and EAM area during Greenland Interstadial 22 and the

following cold event, and equilibrium conditions for both of ST05 and ST06 are

plausible.

The records of Song Terus and SB25-1 are identical, notably, the events recorded

in SB25-1 are ~0.9 ka older than those in SB22. Taking the dating error of the U-series

ages of Sanbao stalagmites (around 1%) into account as well, the ages of ST05 and

ST06 are more likely between ~90 to 85 ka, and the interval between them is very short,

0.5 to 2 ka, estimating with all the errors.

73

It suggests that during MIS5b, the stalagmites of Song Terus Cave kept growing

not only in the GIS 22 warm period, but also in the following GS 22 cold period. During

the cooling transition from GIS22 to GS 22, there was a short time interval without

stalagmite growth and human occupation in the cave.

Fig. 5.6 Comparison of isotopic records between Song Terus and Sanbao Cave within around 95~80 ka. The left vertical axis is for the Sanbao curves, and the right

ones are for ST06 (Upper) and ST05 (lower), all the vertical axes have the some scale.

Fig. 5.7 Comparison between Song Terus isotopic records and China-Cave-based record within the last glacial cycle. The colorful curves are different Chinese stalagmite records (see detail in Wang et al., 2008), grey one is the NHSI (Northern Hemisphere

74

summer insolation, 21 July) at 65°N, and black ones are ST05 and ST06. The Marine Isotopic Stages and sub-stages are indicated by red numbers (1~5.4), and the Chinese Interstadials are marked in black numbers (A1~A24). (Modified from Wang et al., 2008)

6. Conclusion

One rhinoceros tooth fragment and surrounding calcite layer were collected from a

fissure in the Dawung rockshelter, one of the Punung fauna sites in Java. Combined

ESR/U-series dating on the tooth yields an apparent age of 162 ± 17 ka within ±1σ. This

age is older than available TL/OSL age of the breccia (128 ± 15 ka, Westaway et al.,

2007), and also in disagreement with the warm humid climatic context of Punung fauna.

This overestimated age should be related to a poor estimation of the external gamma

dose rate from the sediment, which is the main component of the dose rate and has

could be easily underestimated. The unbalanced U distribution in the sediment and

unknown contribution of the bedrocks should have biased the laboratory measurement

of sediment gamma dose rate.

The U-series dating age of the calcite cementation is ~ 126 1412 and coincides with

the luminescence age. This age provides minimum and close age estimation for the

tooth, and indicates a pre-optimal-Last-Interglacial immigration of the Punung fauna.

There should have already arisen rainforest development on the landbridge, which

allowed the Punung fauna (plausibly with human) to enter the Java Island before it was

submerged by the sea level transgression before 126~128 ka. This assumption is not

contrary to the extant studies about the sea level change and vegetation change in Java

Island.

Two stalagmites representing two human occupation floors were collected from

upper Terus layer of Song Terus Cave. A set of high-resolution MC-ICPMS and

conventional alpha spectrometric dating results yielded from the two stalagmites are

partly disordered. We consider that the deviation is caused by some unknown

75

alternation inside the sample rather than laboratory or dating method bias. According to

the statistic consistency of the dating results, the stalagmites are dated back to 91 ~ 84

ka (ST06) and 91 ~ 82 ka (ST05) respectively, indicating that human occupations in the

upper Terus layer of Song Terus cave have happened approximately from late MIS 5c to

early MIS 5a.

In order to precise the climatic context of the stalagmitic growth, two δ18O records

are yielded on these two stalagmites. The correlated δ18O and δ13C give some

probability to the occurrence of kinetic fractionation. The comparison of these records

with the Chinese-cave-based records is performed based on their variation trend and

amplitude. ST06 is perfectly coherent to the BD22 record around 89.5~ 87 ka,

corresponding to the GIS 22 warm period; ST05 likely corresponds to the beginning of

GS 22 cold period, about 86.5~ 85.5 ka.

Thus, the comparison shows a preliminary coherence between stalagmites isotopic

records in AISM area and EAM area in millennium time scales at around Greenland

Interstadial 22 and confirms the crystallization equilibrium conditions for the two

stalagmites. The chronology coincidence verifies and restricts the ages yielded from

statistic consistency of the U-series data, and suggests a still humid condition in Java

during the MIS5b stadial. The stalagmites of Song Terus Cave kept growing not only in

the GIS 22 warm period, but also in the following GS 22 cold period. During the

cooling transition from GIS22 to GS 22, there was a short time interval without

stalagmite growth and human occupation in the cave.

As future works, performing combined ESR/U-series dating on more dental

samples, especially with in-situ dose measurement in the field would get more precise

and direct age of the Punung faunal assemblage in Dawung rockshelter, and more

sufficient studies on sea level and vegetation change in this region would make the

context of faunal migration before optimal Last Interglacial more clear. The abundant

stalagmites in the Song Terus cave are valuable foundation to yield chronological and

paleoclimatic information with higher resolution for the human occupation and

paleoclimate reconstruction.

76

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