Faculty of Physics and Astronomy

University of Heidelberg

Diploma thesis
in Physics
submitted by
Bente Philippsen
born in Heide, Germany

2008

Hard Water or High Ages?

14
C food crust analysis on Mesolithic pottery
from Northern Germany
This diploma thesis has been carried out by Bente Philippsen
at the Institute for Environmental Physics
under the supervision of Prof. Werner Aeschbach-Hertig.

Abstract
The aim of this thesis is the investigation of the hardwater effect and its implications for the dating of the
first occurrence of pottery in Northern Germany. The hardwater effect denotes the effect of a high carbonate
content of freshwater on radiocarbon dating: the dissolved minerals can lead to spurious, too high ages
of samples from freshwater systems. The possibility of the hardwater effect in food crusts on pottery is
investigated for two sites of the Late Mesolithic Erteblle culture. The first radiocarbon dates from the food
crusts from these sites were surprisingly high. I will examine if the pottery really is so old or if the hardwater
effect is responsible for this. The samples I thus have to analyze are very small. Instrumental development
was needed for the dating of these samples. On-line combustion combined with stable carbon and nitrogen
isotope measurements is developed to minimize the number of steps in the preparation and measurement of
a sample so a reduction of contamination may be achieved. Also the conversion of the CO2 from combusted
samples to graphite, the form of carbon in which the radiocarbon content can be measured, is examined and
some improvements are suggested and tested.

Abstract
Das Ziel dieser Arbeit ist die Untersuchung des Hartwassereffekts und seines moglichen Einflusses auf die
Datierung der fr
uhesten Keramik in Norddeutschland. Der Hartwassereffekt bezeichnet die Auswirkungen
eines hohen Karbonatgehalts von Fl
ussen und Seen auf die Radiokarbondatierung: die gelosten Minerale
konnen zu falschen, zu hohen Altern von Proben aus S
uwassersystemen f
uhren. Die Wahrscheinlichkeit
des Hartwassereffekts in Speiseresten auf Keramik, in der S
uwassernahrung zubereitet wurde, wird f
ur
zwei norddeutsche Fundstellen der sp
atmesolithischen Ertebllekultur untersucht. Die ersten Radiokarbondatierungen von Speiseresten auf Keramik dieser Fundorte ergaben erstaunlich hohe Alter. Ich werde untersuchen ob die Keramik wirklich so alt ist oder ob der Hartwassereffekt daf
ur verantwortlich ist. Die Proben,
die ich daf
ur analysieren muss sind sehr klein. Um diese sehr kleinen Proben datieren zu konnen, ist instrumentelle Weiterentwicklung n
otig. Zum Beispiel soll Fraktionierung minimiert werden. Die Verbindung der
Probenverbrennung mit der Messung von stabilen Isotopen wurde entwickelt um die Anzahl der Probenaufbereitungsschritte zu minimieren. Dieses kann zu einer Reduzierung von Verunreinigungen der Probe f
uhren.
Die Umwandlung des CO2 zu Graphit, der Form von Kohlenstoff in der der Radiokarbongehalt gemessen
werden kann, wird untersucht. Einige Verbesserungen dieses Prozesses werden vorgeschlagen und getestet.

Preface
The influence of the hardwater effect on pottery dating, the necessary methodological and instrumental
developments, and the influence the hardwater effect has on the dating of the first pottery in Northern
Germany will be presented in this thesis. The hardwater effect is the influence of dissolved carbonate on
samples from freshwater systems. It is a long-known and broadly accepted phenomenon. However, the
possibility of a hardwater effect in one sample type is still under debate. Food crusts on pottery in which
freshwater food such as fish was cooked could as well show spurious ages if the freshwater food came from
water systems with a high carbonate content. So far, this effect has not been agreed on. I have therefore
chosen two sites next to freshwater rivers in Northern Germany where a hardwater effect on food crusts
on pottery is probable. I have taken a large number of archaeological samples as well as examined recent
freshwater samples in order to obtain statistically significant results. As the food crust and fishbone samples
from these sites are very small, development in sample processing methods was necessary. A device combining
sample combustion for AMS 14 C dating with on-line stable isotope measurements was advanced and tested.
This device has the potential of reducing the number of steps in sample preparation, the contamination risk,
and the total sample size.
Due to various problems with the ion sources and tandem accelerator, some of the samples could not be
measured before this work had to be finished. A new ion source was constructed and it was planned that
my samples could be measured using this new ion source. Because of several delayals, it was not possible
to start the new ion source for standard 14 C datings before this thesis had to be finished. Therefore, the
old ion source was used for my samples. There are two disadvantages with that: First, the old ion source
is not able to produce enough ion beam current for dating when the samples are very small. Second, the
ion source is only optimised for samples graphitised with cobalt at 700 C. My small archaeological samples
could thus not be measured at all. Normal-sized samples graphitised with iron at 550 C are measured with
a far higher uncertainty than would be the case in the new ion source.

Working in the intersection of physics and archaeology

The topic lies in the intersection of physics and archaeology, an area which is also called archaeometry.
Archaeology is the study of the human past through material remains (Hayashida 2003).
Physics is the study of matter and energy and how they work with each other
(http://simple.wikipedia.org/wiki/Physics on February 26, 2008).
Archaeometry is thus the (e.g. physical or chemical) analysis of material remains to study the human past.
Archaeometry is another term for archaeological science and comprises different scientific technologies which
are applied in archaeology. This can be chemical and physical dating methods, provenance studies of artefacts, study of the distribution and use of artefacts, reconstruction of past landscapes, climate and environment, dietary studies of humans and animals, remote sensing and geophysical surveys, and conservation
techniques (Tite 2003a).
This work will deal with two aspects of science applied to archaeology: radiocarbon measurements for
dating and stable isotope measurements on food crusts for dietary studies. Instumental development
I

and examination of the existing sample preparation methods will form the physical part of the work. At
the same time, it will also deal with the archaeological background on a scientific basis, bearing in mind
the appeal of Dunnell (1993): The attraction, particularly from the physical sciences side, often seems
to be to the non-scientific archaeology of the Sunday newspaperss feature section, and there will be no
basis for integrating archaeometry and archaeology until archaeometrists focus their attention on scientific
archaeology. Tite (2003a) also emphasizes this fact: To ensure that archaeometry remains relevant to
archaeology, it is essential that only real archaeological questions are addressed. This in turn necessitates
the maintenance of a substantial dialogue between archaeometrists and archaeologists together with a holistic
approach that goes beyond reconstruction to a full interpretation within the specific archaeological context
under investigation. On the other hand, archaeologists should be careful not to depend too much on
scientific dates. It is tempting to use for example radiocarbon dates as a calendar for prehistory, thus giving
archaeologists the role of historians. But it has to be kept in mind that reporting the archaeological phase
of a site is often more useful for comparing findings in a larger region than expressing the time horizon in
centuries BC. Absolute chronology may be the aim of archaeology, but it must never be the backbone in a
way that a calendar is the backbone of history (Fischer 1976).
The topic presented in this thesis was especially interesting to me as I had gained insight both in physics
and prehistoric archaeology in my studies. During archaeological studies and in physics projects, I could
learn about physical dating methods and especially radiocarbon dating. In archaeology, I specialized in the
Neolithic in Northen Germany and South Scandinavia, particularly in the Mesolithic-Neolithic transition.
This made it easier for me to take both the physicists and the archaeologists point of view when discussing
the sites I examined and their importance in the cultural development of the region. I hope therefore that I
can avoid some of the possible mistakes that happen when two differnent disciplines meet.

Outline of thesis
The first chapter presents an overview over the methods applied. After an introduction to the basic principles
of AMS radiocarbon dating and stable isotope analyses I will describe the method of pottery dating. In the
second chapter, I will present the development of enhanced techniques for the preparation of small samples.
The third chapter will deal with the sites from where I got the samples as well as their geological and
archaeological background. In the same chapter, the events being dated in this thesis will be put into the
context of cultural development at that time. The fourth chapter will finally deal with the archaeological
samples and the recent test samples which all were used to determine the hardwater effect for the two rivers.
Many of the physical terms may be unknown to archaeologists and, the other way round, physicist are likely
to be unfamiliar with the archaeological terms. A glossary at the end of this thesis may contribute to a
better understanding for specialists of both fields without lengthening the text.

Acknowledgements
First of all I would like to thank the AMS 14 C Dating Center of the University of Aarhus and its director,
Jan Heinemeier, for a warm welcome and the opportunity to work on an exciting topic. I was in the
fortunate position to benefit both from the laboratorys equipment and its know-how as well as from its
contacts to scientists of other disciplines. The laboratory technicians Hanne Jakobsen, Ann-Berith Jensen
and Vibeke Jensen taught me how to use the equipment, helped me patiently whenever I was confronted with
problems. Together with the graduate students Torben Ankjr and Christina Maria Lutz they created a
good working atmosphere. With Marie Kanstrup, I had inspiring discussions about archaeological and
stable-isotope related matters. Egon Jans and Klaus Grossen helped me to build up the new graphitisation
system. Klaus Bahner, although constantly nagging about adverse conditions, measured my samples in the
best possible way at the accelerator together with his team of accelerator operators. Prof. Dr. Claus von
Carnap-Bornheim, director of the Archaeological Museum of Schleswig-Holstein in Schloss Gottorf, paid 30
of the datings and the foundation Prof. Werner Petersen-Stiftung in Kiel, Germany, provided the funds

II

for this. The choice of the topic gave me the chance to interdisciplinary co-operation with the team of
archaeologists from the Archaeological Museum. Sonke Hartz was an enthusiastic co-worker and made the
finds from Schlamersdorf available to me. He also organized the pottery experiments together with Harm
Paulsen and Aikaterini Glykou and introduced me to a number of helpful people: Manfred Pfeiffer from
Neustadt (Holstein) provided the equipment for the fishing attempts in the Alster. Dr. Rainer Brinkmann
from Schlesen and Dr. Mattias Brunke from Flintbek helped establishing the contact to Dipl.-Biol. Dennis
Grawe and Dipl.-Ing. Markus Vainer from Institut BIOTA GmbH who finally caught fish for us in the Alster.
Winfried Dobbrunz from Bad Oldesloe provided us with fish from the Trave. A very warm thank you is
addressed to all the archaeologists from Schleswig for receiving me and my project so cordially. My dear
friend Birte Kruse provided a home for me during my visits to Schleswig and accommodated me even when
I returned from the pottery experiments, sooty and smelling of smoke. My flatmate Oline Laursen made
sure that I was well provided with victuals for long days at the university and that it always was nice
to come home. This thesis was supervised by Prof. Werner Aeschbach-Hertig in Heidelberg. He provided
theoretical knowledge both about the physical aspects of this thesis and about the formalities of a diploma
thesis. Henrik Kjeldsen was my supervisor in
Arhus and helped me with all technical and theoretical aspects
of my work. I want to thank him for support and encouragement throughout the time of research and writing
as well as for interesting scientific discussions. I want to thank my parents who made it possible for me to
study a subject of my own choice and who supported me at all times. As English is not my native language
I am thankful for all the help I received concerning the language - both grammar and spelling as well as
choice of words and the correct use of expressions. The dict.leo.org-community provided a great database
of English expressions and fine nuances of acceptations of words as well as surprisingly fast answers to all
my questions about the English language. Christopher Dege supported me in all my plans and was always
the first reader of my texts. He helped me a lot with critical statements from a linguists point of view and
corrected most of the errors in my manuscript. He was also very helpful in all questions concerning the
typesetting system LATEX which was used for producing this paper. I am solely responsible for all remaining
errors.

III

Contents
1 Methodology
1.1 Radiocarbon dating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.1.1 The history of radiocarbon dating . . . . . . . . . . . . . . . . . . .
1.1.2 Error sources and correction factors in radiocarbon dating . . . . . .
1.1.3 Dendrochronology and the calibration of the radiocarbon time scale
1.2 Accelerator mass spectrometry (AMS) . . . . . . . . . . . . . . . . . . . . .
1.2.1 Reporting of 14 C data . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2.2 Reservoir Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2.3 How the hardwater effect works . . . . . . . . . . . . . . . . . . . . .
1.2.4 The hardwater effect in archaeological material . . . . . . . . . . . .
1.3 Isotopic fractionation and stable isotope analysis . . . . . . . . . . . . . . .
1.3.1 13 C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.3.2 15 N . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.4 Food residues on pottery . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.4.1 Terminology and general remarks on prehistoric pottery . . . . . . .
1.4.2 Dating of pottery . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.4.3 Analyses on food crusts . . . . . . . . . . . . . . . . . . . . . . . . .

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1
1
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12
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29

2 Small sample preparation

2.1 Sample pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2 Graphitisation of small samples . . . . . . . . . . . . . . . . . . . . . .
2.2.1 Experiments with the existing graphitisation system . . . . . .
2.2.2 Establishing a new graphitisation system with smaller reactors
2.2.3 On-line combustion with EA measurements . . . . . . . . . . .

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31
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48

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3 The sites
56
3.1 Geography and research history . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
3.2 Geology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
3.2.1 Water hardness and 14 C in the Trave and Alster . . . . . . . . . . . . . . . . . . . . . 60
3.3 Erteblle and Funnel Beaker culture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
3.3.1 EBK research history and Kkkenmddinger . . . . . . . . . . . . . . . . . . . . . . . 61
3.3.2 The environment of the Erteblle culture . . . . . . . . . . . . . . . . . . . . . . . . . 62
3.3.3 The Erteblle economy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
3.3.4 Erteblle pottery and tools . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
3.3.5 Transition to farming: From Mesolithic to Neolithic or from Erteblle to Funnel Beaker
culture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65

IV

4 The samples from Schlamersdorf and Kayhude

4.1 Selection and pretreatment of samples . . . . . . . . . . .
4.1.1 Water samples . . . . . . . . . . . . . . . . . . . .
4.1.2 Recent fish and molluscs . . . . . . . . . . . . . . .
4.1.3 Recent food crusts . . . . . . . . . . . . . . . . . .
4.1.4 Old food crusts . . . . . . . . . . . . . . . . . . . .
4.1.5 Bone . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2 Dating and stable isotope measurement results . . . . . .
4.2.1 Recent samples from the river Trave . . . . . . . .
4.2.2 Archaeological samples from Schlamersdorf (Trave)
4.2.3 Recent samples from the river Alster . . . . . . . .
4.2.4 Archaeological samples from Kayhude (Alster) . .
4.2.5 Comparison with marine samples . . . . . . . . . .
4.3 Comparison of the sites, discussion and conclustion . . . .

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Chapter 1

Methodology
In this thesis, I have worked with two physical methods which are routinely applied to archaeological research.
The first is radiocarbon dating, a physical dating method that is based on the radioactive decay of the 14 C
atom. The second is stable isotope measurement, in this case carbon (13 C) and nitrogen (15 N). Stable isotope
measurements are used for examining the marine, terrestrial, or freshwater origin of archaeological samples
and for food reconstruction of prehistoric populations. Both methods will be presented here, including their
historical development, the principles, applications, and limitations.

1.1

Radiocarbon dating

Radiocarbon or 14 C dating is a method of age determination of the last uptake of carbon in a sample, for
example in the form of carbon dioxide from the atmosphere. Therefore, it is in principle suitable for the
dating of all organic material. The method can also be used for some inorganic material like carbonates that
are formed from atmospheric CO2 . Radiocarbon dating makes it possible to examine ancient cultures from
all over the world which before could not be dated. A reason for the lack of dates can be that writing was
not known in that culture as is, by definition, the case in all prehistoric cultures. Other reasons include that
the writing is not yet deciphered as for Maya Yucatan and Etruscan Tuscany or that time was unimportant
in an otherwise literate culture such as in India (White 1976). In a culture where time is unimportant,
no dates are bequethed. Radiocarbon dating is probably the technique that has had greatest impact on
archaeology, of particular importance being the investigation of the chronology for the development and
spread of agriculture across the world (Tite 2003a). The introduction of radiocarbon dating as a dating
method for archaeology was therefore called radiocarbon revolution.
Carbon has three isotopes, 12 C, 13 C, and 14 C. The Carbon-14 isotope is radioactive with a half-life of
5730 years. Because of this constant decay rate, it is possible to use 14 C for the measurement of the time
that passed since 14 C was last uptaken by a sample. 14 C decays in the reaction
14

14

N + + .

As time passes, the amount of 14 C decreases while the amount of 14 N increases. The 14 N is here marked with
an asterisk to indicate that it is radiogenic, i.e. originating from the radioactive decay of another element.
For calculating an age, one could therefore measure both the 14 C- and 14 N -amount present in a sample. The
more 14 N there is present compared to 14 C, the more time has passed. Unfortunately, the concentration of
the decay product 14 N in a sample can not be measured. 14 N is ubiquitous as atmospheric air consists to
78% of nitrogen, and 99.634% of natural nitrogen atoms are 14 N. The small amount of 14 N being formed in
a sample is, as all nitrogen under standard conditions, in gas phase. It thus mixes with atmospheric nitrogen
and can not be separated from the 14 N that is present everywhere on earth.
The fact that 14 C decays with a constant rate, can nevertheless be used for measuring time. This becomes

clear when we take a look at the exponential decay law that describes the decay of radiocarbon (equation 1.1).
t

N = N0 e .

(1.1)

From this equation, the time since the last uptake of carbon can be calculated. When the initial concentration
of 14 C, N0 , and its mean life is known, time since death t can be calculated from the following equation
after measuring the present 14 C concentration N :
t = ln

N0
.
N

(1.2)

This equation is derived from the decay law. The mean life of radiocarbon has been measured with sufficient
precision. The present 14 C concentration in a sample can be measured with methods which are discussed
below. Thus, only the initial 14 C concentration of the sample, N0 , is missing before we can calculate the
age of a sample. How is it possible to find the initial 14 C concentration, that was present in a sample an
unknown time ago?
Dating is made possible because the 14 C-content of the atmosphere is reasonably constant. The atmospheres 14 C content in the past can thus be deduced from its recent 14 C content. This constancy is due to
the way of 14 C formation: The radioactive decay is compensated by the constant production of 14 C by cosmic
rays in the upper layers of the atmosphere through the reaction 14 N(n,p)14 C. There is thus an equilibrium
between formation and decay which results in a reasonably constant 14 C concentration in the atmosphere.
The formation of 14 C is here described in more detail: A neutron which is produced by cosmic rays reacts
with Nitrogen-14 which consists of 7 protons and 7 neutrons to form a Carbon-14 nucleus with 6 protons and
8 neutrons, and a proton. 14 C is the radioisotope with the highest atmospheric production rate: 2.2 atoms
cm2 sec1 (Kocharov 1992). About 2/3 of the 14 C production take place in the stratosphere and about 1/3
in the troposphere. Through the following reaction, 14 C and an oxygen molecule O2 react to CO2 :
14
14

C + O2 14 CO + O2
CO + OH 14 CO2 + H

It resides for about 10 years in the stratosphere. In the form of CO2 , the 14 C is being distributed throughout
the atmosphere and then for example built in by plants through photosynthesis. During its life, an organism
incorporates carbon from this well mixed atmospheric reservoir. This is how the constant atmospheric 14 C
concentration leads to a constant 14 C concentration in a living organism. When the 14 C content of a living
plant is measured now, we can assume that a plant living at any time in the past had the same 14 C content
while it was alive. With the organisms death, the carbon uptake ends and the 14 C that decays is not being
replaced by new 14 C. So, the 14 C content of the sample decreases according to the exponential decay law
(equation 1.1, see figure 1.1).
After these explanations, it is clear how the initial 14 C concentration N0 of a sample is estimated. In
reality, though, the situation is a little more complex than it was described here, because there are variations
in the production rate of 14 C. How these variations were discovered will be described in section 1.1.1. These
variations in atmospheric 14 C do not nullify the method of 14 C dating, as one can correct for them. How
this correction is made will be described in section 1.1.3.
Now the method of measuring the present 14 C concentration in a sample has to be discussed. The
concentration of 14 C can either be measured directly via accelerator mass spectrometry (see section 1.2) or
indirectly via decay counting. This is referred to as the conventional method. In the first case, N and N0
denote concentrations of 14 C; in the second case, they denote activities. The 14 C concentration of a sample
is measured as the 14 C/13 C ratio when accelerator mass spectrometry is used. Details will be presented later
in section 1.2. For decay counting, the number of 14 C atoms that decay per time unit is measured. The
number of decaying 14 C atoms is proportional to the total number of 14 C atoms present in the sample. With
measuring the mass of the sample, one can convert the measured number of 14 C atoms to a concentration,
the 14 C/12 C ratio. In both cases, one can not be sure to have counted all 14 C atoms that are present in the
sample. The measured 14 C concentration in the sample is thus being compared to the 14 C concentration of
a standard material with known age. If for example only 10% of the samples 14 C atoms can be detected,
2

Figure 1.1: The radioactive decay of

14

then also only 10% of the 14 C atoms in the standard material can be detected. The limited detection ratios
cancel thus each other out. Section 1.2.1 describes in detail how the age of a sample is calculated from the
measured 14 C concentrations of the sample and the standard.

1.1.1

The history of radiocarbon dating

After the basic principles of radiocarbon dating have been explained above, I have now chosen a historical
perspective to shed light on the development from the discovery of 14 C to the routine measurements of
today. It will be shown that some of the basic assumptions stated above have proven inaccurate, but that
this always led to new knowledge and only made the method of radiocarbon dating more reliable in the end.
An overview over the early years of radiocarbon dating is given by Suess (1992). A lot of the information
presented here as been extracted from his work.
The first list of radiocarbon ages for unknown samples appeared in 1951 (Arnold and Libby 1951) after
the idea had been proposed by Willard Libby in 1946. Two key points lead to the state of knowledge which
provided the basis for 14 C dating. On the one hand, the unstable 14 C carbon isotope was discovered in
1937 (Ruben and Kamen 1941). It was observed that it was produced by cosmic rays and that it had a
half-life between 1,000 and 25,000 years, thus fitting archaeological time scales (Korff and Danforth 1939).
Later, the half-life was determined more precisely to 5568 years, which was used for the first datings. This
half-life had finally to be specified over again: In 1962, a more precise half-life of 14 C was determined - 5730
instead of 5568 years. Even though the half-life was not known exactly, the theoretical knowledge about the
14
C atom and its deccay was hence available in the 1940s. On the other hand, a few weak counting sources
had been constructed, and Libby had invented the screen-wall counter. The practical basis was consequently
also given. Note that this counter measured radioactiviy. It was thus capable of measuring the number of
decaying 14 C atoms and give the activity of a sample. From 1952 to 1955, 7 radiocarbon dating laboratories

were established. One of them has to be named specifically: In 1953, the USGS (US Geological Survey)
Radiocarbon Dating Laboratory started work with acetylene counters under the leadership of Hans E. Suess
and carried out 200 measurements in the first two years. Their most important results were the dating of
the maximum extent of the North American ice sheet, the result that Homo neanderthalensis survived in
selected areas until about 30,000 years ago and the Suess effect which was named after its discoverer. The
Suess effect is the anthropogenic drop in 14 C activity in air which occurred during the industrial revolution,
when 14 C-free CO2 from fossil-fuel combustion was added to the atmosphere. This drop in atmospheric 14 C
concentration is one of the reasons for the fact that the initial 14 C concentration of a sample in the past is
not the same as the present 14 C concentration.
In 1959, de Vries demonstrated the variability of atmospheric 14 C over the past centuries. The atmopheric
14
C concentration is thus not only altered by the Suess effect, that diluted the 14 C concentration, but there
are additional variations. Those variations are called wiggles. In 1971, Houtermans found out from 350
radiocarbon samples that had been dendrochronologically dated that these radiocarbon variations correspond
to a line spectrum with a prominent 200-year line. It took a long time until the existence of those wiggles
were widely accepted, and still they are not fully understood. Dendrochronology is the method of tree ring
dating. This method provides samples of a known age for testing radiocarbon dating - just as Houtermans
did. When 14 C-dating a tree ring of known age, one can therefore calculate the atmospheric 14 C activity of
the time when the tree ring was formed. When this is done for a long stretch of time reaching back in the
past, one can give the initial 14 C activity for each year. The plot of this information is called the calibration
curve, as it can be used for calibrating a measured 14 C concentration to obtain a calendar age. This will be
described in section 1.1.3.

1.1.2

Error sources and correction factors in radiocarbon dating

As mentioned in section 1.1.1, the 14 C concentration of the atmosphere is not completely constant. The
variations in 14 C production that cause the above-mentioned wiggles are due to variations in sun activity
and the earths magnetic field that affect the cosmic radiation. As the cosmic radiation produces neutrons
that, together with 14 N, form 14 C, the 14 C production rate varies according to the variations in cosmic
radiation intensity. Two other important effects are anthropogenic: The Suess effect that was described in
section 1.1.1 and the bomb pulse. The Suess effect is the depletion of 14 C in the atmosphere because of the
combustion of fossil, 14 C-free fuels since the industrial revolution.
The bomb pulse(see figure 1.2) denotes the increase of 14 C in the atmosphere after H-bomb tests during
the 1960s up to twice the normal activity in the mid-1960s and its decrease since then. The 14 C concentration
in the present atmosphere is decreasing exponentially, but with a much smaller half-life than the 14 C half-life
of 5730 years. Not only the decay of 14 C reduces the atmospheric 14 C concentration. The excess 14 C is
also incorporated in the biosphere and in the oceans and so gradually removed from the atmosphere. The
mean life of this decay is around 17 years, so that its half-life is approximately 12 years. Because of this
rapid decrease, the high 14 C concentrations in samples from the last few decades can be used as a tracer
and for high-precision radiocarbon dating (see e.g. Lynnerup, Kjeldsen, Heegaard, Jacobsen, and Heinemeier
(2008)).
Variations in the initial 14 C activity or content can be calibrated with radiocarbon dating of tree rings of
known age. The plot radiocarbon age over calendar years is called the calibration curve. Unfortunately, in
some periods there are ambiguities in that curve, so that it can not be decided which calendar age a certain
14
C concentration belongs to. Calibration will be explained in section 1.1.3.
As we have seen so far, some basic assumptions were made for radiocarbon dating. These are summarized
in the following list (after Browman (1981)):
1.

14

C decays exponentially at a known rate, and the initial measurement of that rate, Libbys half-life
of 556830a, is adequate enough to make reasonable computations of age
2. activity or 14 C content can be measured with acceptable accuracy
3. secular constancy of 14 C concentration in the atmosphere at one point of the earth
4. simultaneity: the 14 C concentration is the same for any two points on the earths surface

Figure 1.2: The bomb pulse in atmospheric CO2 and in the dissolved inorganic carbon in near-surface
seawater. The annual total testing is given in megatons (Clark and Fritz 1997).
5. the atmosphere is the only source of carbon in living organisms
6. isotopic integrity after organisms death, no material added, 14 C/12 C changes only by radioactive decay
7. all organisms are in isotopic equilibrium with the atmosphere i.e. no fractionation occurs
But we have also seen that these assumptions are not completely appropriate, so corrections have to be
applied:
1. the half-life of 14 C is 573040 a instead of 556830 a, and as data is still published with Libbys
half-life, ages have to be multiplied by 1.029
2. background corrections and measurement of standards for setting up the instruments; compensation
of differences between laboratories because of differences in preparation and evalutation of data
3. calibration curve (see section 1.1.3) because of long term variations, caused by geomagnetic field intensity, and short term variations, heliomagnetic modulation of 14 C production, of the atmospheric 14 C
content, which is additionally altered by the Suess effect and bomb tests
4. latitude and altitude effects: samples from the southern hemisphere are 40-80 years older than those
from the north. Because of different reservoir exchange ratios, the ocean surface on the southern
hemisphere is bigger.
5. water plants and animals take carbon from the water; error sources and corrections: see section 1.2.2
6. contaminants that entered the sample after the organisms death have to be removed
7. fractionation takes place on all steps of the food chain, beginning with photosynthesis and has to be
corrected through 13 C/12 C measurements (see section 1.3)

1.1.3

Dendrochronology and the calibration of the radiocarbon time scale

Because of the wiggles in the atmospheric 14 C content (see section 1.1.1 and 1.1.2), the assumption of a
constant atmospheric 14 C concentration is wrong and the radiocarbon ages have to be calibrated to correct
for the variations in atmospheric 14 C content. For calibrating the radiocarbon ages, one needs samples of
known age. Mostly, dendrochronologically dated wood is used for that. The calibration curves used for the
correction of the radiocarbon ages are generated by plotting the wood radiocarbon ages versus the calibrated
(cal.) ages. After a description of dendrochronology and a short overview over its history, the history of
its application for calibration of radiocarbon ages will be given. The spectrum of the variations will be
explained as well as the impact calibration had on archaeology.

Dendrochronology, or tree ring dating, is still the most precise dating method for archaeology. When there
is a sufficient number of rings (100-150 for oak) and the bark ring is preserved, a dating precision of 0.5 to 1
year can be achieved. With preserved sapwood, the precision becomes 5-30 years, but when only heartwood
is preserved, dendrochronology gives a terminus post quem for the felling of the tree. Dendrochronology
was the only scientific method of precise dating until radiocarbon dating was invented. The first successful
attempts of dendrochronological dating were made by A. E. Douglass in 1906. In 1953, conifers in the White
Mountains of California were found that were older than 4000 years, so that Edmund Schulman, a co-worker
of Douglass, was able to construct an unbroken 4600-year sequence. Since a 7104-year tree-ring record was
presented by C. W. Ferguson in 1969, dendrochronology became important not only for dating but also for
examining the long-term variations of atmospheric 14 C and for geophysical research. In 1957, Hessel de Vries
began measuring dendrochronologically dated wood samples after natural variations of the atmospheric 14 C
level were reported by K. O. M
unnich from German oak samples dated by Bruno Huber. The variations are in
the order of magnitude of about 120h (Sternberg 1992). J. C. Houtermans used methods of Fourier analysis
in his above-mentioned work for calculating a spectrum of the variations. He suggested both an approx.
200- and 2000-year period. Later research has supported these suggestions and added other frequencies, for
example a periodicity of 10,000 - 12,000 years, to the spectrum (Sternberg 1992). Although some of the
shorter periods (11, 88, and 210 years) have been identified with solar activity (Damon and Jirikowic 1992),
the radiocarbon spectrum is by no means fully understood (Sonett 1992). The variations are so hard to
understand because there are many possible sources interacting. They influence either the production of 14 C
in the atmosphere or cause changes in the carbon/radiocarbon geochemical system (Sternberg 1992):
Radiocarbon is produced when neutrons produced by cosmic rays interact with 14 N in the atmosphere; thus, it is affected by the galactic primary cosmic-ray flux, modulation of this flux by the
heliomagnetic field and by the geomagnetic field, or by production due to solar cosmic rays. Systematic changes include changes in geochemical reservoir sizes or exchange rates between them,
or in the amount of 14 C in the reservoir or system as a whole.
Unfortunately, the variations in the radiocarbon production are not reflected unaltered in the radiocarbon
content of tree rings: 14 C studies require the consideration of complex transport processes damping out
fast processes and shifting the phase (Kocharov 1992).
The introduction of calibration had such a big impact on dating that it is called the second radiocarbon
revolution. The second radiocarbon revolution involved the re-interpretation of European prehistory
following the introduction of calibration curves, when events in Europe were found to be earlier than (not
just uncomfortably close to) their supposed progenitors in the Near East (Tuniz, Zoppi, and Barbetti 2003).
On the basis of conventional 14 C dates it had previously been assumed that European prehistoric cultures
generally postdate Middle East cultures (Becker 1992).
It has to be paid attention that calibration is applied in the right way, appropriate to the event being
dated. When dating one event by dating many samples associated with that event, the samples have to be
calibrated together. When the samples are calibrated individually, the age distribution for the event becomes
broad, and it becomes the broader the more samples are measured (Ottaway 1986).

1.2

Accelerator mass spectrometry (AMS)

We have witnessed two revolutions so far: The first radiocarbon revolution was the introduction of radiocarbon dating. The second radiocarbon revolution was the introduction of calibration and the re-interpretation
of datings. There is a third event which is called a radiocarbon revolution: the introduction of accelerator
mass spectrometry. For understanding why this is a revolution, we have to remember that radiocarbon
in the first decades was done via decay counting (see section 1.1.1). Only the 14 C atoms decaying during
the measurement period could be detected. The sample masses required for this technique were about 1 g
carbon. Although 1 g of carbon already is a small amount, not all types of samples could be dated. The
carbon yield of different sample materials differs a lot, so that in some cases far more than only few grams

of original sample were needed. Very small samples could thus not be dated, and some other samples are
too valuable for allowing the removal of for example 100 g sample material.
In a modern sample, the average fraction of 14 C decaying per day equals only 3.3 107 of the amount
present. If the number of 14 C atoms present could be counted instead of only the number of decaying ones,
the sample size could be reduced drastically. This is exactly what accelerator mass spectrometry does. It
is in principle a very easy technique: The carbon atoms are extracted as ions from the sample, they are
accelerated, separated from each other, and counted. The separation and counting of isotopes of different
masses is called mass spectrometry. This is where the name accelerator mass spectrometry comes from: it
is a mass spectrometric measurement with the help of an accelerator. The accelerator is needed to produce
high enough ion energies to make a separation of different ions with almost equal masses possible.
First of all, we will follow a 14 C atom on its way from the sample to the final detector for showing how
AMS works in principle. Background levels and precision of AMS will be addressed after that. The impact
of AMS on archaeology and its advantages over decay-counting will be explained thereafter. A short history
of AMS will end this section. A lot of the information presented here can be found in Gove (1992).
From sample to detector
All laboratories have their specific design of an AMS setup. I will try to explain the principles as general as
possible, but when more details are needed, I will refer to the setup that is installed at the 14 C AMS dating
laboratory at Aarhus University. In summary, the carbon ions are extracted from the sample, accelerated
with 0.5-10 MV, separated according to their momentum, charge and energy and finally counted by an ion
detector after identification by nuclear mass and charge. Accelerator mass spectrometry must be able to
separate nuclides of almost equal mass, sort out interfering molecules and measure the abundances of ions
in different orders of magnitude.
The sample is placed into the ion source in the form of elemental carbon, i.e. graphite. A beam of caesium
atoms is targeted at the sample which causes negative carbon ions to leave the sample surface. They are
accelerated towards a positive electrical potential. The most important mass-14 component that disturbs
the 14 C measurement is already removed: 14 N does not form negative ions and is therefore not present in
the ion beam.
When the ions are formed, they have different energies. The ion energy is the sum of the energy they
obtained from the acceleration towards the positive potential, which is equal for all of them, plus the kinetic
energy they obtained from the ionization. Only ions with the right energy are desired to enter the accelerator.
The ion beam is therefore electrostatically deflected. Only ions with the desired energy E are moving on the
trajectory of radius r:
E
M v2

(1.3)
r =
Q
Q
with M = nuclear mass, Q = charge, v = velocity and E = energy of the ion and = electric field. The
kinetic energy of an ion is E = 21 mv 2 .
We have thus obtained a beam of ions with equal energy. Ions with mass 12, 13 and 14 are now selected
for sequential or simultaneous injection into the accelerator. The so-called injection magnet selects the ions
with the desired mass. In a magnetic field, ions are deflected according to equation 1.4.
ME
(Br)2
Q2

(1.4)

E
with B = magnetic field. Only ions with a specific M
Q2 are deflected to the circular path with radius r. As all
ions have the same charge (-1 from the ion source) and as the above-mentioned electrostatical filter selected
ions with equal energy, one can also say, Only ions with a specific mass are deflected to the circular path
with radius r. With varying the magnetic field intensity B, one can now chose between the ions with mass
12, 13, or 14. As this magnet is used for injecting beams of ions of different masses, it is called injection
magnet. Many AMS laboratories cannot accelerate the large 12 C currents and only inject mass 13 and

Figure 1.3: A negative ion beam enters the tandem accelerator, loses electrons in the stripper material and
leaves the accelerator with a charge of 3+.
13
14. The mass-14 beam consists mainly of 12 CH
CH . 14 C is present in this mass-14 beam, but its
2 and
percentage is negligible as the other carbon isotopes are far more abundant.
The ion beam enters now the accelerator. Tandem accelerators are used in this case. The negative
ion is attracted by a positive potential in the middle of the accelerator. Typical acceleration voltages are
2MV for Tandetrons and 6MV for Van de Graaff accelerators. In the middle of the accelerator, a so-called
stripper material is installed. Collisions with the stripper material, gas or foil, remove several electrons, so
that the resulting carbon ions are positively charged. +3 is the most common case for 2MV acceleration
and +4 for 6MV. Figure 1.3 shows a sketch of the tandem accelerator. When losing 3 or more electrons,
13
molecules are not longer stable. 12 CH
CH , for example, are removed from the mass-14 beam. The
2 and
stripper removes thus the interfering molecules. After the accelerator, another magnetical analysis (after
equation 1.4) is necessary: Charge Q and energy E of the ions is different due to the electron stripping and
acceleration. Also the mass M of some constituents of the ion beam can be different, as molecules were
destroyed.
Velocity selectors or Wien filters consist of magnetic and electric fields at right angles to each other and
perpendicular to the direction of the incident ions so that only ions with a specific velocity are not displaced:

v2 = 2

EM
2 B 2
Q2

(1.5)

Afterwords, the ions have to be counted. More abundant isotopes can be counted in faraday cups. These
are devices that just measure the charge that accumulates on them. Less abundant ions are counted with
particle detectors. These have an additional advantage: The rate of the energy loss dE/dx identifies the
nuclear charge Z:
dE
Z2
2
(1.6)
dx
v
The identification of the nuclear charge is only possible when the abundances of the different ions are limited.
When plotting the count ratio of a particle detector, a picture similar to figure 1.4 emerges. The final energy
is the total energy minus the energy loss. One would expect that only 14 C enters the particle detector so
that only a 14 C peak could be observed. This is not the case because ambiquities can occur. It is for example
possible that particles that are removed from the ion beam again enter the beam after small-angle scattering
on residual gas particles (i.e. on gas particles that are not removed although the system is evacuated). In
figure 1.5, the whole procedure for the mass-14 beam is summarized.
Precision and background
High-quality AMS measurements can reach a precision in pmC determination of about 0.2 to 0.3%. The
accelerator background, that is the amount of 14 C atoms that are registered although the sample is 14 C
8

Figure 1.4: Count ratios of

final energy.

14

N,

12

C,

13

C and

14

C in a particle detector as a function of total energy and

Figure 1.5: Following the mass-14 beam through the AMS measurement procedure

free, can go down to a 14 C level according to 60-70,000 years. Dating is normally limited by the chemical
preparation background to 50,000 years but can be better with special techniques (Tuniz, Zoppi, and Barbetti
2003). There are different background sources in different steps of the sample preparation and measurement
process after Kirner, Taylor, and Southon (1995):
1. Machine background:

14

(a) Detector anomaly:

C detected when the sample is

14

C pulse registered when no

14

14

C-free

C ion is present

(b) Ion identification anomaly: particle of same mass/energy ratio as

14

C reaches the detector

(c) Beam-line contamination

2. Combustion/acidification background
(a) Materials contamination from materials in the combustion/acidification tube
(b) Tube contamination
3. Graphitisation background
(a) Materials contamination (e.g. catalyst)
(b) Reaction tube contamination
4. Pseudo

14

C-dead sample background

(a) Sample erroneously assumed to contain no

(b)

14

14

C introduced into material that contains no

14

Detector anomalies, or electronic noise, can be measured by collecting a spectrum for several days without
injecting any particles into the accelerator (Beukens 1992). Charge recombination in the detector creates
a tail from the 12 C and 13 C peaks which underlies the 14 C peak. Nuclear physics techniques of spectrum
analysis can be used to cope with this problem of a tail, but the reduced statistical precision limits the
background level (Beukens 1992).
The ion source can also introduce contamination, because only about 10% of the samples carbon atoms
is turned into negative ions and the remaining 14 C atoms are deposited somewhere in the ion-source region (Beukens 1992).
Kirner, Taylor, and Southon (1995) also observed that the way of sample storing has an effect on the
background value. A geologic graphite sample that was powdered and encapsulated under argon had a 14 C
age of 69,000 BP while samples of the same material that were powdered and encapsulated in air had ages of
58-60,000 BP. The materials contamination from graphitisation could for example been estimated by pressing
pure catalyst into a target and then measuring it in the accelerator. The disadvantage of this method is
that the ion beam current in this case is too small and instable for a general statement (Vandeputte, Moens,
Dams, and van der Plicht 1998).
Impact on archaeology and advantages over decay-counting
The most important background in decay counting, the cosmic radiation, is thus eliminated in AMS. It was
anticipated in the beginning of AMS that the background reduction could make the dating of samples up
to 100,000 years old possible. This is not the case, though, because contamination-free samples can not be
prepared (Kirner, Taylor, and Southon 1995). The introduction of AMS reduced the required sample masses
with a factor of approx. 1/1000 and is therefore sometimes called the third radiocarbon revolution (Tuniz,
Zoppi, and Barbetti 2003). Samples that before were too small or too valuable could now be dated. It is now
for example possible to select only the best samples from a skeleton, minimizing problems with degradation
and contamination. When a bone is reasonably preserved, 14 C dating and stable isotope analysis is possible
without destroying the object (Arneborg, Heinemeier, Lynnerup, Nielsen, Rud, and Sveinbjornsdottir 1999).

10

Only the capital costs and the greater complexity of AMS hardware (Gove 1992) have so far prevented
AMS from completely supplanting decay-counting facilities, although the number of AMS laboratories is still
increasing.
The development of AMS had a strong impact on archaeology, alone by the reduction of required sample
mass to 1/1000 (Harris, Grove, and Damon 1987). A reduction of sample mass in conventional measurements,
the use of small-counter facilities, had the disadvantage of long measurement times: several days for one
sample. AMS with measurement times about half an hour to a few hours per sample is thus much more
effective. The small required sample mass makes it possible to date objects that were too small or too
valuable to be dated with the conventional method. Especially when dating the introduction of agriculture
in different areas, AMS is the only possible dating method that can directly date the key material, single
cereal grains. Those plant remains are too small to be dated conventionally and too mobile to be dated
stratigraphically or via associated finds (Harris, Grove, and Damon 1987).
The advantages of using an accelerator for 14 C mass spectronomy are the following:
no interference with 14 N because it does not form negative ions
the samples are smaller and more easily prepared than for decay counting
it is possible to accelerate all 3 C isotopes, so in principal both the date from
well as additional information from 13 C/12 C is available

14

C/12 C or

14

C/13 C as

It is possible to measure other radionuclides beyond 14 C with the accelerator. The advantage of AMS is
that it can detect long-lived cosmogenic radioisotopes in the presence of vastly larger quantities of their stable
isotopes. Many radionuclides which are produced in measurable amounts in the atmosphere or environment
have decay constants matching temporal scales relevant to the history of hominidae (Tuniz, Zoppi, and
Barbetti 2003). While 14 C can reach 50,000 years ago, when Homo sapiens sapiens started colonizing vast
regions of our planet, can 10 Be and others reach back to 5 million years when Australopithecus appeared. The
different detectable radioisotopes can not only be used for dating. A plenitude of applications in hydrology,
geoscience, materials science, biomedicine, sedimentology, environmental sciences and many other fields
emerged as soon as the AMS detection capabilities of the appropriate isotopes were demonstrated. One
example is the measurement of water flow rates with the 36 Cl bomb pulse: 36 Cl was produced in nuclear
weapon tests in the 1950s by neutrons interacting with the chlorine in the seawater. It was injected into the
biosphere at a level which was two orders of magnitude above the pre- and postbomb test ambient levels.
History of AMS
In 1977, two independent approaches using particle accelerators were taken, one with a cyclotron and one with
a tandem Van de Graaff electrostatic accelerator. In May 1977, 14 C in an organic sample, barbecue charcoal,
was measured via AMS for the first time. The team at the University of Rochester (USA) demonstrated
that negative 14 N ions are unstable (Gove 1992). Thus, the most important disturbing factor in 14 C mass
spectronomy, the 14 N isotope with nearly the same mass, could be eliminated. NH molecular ions are the
only nitrogen species left after the negative ion source (Beukens 1992). Only three weeks later after this
success, another group from the Canadian Simon Fraser University detected 14 C in a AD 1880-90 wood
sample at McMaster Universitys accelerator, also in Canada. Purportedly, neither the Rochester nor Simon
Fraser group was aware of the other groups efforts at that time. It could be said that the time was just
ripe for the development of AMS, after the first accelerator mass spectrometric detections of 3 He already
took place in 1939 and the tandem accelerator employing negative ions had been invented by Luis Alvarez
in 1951 (Gove 1992). Anyway, is took some time until a tandem accelerator was used for 14 C dating. It
was shown in 1977 that if three or more electrons are removed from a neutral mass 14 molecule like 12 CH2 ,
the molecule dissociates in a Coulomb explosion and the resultant fragments are swept aside before reaching
the final detector. Thus, another source of interferences with 14 C could be eliminated. For these first
attempts of AMS radiocarbon dating, existing accelerators were used, but later small tandem accelerators
were specifically designed for AMS, because the high terminal voltages of the big accelerators were not
necessary. At the end of the 1970s, 14 C was measured with completely acceptable sensitivity using small
tandem accelerators with terminal voltages around 2 MV, because all that was required was a negative ion
11

energy high enough to have a reasonable probability of producing charge 3+ ions in the terminal stripper to
ensure the elimination of mass 14 molecules. The first AMS 14 C datings were made in 1978.

1.2.1

Reporting of

14

C data

Stuiver and Polach (1977) developed guidelines for the reporting of 14 C data that still are in use. The
following remarks about calculating and reporting of 14 C data can be found in their article. To find out
which measured 14 C activity or concentration belongs to which age, standard materials of known age have
to be measured. To ensure that results from different laboratories are comparable, all should use the same
standard material. Now, all laboratories report their data either directly related to NBS [Natural Bureau of
Standards] oxalic acid or indirectly by using a substandard which is directly related to the NBS oxalic acid.
The internationally accepted radiocarbon dating reference value is 95% of the activity in 1950 AD of the NBS
oxalic acid normalized to 13 C=-19h PDB (see section 1.3.1 for an explanation of 13 C fractionation and the
-notation). The activity of this standard does not change, because it is the activity measured in a certain
year (1950 AD), although the activity of oxalic acid is changing with time. It is called absolute international
standard activity, AISA. Most laboratories use the activity AON , which is 95% of the measured net oxalic
acid activity / count rate:
2(19 + 13 C)
).
(1.7)
AON = 0.95AOX (1
1000
The expression in brackets accounts for fractionation. The factor 2 considers that fractionation for 14 C is
about twice the fractionation for 13 C. As AON depends on the year of measurement, y, it has to be corrected
for decay between 1950 AD and the year y of actual counting date. The absolute international standard
activity AISA is thus
Aabs = AON e(y1950)
(1.8)
1
with = 8267
years1 . is based on the 5730 years half-life. Terrestrial samples are normalized to 13 C =
-25h VPDB, the postulated main value of terrestrial wood:

ASN = AS (1

2(25 + 13 C)
AS 0.9752
.
) which is an approximation of the more precise ASN =
13 C
1000
(1 + 1000
)2

(1.9)

For the calculation of the radiometric age of a sample, the assumption is made that the atmospheric 14 C
level was constant in all past times and that is by definition equal to Aabs after normalizing to -25h. The
age t of a sample it thus
t = 8033 ln

ASN (1950)
with a half-life of 5568 years and thus a mean life of 8033 years.
AON (1950)

(1.10)

t is independent from the year of measurement, because both sample and oxalic acid lose their 14 C at the
same rate. The years calculated with this formula are called conventional radiocarbon ages in years BP
(before present) with present = 1950 AD.
Another method of giving radiocarbon values is percent modern carbon, pmC:
pmC =

ASN
ASN
100% =
100%.
Aabs
AON e(y1950)

(1.11)

1
Here is y the year of oxalic measurement and = 8267
a1 is based on the 5730 a half-life. The pmC
ASN
is sometimes defined differently, as AON 100% without the factor correcting for decay since the year of
measurement. For archaeological samples, there is almost no difference between the two definitions of pmC,
as the time since measurement is negligible compared to the age of the sample. However, when reporting for
example biomedical samples, it should clearly be stated if the correction for decay since measurement has
been applied or not.

12

The relation between the conventional radiocarbon age t and absolute percent modern carbon pmC is
t+

y 1950
pmC
= 8033 ln
1.03
100

(1.12)

The above calculations belong to measurements of the 14 C/12 C ratio. With accelerator mass spectrometry
(see section 1.2), the 14 C/13 C ratio is measured, and some of the equations have to be adjusted to that fact.
In equation 1.7 for example, the factor 2 is not longer necessary if the 14 C/13 C ratio is measured. The factor
was only introduced in that equation to account for the fact that fractionation between 14 C and 12 C is about
twice the fractionation between 13 C and 12 C. We can assume that the fractionation between 14 C and 13 C is
approximately the same as between 13 C and 12 C. In equation 1.9, the factor 2 of the approximated expression
can be left out because of the same reason. This means that in the exact expression in equation 1.9 the
13
C ) not longer has to be inserted quadratically. This means that the measurement error in
factor (1 + 1000
13
C determination only has half the influence on a date that is obtained measuring the 14 C/13 C ratio. If
the error in the 13 C value for example is 1%, then the age error will be 160 years if the measurements are
based on 14 C/12 C ratios. The same 13 C error will only lead to an age error of 80 years if the measurement is
based on 14 C/13 C measurements. The usual precision of mass spectrometric measurements of 13 C is about
0.1h. The squared 13 C ratio in the 14 C/12 C = ASN formula 1.9 leads to a factor 2 in the age error as the
logarithm of a squared value is twice the logarithm of that value. The age is calculated using the logarithm
of the ratio, see equation 1.10.
The 14 C/12 C ratio of a sample can be expressed in the following way:
(

14
13
14
13
13 CS
14
)S = ( )S ( )S = ( )S ( )V P DB (1 +
).
12
13
12
13
12
1000

The same is true for the 14 C/12 C ratio of the oxalic acid standard. The pmC of a sample after
measurement is thus expressed as
pmC =

25
( 14
1 1000
1
13 )S
( 14
)
)(
13
0.9558
( 13 )Ox
1 + CS

(1.13)
14

C/13 C

(1.14)

1000

1.2.2

Reservoir Effects

The above explained principles of radiocarbon dating only work when the samples obtain their carbon
from the well-mixed atmospheric carbon reservoir or other parts of the earth which are in balance with the
atmosphere. Otherwise is it not possible to estimate precisely the initial 14 C concentration in an unknown
sample with the measurement of a limited number of modern materials (Broecker and Walton 1959). In
terrestrial material, depletion or enrichment in 14 C is only due to isotopic fractionation. In material of
different origin, 14 C depletion can be caused by the long residence time carbon has in the reservoir the
sample comes from. Carbon is in the following way distributed to different reservoirs: the oceans, storing
93% of the total carbon, the biosphere (5%), and the atmosphere (2%). The atmosphere is thus the smallest
global carbon reservoir. The average atmospheric CO2 concentration is 360 ppmv and its partial pressure is
105.5 . The 13 C value of the atmosphere was originally around -6.4h but is now decreasing due to burning
of fossil fuels (Clark and Fritz 1997). In the case of a reservoir with a different radiocarbon content than
the atmosphere, corrections of the initial radiocarbon content or activity have to be applied. Otherwise,
spurious ages would be obtained. The effect the 14 C content of a certain reservoir has on the 14 C age of a
sample is called reservoir effect.
There are different types of reservoirs which cause problems in radiocarbon dating. One is the oceans,
leading to the marine reservoir effect, the other is freshwater with considerable amounts of 14 C depleted
carbon, leading to the freshwater reservoir effect. A lower 14 C activity can also be expected in the neighbourhood of fumaroles where old CO2 is released (Olsson 1976b).
The marine reservoir effect is a well-known and broadly accepted phenomenon. Water that wells up from
the deep parts of the ocean has long been cut off from the atmospheric carbon cycle and contains therefore
13

old CO2 with a low 14 C content: The ocean can be divided into two parts, the surface water and the deep
water. Both are well mixed individually, and there is little exchange between them. In ocean water, the
13 C value of dissolved inorganic carbon is 1h, so that there is a difference of 26h between the atmosphere
with 13 C = -25h and the ocean (fractionation and the -notation will be explained in section 1.3.1). A
difference in the 13 C/12 C ratio of 26h means a difference of approximately 52h or 5.2% in 14 C/12 C, so that
the ocean, compared to the atmosphere, should have a 14 C activity of 105.2% (Lanting and Van der Plicht
1996). Rapid exchange with the atmosphere, though, only takes place in the surface water, so that these
considerations do not apply to the deep ocean. There is 102 times as much deep water as surface water. In
average, the proportion of carbon that circulates down into the deep water is about 102 times as great as
that which rises up. The 14 C in the deep water has more time to decay and thus the activity of deep water
is less than the activity of surface water (Olsson 1976b). Via photosynthesis, plants incorporate the carbon
from this CO2 . From the phytoplankton via the zooplankton and fish, this old carbon finally also ends
in food for animals living on land. One example are recent polar bears from Svalbard and East Greenland
who had 14 C ages of 48070 and 49545 years, respectively. The same effect can be found in humans - a
person who eats much fish will naturally have lower 14 C activity than a person who eats mainly terrestrial
food (Olsson 1976b). This effect perhaps is conserved as a charred residue in a cooking pot, when the fish
had been cooked. The radiocarbon age of this food residue now is older than its actual age.
Corrections of the marine reservoir effect are made by subtracting the reservoir age of the ocean from
the measured radiocarbon age of the sample. The reservoir age is about 400 years for the North Alantic
according to measurements and model calculations; see Stuiver, Pearson, Branziunas (1986). Reservoir ages
of different parts of the oceans can vary strongly depending on sea currents and local seabed/coast shape.
The age differences between surface ocean and atmosphere are generally greater at high latitudes than in
the tropics (Gillespie and Polach 1976). For finding out if a sample has marine origins that necessitate
reservoir corrections, the content of the stable carbon isotope 13 C is measured. 13 C values differ significantly
for organic material of marine and terrestrial origin. When 14 C dating human bones, the percentage of
marine food has to be estimated for calculating a marine reservoir correction. One example is the stable
isotope analysis and 14 C dating of Greenland vikings. The endpoint for a 100% terrestrial diet of 13 C =
-21h is easy to find as there are many populations who solely live on terrestrial products. The endpoint for
a 100% marine diet is harder to find because no human population a priori can be expected to have a 100%
marine diet (Arneborg, Heinemeier, Lynnerup, Nielsen, Rud, and Sveinbjornsdottir 1999). Therefore, the
13 C value of -12.5h of the most marine individuals that the authors were aware of, Thule culture Eskimos,
was used. The 13 C value of the viking bones is an indicator of the percentage of marine food and thus of
the extent of reservoir correction that has to be applied. When correcting the 14 C dates in this way, the
ages of the human bones fit well historically assumed ages and the ages of associated terrestrial material like
textiles. In this case, a simple linear mixing model could be applied as the population on Greenland mainly
lived on proteins from meat and dairy products because agriculture was not possible in the cold climate on
Greenland (Arneborg, Heinemeier, Lynnerup, Nielsen, Rud, and Sveinbjornsdottir 1999).
There are different sources of 14 C depleted carbon in freshwater environments. The most important is the
dissolution of geologic carbonates, which because of their high age are almost 14 C free. Other explanations
include inputs of old soil humus, residence time of for example ground water in an aquifer, or vital effects
of the species studied (Culleton 2006). Carbon can also be dissolved from rocks other than carbonates, for
example from vulcanic glasses. This accounts for example for high reservoir ages in Icelandic groundwaters
although there are no carbonaceous rocks on Iceland. The effect of CO2 from the decomposition of vulcanic
glasses can be corrected with measuring the boron concentration in the water, as carbon and boron are
orsson 1995). In
released in stoichiometric relation from the glass (Sveinbjornsdottir, Heinemeier, and Arn
lakes with a large depth to surface ratio in combination with good wind protection, the CO2 exchange ratio
between the atmosphere and the lake water is low and can also lead to a 14 C depletion in the water (H
akansson
1976).
If the 14 C depletion of the freshwater system is caused by dissolved bicarbonates and carbonates, the
freshwater reservoir effect is also called hardwater effect. The water hardness is defined as the concentration
of the alkaline earth metal ions, predominantly calcium (Ca) and magnesium (Mg). They originate often

14

from carbonates. The water hardness is therefore an indicator of the carbonate concentration and thus of
the amount of 14 C-dead material in the water. Hard water can be found in regions where limestone and
sandstone are dominating.
The effect of dissolved bicarbonates on the radiocarbon age has already been anticipated during the first
radiocarbon datings, when Godwin (1951) examined dates from British lake deposits:
Too great an age may result from introduction of inactive Carbon, as with bicarbonate derived
from ancient limestones, brought into a lake, where it is fixed in organic compounds or precipitated
through biological activities.
In 1954, Deevey et al. examined a hardwater lake and dated water samples as well as plant samples, also
from terrestrial plants. The water samples had an apparent age of 2200 years, and also the clams and plants
from the lake which use bicarbonate as a carbon source had comparable ages. Deevey, Gross, Hutchinson,
and Kraybill (1954) conclude: Great care must be clearly be exercised in the future when material from
highly calcareous regions is being examined.
In 2006, B. J. Culleton measured paired samples of charcoal and shells from lake sites in California
and found a 340 years discrepancy between them as well as a greater variability of ages among the shells
than among the charcoal. This might be an evidence for genus-specific reservoir corrections, maybe based
on habitat differences (Culleton 2006). A freshwater reservoir effect also explains the difference between
archaeological and radiocarbon-based chronology for the Catacomb cultures of the North-West Caspian
steppe (Shishlina, Van der Plicht, Hedges, Zazovskaya, Sevastyanov, and Chichagova 2007). Seeds and
fishbones that were found in the same grave had an age difference of 64060 14 C-years, and the 15 N values
of human bone indicated that aquatic protein accounted for 70% of the total protein supply so that a reservoir
correction of about 400 years has to be made for the human bone radiocarbon dates. More examples for the
freshwater reservoir effect in archaeological material will be given in section 1.2.4.
The occurence of the hardwater effect on food crusts on pottery was first proposed in 2003 (Fischer and
Heinemeier 2003). The results of Fischer and Heinemeier (2003) have been doubted, though. Apparently, the
number of dated samples was small enough to explain the age difference between terrestrial and freshwater
samples with statistical methods so that the hardwater effect was not necessary as an explanation. Instead
of a real radiocarbon age difference, Hart and Lovis (2007) explain the measured values with a single outlier
and statistical variations. The basics of the hardwater effect will be explained in section 1.2.3.
In coastal areas as for example the Danish fjords, a mixing of two carbon reservoirs can be observed:
the marine and the freshwater reservoir. Danish Baltic Sea areas like the Skagerrak-Kattegat and the Belts
show the same reservoir age as the North Sea and North Atlantic: about 400 a (see a description of the
marine reservoir effect above). In contrast to that, the Danish fjords have higher and more scattered ages
between 400 and 900 years and are thus not part of the uniform marine reservoir. The variability in the
reservoir ages of the fjords can best be explained with different concentrations of old dissolved carbonate in
the soil (Heier-Nielsen, Heinemeier, Nielsen, and Rud 1995).

1.2.3

How the hardwater effect works

The mechanisms leading to the hardwater are explained in Clark and Fritz (1997) and Fontes and Garnier
(1979) where a lot of the information presented here can be found. Normally, there is no reason for dating
river water, because its age is known as modern. It is only used for estimating the hardwater effect that
influences the age of freshwater organisms. Most research in order to understand the mechanisms that
produce the high water ages has therefore been done in the area of groundwater dating. Groundwater
dating is an important part of water resources management. For human use over a long period of time, only
groundwaters that are recharged constantly provide sustainable solutions. Using groundwaters that are not
actively recharged is mining (Clark and Fritz 1997), because the groundwater reservoir will be exhausted
after a certain period of water extraction. Dating the water is a method to decide whether a groundwater
reservoir is actively recharged or not.
The hardwater effect makes it complicated to date groundwaters because the disolved carbonate makes
the initial activity of the water smaller than 100 pmC. pmC is the abbreviation for percent modern carbon
15

and is a measure of 14 C activity. 100 pmC is the activity of the atmospheric carbon before the beginning of
the bomb tests. For estimating the correct initial 14 C activity, model calculations had to be done and the
mechanisms of solution and transport of the different carbonaceous species had to be understood. Groundwater dating is therefore an important field of study also regarding the hardwater effect in other freshwater
systems. The measurement of the tritium content of a groundwater is a possibility for deciding if the water
is affected by the hardwater effect. The half-life of tritium is only 12.26 years so that tritium-containing
groundwater must be post-bomb, i.e. relatively young water. A hardwater effect in groundwater has for
example been reported by Boaretto, Thorling, Sveinbjornsdottir, Yechieli, and Heinemeier (1998) from Hvinningdal in Denmark. Tritium values showed that the water was post-bomb water, but its 14 C content was
30 to 100 pmC.
There are two sources of dissolved carbon in groundwaters and so two sources for an explanation of
high 14 C ages in young water: relatively active carbon comes from the soil zone and less active carbon is of
inorganic origin. The carbon of inorganic origin is itself a mixture of active carbon from soil gas CO2 and
old carbon from carbonate in the subsurface. It is also called DIC, as an abbreviation for dissolved inorganic
carbon. This will be described first. Later, I will explain the effect of DOC, which means dissolved organic
carbon. DOC and DIC 14 C values can differ significantly in groundwater, with DOC in most cases being
younger, but are often in the same order of magnitude (Long, Murphy, Davis, and Kalin 1992). DOC can
in single cases also lead to a spurious, too young radiocarbon age of the water, when young DOC enters
old water. Carbon transformations are linked through acid-base and redox reactions which are most often
mediated by bacteria (St-Jean 2003). Bacteria act as catalysts and can in these cases influence isotopic ratios
because they prefer to break the looser molecular bonds. The hardwater effect is expected to be greater
in running, i.e. river water, than in stagnant water like lake water. If there is not a noticeable meltwater
component, river water consists largely of groundwater (Lanting and Van der Plicht 1996). This is another
reason why groundwater research methods are being discussed here. The definition of DIC comprises four
species:
Carbon dioxide CO2
Carbonic acid H2 CO3
Bicarbonate anion or hydrogencarbonate HCO
3
Carbonate anion CO2
3
The first two species, CO2 and carbonic acid, are often summed up as CO2 because the carbonic acid only
exists in aqueous solution. The bicarbonate anion HCO
3 is an amphoteric substance. That means, it can
both act as acid and base because it both can donate and accept protons. Bicarbonate is the conjugate base
of carbonic acid H2 CO3 and the conjugate acid of the carbonate ion CO2
3 :

H2 CO3 + 2OH
HCO
CO2
3 + 2H2 O
3 + H2 O + OH

+
+
H2 CO3 + 2H2 O HCO3 + H3 O + H2 O CO2
3 + 2H3 O

(1.15)

2
The concentration of HCO
3 and CO3 together is called carbonate alkalinity. Alkalinity denotes the concentration of dissolved species which act as proton acceptors and buffer pH, i.e. consume acidity.
In the soil, root respiration and the decay of organic material release CO2 . In contact with water, a
small amount of this CO2 forms carbonic acid (H2 CO3 ) which can dissolve lime from the surrounding rock.
The dissolved lime hardly contains any 14 C because of the high age of the lime stone. Carbonic acid is the
predominant acid in natural waters and most responsible for rock weathering (Langmuir 1997). Water plants
convert CO2 and water to glucose and oxygen and use the glucose as an energy source and a basic material
for other organic matter. When an extensive amount of the CO2 in the water has a high age, then the plant
will accordingly show a spurious, high radiocarbon age. Correspondingly, fish that feed on these plants and
humans that eat these fish, will also show too old radiocarbon ages. This effect could also be transferred to
the food crusts on pottery in which a considerable amount of aquatic food was cooked. This freshwater part
of the carbon cycle will be examined more detailed below.

16

Figure 1.6: The pathway and associated fractionation of 14 C and 13 C in CO2 during photosynthesis, respiration in soils, and dissolution by groundwaters (Clark and Fritz 1997).

17

Fresh groundwater originates exclusively from precipitation, which in most cases percolates through soil
and geosphere. The CO2 in the root zone, which is dissolved by rainwater, has a recent 14 C activity
and its 13 C is approximately -25h. The amount of CO2 that can dissolve depends on temperature, initial
water pH and the partial pressure of CO2 . Although rainwater contains some CO2 from the atmopshere,
the groundwaters radiocarbon signal is dominated by the carbon from the soil zone. In the deeper subsoil
exchange takes place between this dissolved CO2 and fossil marine carbonate (e.g. limestone) which has
no 14 C activity and 13 C = +1h (see above). When finally equilibrium is reached, CO2 in groundwater
has only half the recent 14 C activity and its 13 C is c. -12h (Lanting and Van der Plicht 1996). Other
processes like the dissolution of extra CO2 and exchange processes in the unsaturated zone can alter the
14
C and 13 C concentrations additionally. To correct the measured 14 C concentration, the 13 C value of the
water can be measured. If assuming that fossil carbonate has a 13 C value of about 0h and CO2 from the
root zone has -25h, the corrected 14 C activity of the water is
Ad = Am

25
13 C

(1.16)

with the measured activity Am . The activity Ad has now to be taken to calculate the age, as the uncorrected
measured activity Am would overestimate the age (Boaretto, Thorling, Sveinbjornsdottir, Yechieli, and
Heinemeier 1998). The 14 C age measurement can also be corrected by estimating the initial 14 C activiy Ain
that originates from the dilution of the atmospheric activity Aatm with fossil carbonate:
Ain = Aatm

13 Cm
25

(1.17)

Boaretto, Thorling, Sveinbj

ornsd
ottir, Yechieli, and Heinemeier (1998) discovered that Am is correlated
with the oxygen concentration of the water. One can therefore assume that besides the dissolution of
carbonates, the oxidation of old organic carbon in the soil dilutes the 14 C concentration, as will be explained
below when discussing DOC.
The existence of a three phase system consisting of gaseous CO2 and aqueous and solid carbon allows significant isotopic exchange. Isotopic exchange is for example represented by the following reaction:

14
12
14
14
CO2 +H12 CO
C contents significantly higher than
3 CO2 +H CO3 . This process is responsible for
those indicated by the single dissolution process in modern groundwater. It is known since M
unnichs research in 1957 (Fontes 1992). Each stage of the series of chemical reactions is isotope fractionating: when
CO2 gets dissolved in water, when it forms carbonic and bicarbonic acid and when the CO2
forms solid
3
carbonate. Furthermore, each single compound will exchange with the other coexisting carbon species. However, because of differences in reaction rates and large variations in the relative amounts of coexisting carbon
species, isotopic exchange reactions may not reach equilibrium for each compound.
The inorganic carbon is mainly controlled by acid-base reactions. The distribution of the three species
2
of dissolved inorganic carbon, CO2 (dissolved CO2 ), HCO
3 (bicarbonate ion) and CO3 (carbonate ion),
is largely a function of pH (St-Jean 2003). The three DIC species are related in the following pH controlled
chemical equilibrium:
+
2
CO2 + H2 O H2 CO3 H+ + HCO
(1.18)
3 2H + CO3
The most important component of inorganic carbon in natural waters is bicarbonate. It is produced in
the reaction CO2 + H2 O + MeCO3 Me(HCO3 )2 with Me = Ca2+ , Mg2+ or 2Na+ . Dissolved CO2 or
carbonate, depending on the pH, generally accompanies bicarbonate in the unsaturated zone and in the
aquifer. The higher the CO2 concentration is in the soil atmosphere, the lower is the initial pH. The low
pH is then buffered by mineral weathering in soil and upper bedrock. The most common and most effective
buffering reaction is calcite dissolution with Me = Ca2+ in the reaction above. Carbonate dissolution is often
automatically considered as an index of 14 C dilution and reported as hardwater effect. But single examples
show exceptions from this general rule (Fontes 1992) so that the measurement of the water hardness is not
sufficient to trace the dilution of 14 C content in the water.
Carbonate is not the only mineral that gets dissolved in natural waters; silicate is another important
component. There is a major difference between carbonate and silicate dissolution regarding the 14 C/12 C
18

of DIC. For systems in contact with the atmosphere, each equivalent of Ca, Mg, Na, and K ions dissolved
from silicate minerals is accompanied by the addition of 1 mole of atmospheric CO2 (see equation 1.20).
For carbonate, 1/2 mole of atmospheric CO2 is added to the system for each equivalent of Ca and Mg
dissolved so that 1/2 of the total CO2 is 14 C-free while the other half has atmospheric concentration (see
equation 1.19). In contrast to that, no 14 C-free HCO
3 is added in the case of silicate solution (Broecker and
Walton 1959). The only change to the carbonate system is the increase in pH that is associated with silicate
dissolution. This increase in pH shifts the distribution of DIC species to the HCO
3 field. If this occurs
under non-saturated conditions in an open system, additional CO2 will be dissolved from the soil zone. In
any case, the DIC from silicate weathering is derived solely from soil CO2 .

CaCO3 + H2 O = Ca++ + HCO

3 + OH

OH + CO2 = HCO3
CaCO3 + H2 O + CO2 = Ca++ + 2HCO
3

(1.19)

In the following example of silicate dissolution, the plagioclase feldspar anorthite CaAl2 Si2 O8 is dissolved.
CaAl2 Si2 O8 + H2 O = Ca++ + 2OH + Al2 O3 + 2SiO2
2OH + 2CO2 = 2HCO
3
CaAl2 Si2 O8 + H2 O + 2CO2 = Ca++ + 2HCO
3 + Al2 O3 + 2SiO2

(1.20)

These reactions are based on the assumption that nearly all the dissolved CO2 in fresh-water bodies is in
the bicarbonate ion form (Broecker and Walton 1959). After the bicarbonate is formed, its 14 C/12 C ratio is
controlled by the second factor, the exchange ratio of CO2 with the atmosphere. In igneous areas, silicate
solution is dominant so that the majority of dissolved bicarbonate has atmospheric origin. Rivers which are
flowing over sedimentary rocks dissolve both silicate and carbonate minerals (Broecker and Walton 1959).
The 14 C/12 C ratio of the dissolved bicarbonate in fresh waters is thus controlled by
1. the ratio of the amount of carbonate to the amount of silicate dissolved
2. the rate of exchange with CO2 in the atmospheric reservoir
CO2 exchange rates for rivers can be as high as 100 moles/m2 , whereas CO2 exchange rates in inland lakes
are about 5 moles/m2 (Broecker and Walton 1959).
Age distortion can also be introduced by dissolution of secondary calcite precipitated under open-system
conditions. Fractionation between dissolved HCO
3 and solid calcite is probably very small. When calcite
13
that emerged from dissolved HCO
C content of the
3 is than dissolved again, it is hardly noticeable in the
TDIC, and may lead to apparent aging of the TDIC (Fontes 1992). TDIC means total dissolved carbon.
Thus the age of the DIC changes without changes in the 13 C content that may indicate the age distortion.
One example for this overestimation of 14 C ages can be found in Aeschbach-Hertig, Stute, Clark, Reuter,
and Schlosser (2002). 14 C can further be diluted by sulphate reduction and methanogenesis, 2CH2 O CO2
+ CH4 .
CO2 produced from oxidation of organic matter most likely will alter the 14 C activity of the DIC as
CO2 is one of the DIC species, no matter what its origin may be. A lower pH that is associated with the
higher concentrations of dissolved CO2 will additionally dissolve calcite if present and so further alter the
14
C activity in the DIC (Long, Murphy, Davis, and Kalin 1992). As Boaretto, Thorling, Sveinbjornsdottir,
Yechieli, and Heinemeier (1998) noticed, is the 14 C concentration of the water after correction for carbonate
dissolution correlated to the oxygen content of the water. For estimating the extent of oxidation of old organic
matter in the soil, the highest measured oxygen concentration in the water body is taken as the initial oxygen
contentration [O2 ]i n. We assume that the missing oxygen was used for the oxidation of organic matter, Co rg
+ O2 = CO2 . The fraction F of the total inorganic carbon in the water that was derived from the oxidation
of organic matter is thus calculated to
F = 1.38

[O2 ]in [O2 ]

[CO2,total ]

19

(1.21)

where 1.38 is the ratio of the molecular weights. The

dissolution and organic carbon oxidation is thus
Acorr = Am

14

C activity of the water when corrected for carbonate

25
.
13 Cm + 25F

(1.22)

The dissolved organic carbon DOC is the result of decomposition of higher organic matter, such as
plants, in the soil. Its particle size is smaller than 0.45 m. Organic carbon with particle sizes bigger than
0.45 m can also be present in groundwaters and is called particulate organic carbon. The DOC originates
from chemical and physical changes in soil organic matter (SOM) that becomes soluble (St-Jean 2003) and
is stored in the soil waters. The concentration of DOC in soil moisture can reach a maximum of 10 to
100mgC/L in the root zone. This concentration drops off towards the water table. Groundwaters often
have less than 1 to 2 mgC/L DOC, although groundwaters in certain environments can recharge with much
higher DOC concentrations (Clark and Fritz 1997). DOC species comprise the so-called humic substances
that are responsible for the dark colour of soils and some waters. Humic and fulvic acid are both humic
substances and they are often the reason for contamination with younger carbon in archaeological samples.
DIC can be extracted from the water sample by acidifying it. The procedure used for my water samples
will be described in detail in section 4.1.1. DOC can be extracted afterwards when the DIC is removed.
One isolation technique for DOC is photo-oxidation, e.g. irradiating 2L of water with a 1200W UV-lamp
after adding Na2 S2 O8 to expedite oxidation. In another isolation technique, water is passed through a
series of columns packed with pre-cleaned resin materials to collect DOC of different sizes (Long, Murphy,
Davis, and Kalin 1992). In 10 to 120L filtered water, liquid chromatography separation of hydrophobic
substances, fulvic and humic acids, is possible (St-Jean 2003). Whatever method is used, DOC analysis is
regarded as difficult and time-consuming and requires large samples (St-Jean 2003). High molecular weight
substances, for example humic acids, are insoluble below a pH of 2. They precipitate when DIC is removed
by acidification, and that makes them more resistant to oxidation (St-Jean 2003).
When measuring the reservoir age of a water system, it has to be taken into account that the 14 C content
of the water can be subject to seasonal or secular changes. The dating of one water sample only, taken at
a special time, can therefore be not more than an estimate of the reservoir effect (Geyh, Schotterer, and
Grosjean 1998). Lakes are subject for the biggest changes because in them there is no continuous flow of
water. Bicarbonate for example is probably periodically concentrated in lakes by evaporation (Culleton
2006). A very slowly running river or a lake can regain recent activity due to exchange with atmospheric
CO2 . The extent of the hardwater effect is for example dependent on the surface-to-volume-ratio of a lake. It
is thus basically dependent on the water depth, as the surface of a lake with outflow only changes minimally
when the water depth decreases because of sedimentation (Geyh, Schotterer, and Grosjean 1998). The
reason for the dependence on the surface-to-volume-ratio is that exchange with the atmosphere only takes
place at the water surface while the dissolved inorganic carbon reservoir is proportional to the entire volume.
When thus the water depth decreases because of a rising of the lake ground due to sedimentation, the water
volume gets smaller while the lake surface still is the same. There is thus the same exchange with CO2
from the atmosphere while the total amount of dissolved inorganic carbon decreases with the decreasing
amount of water in the lake. Sedimentation in a lake is thus a reason for secular changes in the reservoir
age. Sedimentation could also cut off the supply of groundwater to the lake so that the amount of dissolved
inorganic carbon decreases that is transported with the groundwater into the lake.
Temporal changes in the hardwater effect are due to water temperature and biological activity. In late
summer, lakes are often thermally stratified with warm water in the upper layers and colder water in the
bottom of the lake. Towards winter, the upper layers cool down due to the sinking air temperatures until
their density exceeds that of the layers below, which are still a little bit warmer. Cool water from the upper
layers sinks thus down and the lake water gets mixed by this process. When water with different bicarbonate
concentrations gets mixed, an excess CO2 concentration builds up which increases during winter due to the
decomposition of organic matter. In spring, the upper water layers warm up and biological activity begins.
Inorganic carbon precipitates due to the biological removal of CO2 and to a lesser extend due to degassing in
the warm summer. This takes place in the upper layers of the lake where there is enough light for intensive
biological activity. Carbonate that was precipitated through this process reaches the lake ground only when
20

the water in the bottom layers is supersaturated with CO2 . Sedimentation takes thus mainly place at the
end of the warmer season. Total dissolved inorganic carbon (TDIC) and precipitated carbonate should be
in equilibrium, but as there can be more exchange with atmospheric CO2 the more carbon in the original
DIC reservoir is biologically removed, the 14 C value increases with decreasing carbonate sedimentation rate
(Geyh, Schotterer, and Grosjean 1998). The possible extent of the hardwater effect at the regarded sites on
the rivers Trave and Alster, respectively, will be described in section 3.2.1.

1.2.4

The hardwater effect in archaeological material

One example for the measurement of too high radiocarbon ages on human material is the Iron Gates region,
at for example the sites Lepenski Vir, Vlasac and Schela Cladovei (Cook, Bonsall, Hedges, McSweeney,
Boronean, Bartosiewicz, and Pettitt 2002). The measurement of human bone and associated charcoal or
ungulate bones showed an age difference of some hundred years. This difference, the reservoir age, comes
from the consumption of fish from the Donau. As protein is the only source of nitrogen in human bones
(see section 1.3.2), it is possible to reconstruct the percentages of riverine and terrestrial food that were
consumed with measuring the 15 N value of the bones. The stable carbon isotope 13 C is not so well suited
for this purpose because the carbon in bones can originate not only from the consumed proteins, but also
carbohydrates and lipids (Cook, Bonsall, Hedges, McSweeney, Boronean, Bartosiewicz, and Pettitt 2002).
13
C values reflect therefore not exclusively the meat consumption so that it is hard to differ between protein
sources from different reservoirs. In contrast to that, there is a linear relation between the 15 N value and
the proportion of freshwater, marine or terrestrial food. The relation between the 15 N value and the age
offset, which is caused by the consumption of freshwater food, is therefore linear, too (Cook, Bonsall, Hedges,
McSweeney, Boronean, Bartosiewicz, and Pettitt 2002). The 15 N value for the terrestrial diet end-member
is 8h, while 15 N for the aquatic resources end-member is 17h. A 15 N value of 15h that was found
for some individuals indicates so a diet with 79% aquatic protein: 0.79*17 + 0.21*8 15. As the average
reservoir age for those individuals was about 425 years, the reservoir age for 100% riverine food is expected
to be 540 years, as 540 * 0.75 425 (Bonsall, Cook, Hedges, Higham, Pickard, and Radovanovic 2004).

1.3

Isotopic fractionation and stable isotope analysis

All isotopes of an element have similar chemical properties and can for example form the same kinds of
molecules. They consist of the same number of protons. As atoms are neutral, isotopes of one element have
the same number of electrons, too. This is the reason for the similar chemical properties, as the electrons
are responsible for the formation of molecules. The name isotope consists of the Greek words isos=equal
and topos=place, because isotopes of an element are situated at the same position of the periodic table of
elements. The differences between the isotopes of one element are the mass and physical properties, because
the isotopes contain different numbers of neutrons. The mass of a 13 C atom is for example 8% greater than
that of 12 C, whereas 14 C is 17% heavier than 12 C (Browman 1981). Although the mass differences do not
change chemical properties totally, they can change reaction rates, because heavier isotopes are not as mobile
as lighter ones. Isotopic fractionation (in the following shortened to fractionation) is the enrichment of a
certain kind of isotope of an element. Evaporation, for instance, is a fractionating process, as the remaining
liquid is enriched with heavier isotopes. Fractionation is enlarged with a bigger mass difference. Therefore,
the extend of fractionation caused by isotopes of a certain element is the greater the smaller the molecules
are that contain this isotope. Fractionation between the different carbon isotopes is for example big when
CO2 diffuses into leaves, but is smaller for the transport of photosynthesis products like sucrose C12 H22 O11 ,
where the exchange of one carbon atom with another isotope does not affect the molecular mass so strongly.
I will restrict the following discussion of stable isotope measurements to the stable isotopes of carbon,
13
C, and nitrogen, 15 N. These stable isotopes are most used in archaeological research, and they are also the
ones I examined on my archaeological samples.
Stable isotope diet analysis began in the 1970s, after the different fractionation between C4 (in this case
maize) and C3 plants had been observed (Tykot 2003). Measurements of stable isotopes make it possible to

21

reconstruct past diets. A population that mainly lived on C4 plants is expected to have other 13 C values
in their bones as a population that mainly lived on C3 plants. There are also differences in the 13 C or 15 N
values in bones of populations that lived mainly on terrestrial or marine food, respectively. First, the stable
carbon isotope 13 C will be discussed.

1.3.1

13

The measurement of the 13 C value of a sample can be used for more than past diet reconstruction. Fractionation of carbon isotopes has to be taken into account for radiocarbon dating, because it influences the
14
C/12 C or 14 C/13 C ratio which is used for calculating the age. When measuring the 13 C content of a sample, one can estimate from this the extent of fractionation that affected the carbon. As the mass difference
between 14 C and 12 C is approximately twice the mass difference between 13 C and 12 C, one can assume that
fractionation affects 14 C twice as much as 13 C. The 13 C content of a sample is measured compared to that of
a standard and noted in the form 13 C = (13 Rsam 13 Rstd )/(13 Rstd ) 1000h where 13 Rsam and 13 Rstd are
the isotope ratios of the sample and of a standard, respectively. The standard most often used is Cretaceous
belemnite from the Peedee formation in southeast USA. It was formed during the Cretaceous period from
the fossils of the marine cephalopods Belemnoidea, in this case Belemnitella americana (Tuniz, Zoppi, and
Barbetti 2003)). So, 13 C values are reported in the -notation with respect to Peedee belemnite, abbreviated wrtPDB or just PDB. As the original PDB standard material is exhausted, newer measurements are
reported with respect to another standard: Vienna PDB, abbreviated VPDB. It was calibrated against
the standard material NBS 19, which also is a carbonate. The -notation is also used for the notation of
other isotope ratios, with the suitable standard for the particular isotope.
Fractionation processes of 13 C will be regarded in the following, beginning with atmospheric CO2 , and
ending in plants, animal and human bones, and soils. The fractionation mechanisms describes in the following
have similar effects on 13 C and 14 C, so that the 13 C fractionation can be used for correcting the 14 C age.
Informations about 13 C measurements and fractionation were taken from Lanting and Van der Plicht (1996)
and Clark and Fritz (1997), if not indicated differently.
The first big fractionation from atmospheric carbon takes place during photosynthesis, i.e. during CO2
diffusion into the leaf stomata and dissolution in the cell sap, and during carboxylation (carbon fixation)
by the leafs chloroplast, where CO2 is converted to carbohydrate (CH2 O). This results in a depletion of
13
C and 14 C. The degree of depletion depends on the photosynthesis pathway and results in a 5 to 25h
depletion of 13 C. The radiocarbon standard of 100 pmC for example is calibrated to wood that grew in
1890 and has 13 C=-25h. The 13 C value of atmospheric CO2 , prior to the combustion of fossil fuel, was
about -6.4h. The 13 C depletion in this case is thus 18.6h. The strong fractionation during photosynthesis
that causes this depletion of 13 C will also affect the 14 C. It is assumed that the fractionation for 14 C is twice
the fractionation for 13 C so that atmospheric CO2 was 37.2h enriched. If the mass factor of 2.3 instead of
2 is used that was determined by Sali`ege and Fontes (1984), the atmospheric CO2 was even 42.8h enriched.
The oldest photosynthesis pathway, called Calvin or C3 cycle, is particularly suited to wet and mesophytic,
i.e. moderately humid, environments (Browman 1981). It is called C3 cycle because the first product of
photosynthetic CO2 fixation is a 3-carbon-compound (Hibberd and Quick 2002). It operates in about
85% of plant species, including most trees and agricultural plants. Plants growing higher than 40 degrees
of latitude use exclusively the C3 cycle. The C3 cycle is the cheapest energy path for photosynthesis and
developed when the earths atmosphere contained more CO2 than today. C3 plants fix CO2 with the Rubisco
enzyme, which also catalyses CO2 respiration through reaction with oxygen. In the present days atmosphere
is CO2 respiration an inefficiency, only remaining as an artefact from development in an atmosphere with
high CO2 . Diffusion and dissolution of CO2 lead to a net enrichment in 13 C, whereas carbon fixation leads
to a 29h depletion. The 13 C values for C3 plants end up as -24 to -30h with an average of about -27h.
C3 plants are preferred by herbivores because they are more digestible. Overgrazing causes therefore plants
with other photosynthesis pathways to become dominant.
The more efficient C4 pathway evolved as atmospheric CO2 concentrations began dropping in the early
Tertiary. Under low CO2 :O2 conditions and at higher temperatures, increased respiration in C3 plants
interferes with their ability to fix CO2 . C4 plants add an initial step where the PEP carboxylase enzyme
22

Figure 1.7: Ranges for 13 C values in selected natural compounds (Clark and Fritz 1997)
[Phosphoenolpyruvate carboxylase] acts to deliver more carbon to Rubisco or for fixation. The name C4
comes from the 4-carbon-compound which is the first product of photosynthetic CO2 fixation. After its
discoverers, this pathway is also called Hatch-Slack cycle. C4 is a partly closed system and not able to
discriminate as completely against the more energy-expensive heavier isotopes as C3 . One could also say,
it is capable of using all isotopes and is therefore more efficient. C4 plants incorporate so a bigger ratio of
13
C and 14 C than C3 and appear too young when they are compared to contemporaneous wood samples.
They have 13 C values of -12.5h in average, ranging from about -10h to about -16h. 5% of plant species
are C4 plants. They dominate in hot open ecosystems such as tropical and temperate grasslands. Some
important agricultural plants like sugar cane, corn and sorghum are C4 plants. Some C3 plants might have
the potential to develop C4 photosynthesis, as recently was found out for tobacco. Cells which are far away
from the stomata through which atmospheric CO2 enters the plant are provided with CO2 from the cell
sap. These photosynthetic cells possess high activities of enzymes characteristic of C4 photosynthesis, which
allow the decarboxylation of four-carbon organic acids from the xylem and phloem, thus releasing CO2 for
photosynthesis. These biochemical characteristics of C4 photosynthesis in cells around the vascular bundles
of stems of C3 plants might explain why C4 photosynthesis has evolved independently many times (Hibberd
and Quick 2002).
Another photosynthesis pathway developed under water stress in arid regions: The Crassulacean acid
metabolism (CAM) cycle which is used by about 10% of plants. This pathway sometimes operates as an open
and sometimes as a closed system, determined by environmental conditions. Therefore, it is well adapted
to water-stressed environments. CAM plants have the ability to switch from C3 photosynthesis during the
day to the C4 pathway for fixing CO2 during the night. Many CAM plants can shift to a C3 -like mode of
photosynthesis when there is enough water so they can grow faster (Browman 1981). The 13 C values of
CAM plants span therefore the whole range of C3 and C4 plants, usually having intermediate values. In
figure 1.7, the ranges for 13 C values of different materials are given, including the atmosphere, plants with
different photosynthesis cycles, and soil CO2 .
Further fractionation takes place along the steps of the food chain, although 13 C values generally only
increase only with less than one permil (Schoeninger and DeNiro 1984). Even in different materials from the
same organism, different 13 C values can be found. An African browsing ungulate, for example, had a 13 C
value of -21.2h for the bone collagen, but -28.9h in the fat (Browman 1981). Proteins in tissues of the
23

consumer are derived from proteins in the food, and carbonate in bone apatite is derived from blood CO2
and ultimately from all energy supplying components in the diet, including excess protein. The carbonate
fraction therefore reflects the mean isotopic composition of the whole diet. Experiments with rats show
that 13 C values in bone collagen not only depend on the 13 C values of the protein in the food but also
on the amount of protein and on the difference in 13 C values of protein and non-protein fractions. The
13 C values in bone collagen could thus overestimate the amount of protein in the food, especially when this
contains small amounts of protein. The explanation is that proteins are used in the first place to produce
tissues like collagen, and are only used as energy suppliers in case of excess. This means that linear mixing
models, using values of 13 C in bone collagen of the consumer, and in the different components of the
diet, cannot be used in paleo diet studies. On the other hand, 13 C in carbonate in bone apatite reflects
the whole diet composition with such fidelity that it should be routinely analyzed along with 13 C in bone
collagen (Lanting and Van der Plicht 1996). The 13 C value might thus overestimate the amount of proteins
in the food, but it is already interesting enough to examine how a population got the proteins they needed,
for example regarding the question if marine resources played a big role in a certain culture.
Food chains in marine and freshwater environments are different, and so are isotopic values. Although
the difference is biggest for 15 N (see section 1.3.2), one can also see a small difference in 13 C values. 13 C
values for marine animals are in average 5.5h less negative than for terrestrial animals, but there is an
overlap of 8h between the two groups, so that they are not very sharply devided. Animals which at least
stay a part of their life in freshwater have more or less terrestrial 13 C values, maybe because terrestrial
carbon is incorporated by the freshwater organisms (Schoeninger and DeNiro 1984). Humans, for example,
who live mainly on marine food have 13 C values in their bone collagen of -131h (Lanting and Van der
Plicht 1996). Chisholm, Nelson, and Schwarcz (1982) expected 13 C values of -13h for purely marine and
-20h for purely terrestric nutrition. One surprising example for the application of 13 C measurements for
diet reconstruction are 13 C measurements from many Mediterranean coastal sites where the 13 C values were
not consistent with marine food consumption as a staple during the Mesolithic, Neolithic, or Bronze Age
periods and seafood [was] only measurable important for some Mycenae elites (Tykot 2003). At the
end of freshwater food chains, 13 C values in bone collagen are expected to be between -24h in lowland
rivers and -20h in lakes and canals. 13 C values of bone collagen give a mean value over the last 10 years
before death because of the long turnover times of bone collagen. In areas where both C3 and C4 plants are
growing, those animals feeding on a mixture of marine and terrestrial foods could not be distinguished from
those feeding exclusively on terrestrial foods (Schoeninger and DeNiro 1984).
Because of the above-mentioned effects, it is hard to find out what a person really lived on by measuring
13 C of bone collagen, as Lanting and Van der Plicht (1996) explain: With 13 C values alone it is not
possible to decide whether less negative values are caused by consumption of marine fish or of C-4 [C4 ] food,
or whether values around -21h are the result of an almost vegetarian diet or of consumption of terrestrial
meat and freshwater fish. A high consumption of a mixture of seafood and freshwater fish gives 13 C values
comparable to a completely terrestrial diet. 15 N measurements (see section 1.3.2) can help deciding such
questions because 15 N is far more positive in fish than in terrestrial food. Even if the diet contains only a
low protein content, most of the carbon in collagen comes from the protein (Ambrose 2001). In tidal waters
and estuarine systems, a run-off effect of biogenic carbon can happen which causes the 13 C values in
these areas to have terrestrial values (Chisholm 1989). People living mainly on fish could so have the same
13 C values as a population which is living solely on terrestrial food.
The decay of organic material in the soil does not lead to further fractionation. Aerobic bacteria convert
much of the organic material back to CO2 , and this CO2 has much the same 13 C concentration as the
vegetation itself. The CO2 concentration of soils is 10 to 100 times higher than that of the atmosphere, and
it is diffusion of CO2 along this steep concentration gradient that results in a 13 C enrichment of the soils.
13 C in soils hosting C3 plants is about 23h, whereas it is -9h in a C4 landscape (Clark and Fritz 1997).

1.3.2

15

There are only two natural nitrogen isotopes: 14 N and 15 N, while the mass numbers of artificial radioactive
nitrogen isotopes span from 12 to 19. 99.634% of nitrogen in atmospheric air consists of 14 N, 0.366% of 15 N.
24

The 15 N isotope was discovered in 1929. Since the first experiments in 1943, it was used as indicator for
investigations of the nitrogen cycle in cropping soils and plants as well as for investigations of the conversion
of proteins. 15 N is, just like 13 C (see above) expressed in the delta notation. The standard material for 15 N
is atmospheric air.
There is a step-wise increase in 15 N between trophic levels (Ambrose 2001). This means that there is 15 N
enrichment from plants to herbivores to carnivores. Marine and freshwater zooplankton, for example, 15 N
values that are on average 3h more positive than associated phytoplankton (Schoeninger and DeNiro (1984)
and references therein). In marine systems, food chains are generally longer so that more 15 N enrichment
steps can take place as in terrestrial systems. Enrichment between to steps in a food chain is normally about
3h, as is the case for plankton, but there are big differences between species and even between different
groups (Ambrose 2001). The reason for that is that trophic levels within food webs can overlap to a large
extent (Schoeninger and DeNiro 1984). It is possible to reconstruct the trophic level of animals which are
exclusively feeding on terrestrial or exclusively feeding on marine food with their 15 N values. Schoeninger
and DeNiro (1984) observed that marine animals with bone collagen 15 N values less than +13h fed on
invertebrates whereas those with 15 N values greater than +16.5h fed on other vertebrates. Schoeninger
and DeNiro (1984) give some examples of average 15 N values in bone collagen (table 1.1).
Table 1.1: Average 15 N values in bone collagen of different terrestrial and marine animals (Schoeninger and
DeNiro 1984)
Carnivorous terrestrial animals
Herbivorous terrestrial animals
Marine animals feeding on fish
Marine animals feeding on invertebrates
Freshwater fish feeding on fish
Marine fish
Marine birds
Marine animals in total
Terrestrial animals in total

+8.0h
+5.3h
+16.5h
+13.3h
+8.0h
+11.4 to +16.0h
+9.4 to +17.9h
+9.4 to +23.0h
+1.9 to 10.0h

The overlap between terrestrial and marine animals is only 1h and the mean for marine animals is almost
9h more positive than the mean for terrestrial animals. The reason is, as mentioned above, the difference
length of food chains in marine and terrestrial systems. If only mammals are considered, the difference
between the mean values is bigger by almost 10h. Additionally, there is not an overlap between the two
ranges but they are separated by about 2h.
As virtually all of the nitrogen that humans assimilate is derived from protein, 15 N values recorded in
the human bone collagen allow to reconstruct past diets and for example calculate how much protein in
the humans nutrition derived from aquatic and how much from terrestrial animals (Bonsall, Cook, Hedges,
Higham, Pickard, and Radovanovic 2004). This would be impossible if the nitrogen assimilated in humans
would derive from for example air.

1.4

Food residues on pottery

Pottery is one of the most important categories of archaeological finds and often used for the definition and
separation of archaeological cultures. Potsherds are often the most plentiful artefacts found in archaeologic
excavations, can form the basis of useful chronologic sequences used to trace the development of a region
or culture (Johnson, Stipp, Tamers, Bonani, Suter, and Wolfli 1986), and are used as markers to correlate
widespread sites and summarize the overall development of diverse civilizations or cultures. The dating of
pottery that was found at a certain site gives valuable information about the occupation endurance of that
25

site, because it is directly related to human activity. In contrast to that, charcoal for example could stem
from old wood, such as drift wood, dead wood collected in a forest, or the inner parts of a log and so provide
too high ages. Before explaining 14 C dating of food crusts on pottery, I will give an introduction to pottery
as an archaeologic material and explain basal terms.

1.4.1

Terminology and general remarks on prehistoric pottery

Tite (2003b) gives a comprehensive introduction to prehistoric pottery. A big part of the information
presented here is derived from his text. The first step in pottery-making is the preparation of the clay. It
should be sufficiently plastic for forming, but its drying shrinkage should be limited to minimize the danger
of cracking. Therefore, in some cases clays with different properties can be mixed, while in other cases
non-plastic inclusions have to be removed or temper has to be added. Temper usually consists of more or
less fine material which is capable of absorbing the water that gets released from the pottery while firing.
This water can come from the pores between the clay minerals (the fraction that did not evaporate while
drying) or from inside the minerals (this water can not be removed with drying the pottery and is only
released at high temperatures). If the water evaporates, the pot shrinks while water vapour fills the pores.
This would then cause the pot to crack.
Some examples of temper that prevent the pot from cracking are sand, grog (i.e. crushed sherd), organic
material (e.g. chaff), crushed flint, shell or limestone. The temper is often exclusively of one kind for a
certain ware, sometimes even having a symbolic value: Grog temper, obtained from the crushing of ancestral
pottery, for example, can be seen as an act of rebirth through which a reversal of time is achieved.
There are different methods of forming the lump of clay into a pot, for example pinching, drawing or
beating (using a paddle and anvil); pressing or pounding into a mould; building up from coils or slabs; and
throwing on a wheel. The pottery of the examined period is built up from coils (see section 3.3.4), which
can for example be seen on the sides of the sherds and on the shape of cracks. It is likely that in the
Neolithic, a household production of pottery took place. This can be inferred from the simple shapes and
building technique of the pots as well as from a limited standardization in the raw material composition.
The pots were hand-formed and open-fired in a bonfire, so that they easily could be made by part-time,
non-specialist potters. There are ethnographic examples, though, that hand-formed, open-fired and not
decorated or specialized pottery is made by a specialized group of people (H
aland 1979).

1.4.2

Dating of pottery

The oldest method of pottery dating uses style and technique to build up chronologies. A precondition for
this dating method is that different pieces of pottery, looking the same and made and decorated in the same
way, are contemporaneous. Another is that changes only occur gradually, so that it is possible to build up
a so-called typological sequence. Apparently, people in certain cultures and in certain times all used the
same techniques and shapes for producing pottery, although many different kinds of pottery would serve the
same purpose. As Hayashida (2003) remarks, There may be many ways to make a sturdy cooking pot given
available materials but the particular clays chosen and the techniques used to form, finish, and fire the vessels
are linked to such diverse factors as the organisation of the potters, their social identity, the perception of
different raw materials and fuels, and the integration of pottery-making with other activities. This method
is the least expensive one and done by the archaeologist himself so that the result is immediately available.
However, this method only provides relative datings and is subjective. For absolute datings, other scientific
methods have to be applied.
There are different physical methods for dating of pottery. Thermoluminescence (TL) dating is one
example. It dates the moment of the last heating of a sample containing minerals, as the firing of pottery.
A thermoluminescence signal builds up as a mineral is exposed to natural radioactivity. The TL signal
is zeroed when the mineral is heated. When zeroing a mineral in the laboratory, a measurement of the
thermoluminescence signal, the amount of light emitted by the mineral, is a measure for the time since the
last zeroing. The advantage of TL dating is that it avoids the old charcoal problem and that it is not so
expensive as AMS. Limitations are that a sherd may have been accidentally reheated after original firing,
26

that it may not have been completely zeroed in ineffective firing and that some ceramics do not hold
a TL signal (Johnson, Stipp, Tamers, Bonani, Suter, and Wolfli 1986). Also when applying radiocarbon,
some restrictions have to be taken into account. Nonetheless, I now will focus only on radiocarbon and not
describe other methods in more detail.
The main restriction when trying to radiocarbon-date pottery is the limited extent to which carbon can
be found in pottery. Radiocarbon dating of pottery was first made possible with the introduction of AMS
(see section 1.2). Conventional 14 C dating (with beta-decay-counting) could only be applied to associated
samples of another material, for example charcoal, or implied the destruction of large quantities of sherd
material (Johnson, Stipp, Tamers, Bonani, Suter, and Wolfli 1986). Other problems originate from the
variety of possible carbon sources and the different points in time they belong to: carbon originally present
in the clay, carbon added as organic temper, carbon from soot deposits made during manufacture or use,
carbon from food residues, and secondary carbon contamination after deposition (Feathers 1993). All these
different carbon sources may have different ages (Hedges, Tiemei, and Housley 1992). Pottery normally
consists of 50 to 70% clay. Carbon originally present in that clay has normally infinite ages, although it can
be younger (a few thousand years) when it closely underlies surface vegetation. In each case, it tends to
increase the apparent age of the potsherd. Quarried clays may contain up to 20% organic matter. 20 to 50%
of a potsherd consist of temper which is likely, but not exclusively, contemporaneous with the production of
the pottery. If consisting of organic matter, temper is generally useful for dating. Though being useful for
dating, it is not very probable that enough temper survives the firing process. Gabasio, Evin, Arnal, and
Andrieux (1986) studied modern pottery with known composition of clay (known carbon content), different
temper and different amounts of organic admixture. Experiments with reconstructed neolithic kilns showed
that the addition of up tp 10% organic matter did not change the carbon content of the pot after firing. In
the case of the pottery examined in this thesis, granite chippings were used as temper. The temper provides
thus no carbon contemporary with the pot for radiocarbon dating. Carbon from soot deposits made during
manufacture is also regarded as useful for dating although the old wood effect has to be taken into account.
The more porous a pottery is, the more soot can be deposited during firing. Also the use of primitive
kilns enlarges the fraction of carbon deposits in the pottery, because pottery in primitive kilns is in direct
contact with the fuel. Generally, the fire in primitive kilns is fed by wood or dry grass so that a lot of soot
develops. It is therefore expected that pottery of protohistoric times contains enough carbon from the fire
to date the firing process whereas more advanced pottery from historical times is expected to be difficult to
date (Gabasio, Evin, Arnal, and Andrieux 1986). However, pottery from historic epochs can normally be
dated more easily and precise by style than by scientific methods.
There are two datable moments when analysing pottery: The firing and/or last heating as well as the
last use for processing food. It is hard to date the firing of the pottery with radiocarbon, because it is not
completely clear which material is associated with that process. One possible material is organic temper, if
it had been used and did not burn away completely (see above), and if it can be extracted from the sherd.
Often only imprints of burnt temper particles remain. But even if present, organic temper is hard to separate
from other organic material that was in the clay long before it was formed and burned (the organic material
could even originate from the time of formation of the clay). The carbon in the clay can thus have geological
ages (Hedges, Tiemei, and Housley 1992).
Carbonaceous compounds such as humic acids can be introduced from the burial context. Although
this is regarded as contamination, it possibly tends to reflect the date of the burial stratum and often
does not seriously alter the dating of the sherd. Bacterial activity has also to be taken into account if the
sherd was buried in an organic-rich deposit (Hedges 1992). Bacteria, though, normally do not change the
isotopic composition of the carbon to a significant extent because they use carbon from the sample instead
of introducing carbon from other sources.
The last use for processing food can be dated when a crust of charred material is found on the sherd.
As a pot with a thick, charred crust is not best suited for the preparation of well-tasting food and as it is
impossible to completely clean such a porous pot, one can assume that the pot was not used for a long time
after the formation of the crust. Apart from its potential for dating, the existence of food crusts provides
the knowledge that the examined type of pottery was used for the processing of food and not, for example,

27

only for carrying or storing water (Andersen and Malmros 1984). Because the sherds appear thick, fragile
and porous when excavated, it was doubted for some time that the pots had been suitable for cooking.
Klinge (1932)for example tried to boil water in rebuilt Erteblle pots, but he did not succeed because the
water was evaporating through the pores of the pot already at 70-90 C. Therefore, he concluded that the
pots were only used as salterns for sea water. Later findings of Erteblle pots in the inland, far away from
supplies of sea water, contradicted this interpretation. Later experiments in which starch or fat had been
added to the liquid in the pot also disagree with Klinges conclusion: the pores of the pot were sealed with
starch or fat so that the content could be heated up to the boiling point (Andersen and Malmros 1984).
Our experiments support this statement and show the suitability of Erteblle pots for food processing (see
section 4.1.3). In contrast to that, a charred crust on the inside of a pot can have a completely different
reason, as ethnographical observations indicate: In Western Sudan, simple clay pots have been waterproofed
by filling them with grass or stray before firing them upside down. The soot layer in the pots prevented
water from soaking through the pores so that the pots were suitable for boiling water (H
aland 1979).
On many pots of the Late Mesolithic Erteblle culture, crusts of charred organical material are preserved,
especially in coastal and bog areas. In the material from Schleswig-Holstein, food crusts from pots at coastal
settlements are always thicker than those from inland sites, an observation that is not yet understood (pers.
comment S. Hartz 2007). A possible reason could be the better preservation environment for organic samples
at coastal sites so that the food crusts there stay more intact than those from inland sites. As the crusts
are charred and the thickest crusts occur on the inside of the pots, especially in the bottom half of the pots,
they are interpreted as burnt food remains and therefore called food crusts. Crusts on the upper outside of
the pots are explained to come from a liquid content boiling over, for example a soup. The reason for the
absence of such crusts on the outside of the bottom half of the pot could be that the food remains there
were completely charred away by the hearth fire (Andersen and Malmros 1984). Crusts on the outside of
the pots could also come from soot, when the food was prepared over an open fire. The soot is expected to
give the same or a higher age as the pottery, depending of the kind of fuel that was used (short-lived organic
material or old wood).
One example for the dating of food crusts from the EBK is the submarine settlement Tybrind Vig on
the western coast of the island Fyn in Denmark. The pottery at this site was embedded in the gyttja of the
waste zone and is therefore well preserved. The site is radiocarbon dated to 4400-3200 BC (in uncalibrated
14
C-years), whereas the pottery is from 3700-3500 BC (in uncalibrated 14 C-years) (Andersen and Malmros
1984). The calibrated date for the site is approximately 5400-4000 BC and for the pottery approximately
4500-4350 BC.
A possible hardwater effect on pottery has been shown by Fischer and Heinemeier (2003), see section 1.2.2.
Pottery dating from Estonia has in one case given a date that was 1000 years older than expected (Kriiska,
Lavento, and Peets 2005). It could be that this dating is correct and that the archaeological assumption
has to be corrected, but it could as well be that the hardwater effect contributed to the high age of the
pottery which was found on a site at a river bank (Kriiska, Lavento, and Peets 2005). Nakamura, Taniguchi,
Tsuji, and Oda (2001) report ages as high as 15,710-16,540 cal BC for the earliest Japanese pottery. It had
been assumed before that the use of pottery started with the Jomon Culture in the Holocene after a series
of climatic fluctuations. The AMS dating of pottery, though, suggest that the first pottery was already
made during a cold climate period predating such climatic fluctuations by about a millennium. It would
be interesting to examine this pottery closer to find out if it also had been influenced by the hardwater
effect or if those surprisingly high radiocarbon ages also correspond to high historical ages. Up to now, the
younger ages of charcoal samples have been explained with the assumption that these charcoal pieces really
are younger and have been anthropogenically or naturally mixed into the layers in which the pottery was
found (Nakamura, Taniguchi, Tsuji, and Oda 2001).
It has been tried to extract protein for food crust dating from some Swedish sites (Segerberg, Possnert,
Arrhenius, and Liden 1991). For obtaining one milligram carbon, 1 gram food crust is needed from which
proteins are extracted with the Lowry-method. Amino acids are split using high performance thin layer
chromatography (HPTLC). From the resulting 3 mg amino acids, 1 mg carbon can be gained. The surprising
result of the amino acid extraction was that the amino acid which normally is most abundant in all nutritives,

28

glutamine, was totally absent on one sherd and only detectable on another one. Alanine, though, a simple
non-essential amino acid, was found in large amounts on another sherd. This can be explained by the fact
that alanine is the simplest of all amino acids and large quantities of it are present in strongly deteriorated
products. The amino acid composition of the potsherds is thus an indicator for the fact that they are broken
down by natural or man-made processes.
Another attempt is the extraction of lipids from the entire sherd. Hedges, Tiemei, and Housley (1992)
tried this using Soxhlet extraction in acetone. Many of the archaeological sherds they examined contained
extractable lipids at the level of 0.02 to 0.4% and seem to be a good dating material. Lipids are rather
immobile and lipid concentrations in soils are low so that little exchange between sherd and burial context
can be expected. Nevertheless, only 3 out of 7 examined sherd provided reasonable (not necessarily accurate) lipid ages. Therefore, they only denote food crusts as fairly reliable samples if no organic temper
remained. Stott, Berstan, Evershed, Hedges, Bronk Ramsey, and Humm (2001) also used lipid extraction
for radiocarbon of potsherds but they extracted different fatty acids from the sherd material. Stearic (C18:0 )
and palmitice (C16:0 ) acid and the C18:1 unsaturated acid provided high enough concentrations for radiocarbon dating when examining potsherd samples of about 10 g. After extraction, the lipids were derivated
and purified. Gas chromatography (GC) was used for extracting the single fatty acids. This method proved
to be very time-demanding: To obtain sufficient material for precise dating repetitive, accumulating, GC
separation is necessary. About 100 runs were needed for each sample.

1.4.3

Analyses on food crusts

Organic residue analysis gives information both on the use of the pottery and on past diet and has therefore
the potential for contributing to our understanding of the reasons for the adoption of pottery in different
regions (Tite 2003b).
13
C analyses of food crusts from Tybrind Vig showed terrestrial origin (two samples had -22.1h, one
-26.6) although the visible remains mainly came from cod (scales and bones) and to a smaller extent from
grass. This was interpreted as the remains of a fish soup with a big fraction of terrestrial plants (Andersen
and Malmros 1984). Also Arrhenius and Liden (1989) found bones and scales of fish on the pottery, but the
low protein content, the high fat content and the presence of phytoliths indicate that fermented porridge
of vegetable origin (Arrhenius and Liden 1989) was prepared in the pots. One crust had 47% lipid content,
but only 1.08% protein content. Protein content in some recent reference material (Baltic herring) was
comparably low, but the authors claim that with the ageing of the sample, normally a protein-enrichment
takes place. A conclusion could be that the pots first were used for the preparation of plant food and later
as waste bins for fish rests. The fact that macrofossils found by Andersen and Malmros (1984) were only
present in the upper layers of the food crusts indicates that they came into the pot after the formation of the
crust. Otherwise would they have been sunken to the bottom of the pot. The fact that they are imbedded
in the crust, though, indicates that they were put into the pot when the crusts still was wet (Arrhenius and
Liden 1989).
The protein composition of the pots investigated by Arrhenius and Liden (1989) from Tybrind Vig show
a similar pattern. Dominating are alanine, glycine, methionine and to a certain extent also glutamic acid.
Alanine, a simple nonessential crystalline amino acid, can be found in high concentrations in animal products,
nuts and mushrooms and even in decomposed materials. Glycine is a sweet crystalline amino acid obtained
especially by hydrolysis of proteins and can be found in high concentrations in animal products. Methionine
is a crystalline sulphur-containing essential amino acid that mainly can be found in nuts. Glutamic acid, a
crystalline amino acid, is widely distributed in plant and animal proteins and is the dominating amino acid
in all food products, except some fruits and roots.
The amino acid cysteine, which is characteristic for fish, is completely missing in the material from
Tybrind Vig which again is an argument against Andersens and Malmros (1984) interpretation of charred
fish soup remains. According to Arrhenius and Liden (1989) are bubbles in the crusts further evidence for
fermented porridge. The high fat content of the crusts could indicate the use of plant oil such as beech-nut
oil (Arrhenius and Liden 1989), but it could also be a question of conservation: Because of their hydrophobic

29

properties, lipids survive on pottery and the migration of lipids from the soil in which the pottery was buried
does not normally seem to occur to any significant extent (Tite 2003b).

30

Chapter 2

Small sample preparation

Some of the sample types that are analyzed in this work are quite small. The normal sample size required
for 14 C dating is 1 mg carbon. Fishbones and food crust, though, are expected to yield smaller carbon
masses. The carbon mass of these sample types was often below 200 g and in one case only 30 g. Also
some bones of terrestrial animals had so small carbon yield, when the samples were quite small and badly
preserved. A detailed description of the samples can be found in section 4. The smallest sample mass that
nowadays is routinely dated at the AMS 14 C laboratory at Aahus university is 350 g carbon. For being able
to measure the samples mentioned above, instrumental development was thus needed to reduce the sample
size. For seeing if such a sample size reduction is possible in principal, the results of other groups have been
checked. It has been reported that samples as small as 50 g carbon can be measured without significant
isotopic fractionation. Also the measurement of samples with 15 gC should be possible, but the introduced
fractionation must then be corrected by processing and measuring standards of the same size (Tuniz, Zoppi,
and Barbetti 2003). It is thus worthwile optimising our equipment to the preparation of samples in the range
of few tens of micrograms.
I will take a look at all steps in sample preparation. I will also include the steps where I did not
develop new techniques myself to obtain a complete description of the sample preparation. There are two
fundamental steps in sample preparation. The first is the removal of contamination from the sample. This
step is also called chemical pretreatment or simply pretreatment. The second step is the conversion of the
pretreated sample to a form in which the abundance of 14 C can me measured. In our case, this is elemental
graphite. After the chemical pretreatment, the sample is thus combusted to CO2 which then is reduced so
that elemental carbon, graphite, is obtained. This last procedure is called graphitisation. First, I will take
a short look at the chemical pretreatment. Then, the graphitisation of small samples will be examined. The
influence of the material that catalyzes the reaction will be analysed. A reduction of the reaction volume
will be shown to provide better conditions for the graphitisation of small samples. In the end, an outlook to
a new combustion method that combines the production of CO2 for 14 C measurement with stable isotope
analysis will be presented.
A constant amount of contamination introduced during the sample preparation process is as bigger a
problem as smaller the sample mass is. As each step in the sample preparation bears the risk of contamination
and/or fractionation, each step has to be optimised for small samples. A reduction in the sample preparation
effort would not only save time and money, but also help getting better results with reducing the number
of steps in which fractionation or contamination could be introduced. This applies also to the chemical
treatment: as many steps as needed to get rid of most of the contaminants have to be applied, but as few
as possible to reduce the risk of laboratory contamination.

31

2.1

Sample pretreatment

A good overview over sample pretreatment can be found in Hedges (1992). Some of the information presented
here has been extracted from that paper. The basic assumptions in radiocarbon dating include after Hedges
(1992) the following:
1. The planetary distribution of

14

C in the biosphere is uniform in time and space;

2. The sample, as measured, contains carbon that came only from a living organism (or similar system
that ceases to be in chemical exchange with the biosphere), and that the living organism took its
carbon only from the biosphere
The first assumption is only approximately true, but can be corrected (see section 1.1.3 and 1.2.2). To be
sure that the second assumption is right, one has to remove all the contaminants from the sample and only
use the most reliable fraction of the sample, for example the collagen from bones, for dating. Only the
fraction of carbon that was incorporated during the organisms life should be used for dating. A problem
with the second assumption is the hardwater reservoir effect which was described before in section 1.2.3:
Carbon in the water organisms is not likely to be purely atmospheric. Contamination of a sample is the
admixture of carbon with a different 14 C concentration to the sample. Contamination can to a great extent
be removed chemically. The chemical pretreatment thus isolates and purifies the chemical phase or phases
that represent the ecent or archaeological culture or geologic stratum to be dated (Long 1992).
Some chemical pretreatment of the sample is needed, anyway, also if assuming that no contamination
entered the sample, as the sample has to be converted to another form: The chemical conversion of a sample
in its pristine state to the form in which the abundance of radiocarbon can be directly measured is the main
link between the radiocarbon date and the basic assumptions upon which this date rests. In the case of AMS
at Aarhus University, the samples have to be converted into graphite, because that is the form in which the
abundance of radiocarbon can be directly measured with the accelerator. So, after chemical preparation to
remove contaminants, the samples are combusted to gain CO2 and then reduced to pure carbon (graphite).
Routine methods were developed for the pretreatment of samples for conventional radiocarbon dating
and after some time been taken for granted. AMS brought about changes in pretreatment methods, both
because the sample is measured in another form (graphite instead of counting gas or liquid) and because
the sample size is reduced by a factor of at least a thousand. This has stimulated a re-examination of
many pretreatment methods, and thereby enabled the link between assumption and date to be more closely
controlled.
Two important classes of contaminants that enter archaeological samples during burial are carbonates
and humic substances. Carbonates are transported with the soil water and can for example be incorporated
by the mineral fraction of bones, but they are also incorporated by other sample types. They can be removed
with acidifying the sample with hydrochloric acid, HCl. Humic substances are a fraction of the dissolved
organic carbon in soils (see section 1.2.3). The characterization of different humic substances is largely based
on separation methods. Humic substances have the relatively high molecular weight in common that can
be up to several 100,000 mass units, or several 100kD. They are refractory, heterogenous, alkali soluble and
give the dark colour to soil and water (Clark and Fritz 1997). Humic substances include humic acids, fulvic
acids and insoluble humic substances. Humic acids precipitate from solution at pH < 2. Fulvic acid is
soluble at all pH values. Both humic and fulvic acid derive from humification of vegetation, for example
from cellulose and other carbohydrates, proteins, lignins and tannins, by bacterial metabolism and oxidation.
Humic substances are removed with sodium hydroxide, NaOH, from the samples.
The pretreatment methods that were used for big samples were adjusted slightly to pretreat smaller
samples. The concentration of NaOH was for example weaker for the smalles samples so that the danger of
dissolving the sample completely was minimized (see section 4).

32

2.2

Graphitisation of small samples

The samples have to be converted into a form in which the abundance of 14 C can be measured directly. For
AMS measurements, the samples have to be pure carbon, i.e. graphite. To obtain this graphite, the sample
is first combusted or acidified to form CO2 and then reduced to get pure carbon (or graphite) after the
reaction CO2 + 2H2 = 2H2 O + C. This reaction will in the following be called graphitisation.
This reaction can only take place in the presence of a catalyst. Here, cobalt and iron are used. They
serve not only as catalysts, but also as carrier material for the measurements in the accelerator. They
have different properties, as will be explained in the following. The catalyst is filled into the reaction tube
(reactor) before the sample CO2 comes in. With the help of a magnet, the catalyst particles get raised up
so that the reaction surface gets bigger. The reactor with the catalyst is then evacuated and 380 to 400 torr
H2 are filled in to prepare the catalyst. H2 remains for one hour in the reactor at 400 C. After that, the H2
is pumped away and the reactor is ready for the graphitisation of a sample.
The combusted sample, in the form of CO2 in a quartz tube, has to be transferred to the graphitisation
system. For this, the quartz tube is placed into a tube cracker. This is connected to the graphitisation system
and is evacuated. After closing the valves to the pump, the tube is cracked and the sample transferred to
a coldfinger with the help of liquid nitrogen. Nitrogen has a boiling point of -196 C which is below the
freezing point of CO2 (-78.5 C). On the transfer line, the sample has to pass a coldfinger which is cooled by
a mixture of ethanol and liquid nitrogen. It has a temperature between -72 and -80 C. Water vapour as well
as some other contaminating gases like H2 S or SO3 which might have been in the sample freezes here and
is so not transferred with the sample. The rest gas which can not be frozen at -196 C is pumped away. It
is mostly sulphur and especially with bones, quite big percentages around 30% can normally not be frozen.
Other samples such as oxalic acid or charcoal normally only contain minimal amounts of rest gas. When the
rest gas is pumped away and thus only CO2 remains in the cold finger, the coldfinger is closed off from the
rest of the system and the pressure is measured. From the pressure in this standardised volume, the carbon
mass can be calculated.
From the coldfinger, a CO2 amount corresponding to approximately 1.1 mg carbon (mgC) is transferred
to a reactor. About 0.2 mgC are transferred to a vial for 13 C-measurements. These transfers also are done
with liquid nitrogen. Figure 2.1 shows the reactors. On the picure, Peltier coolers are already placed on
the glass tubes where water is frozen during the reaction. Before placing the Peltier coolers there, the same
glass tubes are used for transferring the sample with the help of liquid nitrogen. The CO2 pressure in the
reactor is measured. For 1.1 mgC, it is around 440 torr at system 1 and 400 torr at system 2. The amount
of H2 needed for the reaction is calculated:
pH2 = pCO2 2.1

(2.1)

For the reaction CO2 + 2H2 = C + 2H2 O, the H2 amount has to be twice as large as the CO2 amount. The
factor is 2.1 instead for 2 in order to have a little H2 excess and definitely enough for so the reaction is as
complete as possible. Moreover, a higher pressure at the beginning can accelerate the graphitisation process.
The water which is produced in the reaction gets frozen with a Peltier cooler. The reaction normally takes
place at 700 C and usually lasts a couple of hours and is therefore done overnight. On the next morning,
after the ovens have been removed, the end pressure is written down. Thereafter, excess H2 and CO2 that
might have not reacted are pumped away. The Peltier coolers are removed and the water vapor is pumped
out as well. To avoid that the first contact of the graphitised sample is with air and to make it easier to
remove the (now evacuated) reactors, they are filled with Argon at atmospheric pressure.
The graphite yield or graphitisation efficiency is the ratio of the pressure difference for an actual reaction
to the pressure difference of a theoretical 100% reaction. In the reaction CO2 + 2H2 = C + 2H2 O, each
unit of CO2 reacts with two units of H2 so that after a complete reaction three units of pressure should be
missing and only the excess hydrogen should be left. The theoretical pressure difference of a 100% reaction
is therefore three times the CO2 pressure. The graphitisation yield is defined after Hua, Jacobsen, Zoppi,
Lawson, Williams, Smith, and McGann (2001) in the following way:
Graphite yield =

Initial pressure Final pressure

%
3 CO2 pressure
33

(2.2)

Figure 2.1: Normal-sized graphitisation reaction tubes. The peltier coolers are placed at the glass tube in
which water is frozen. On top, a pressure transducer is installed. To the left, the green valve connects the
reaction volume with the rest of the system. The reaction tube can be seen as the oven is not yet put upon
it.
Applying this definition to our situation will not lead to precise values for the graphitisation yield because the
initial and final pressure are measured while the Peltier coolers are switched on, whereas the CO2 pressure
is measured at room temperature. Anyway, it is a good indicator of reaction completion and can be used
to compare the yield of graphitisations which are done in different ways. Let us assume that a reaction was
completed and that all pressures were measured at the same temperature. For 1 torr of CO2 in the reactor,
2.1 torr H2 are filled in. The initial pressure is thus 3.1 torr. The final pressure is the initial pressure reduced
with the amount of CO2 and H2 that reacted, so that the final pressure for a completed reaction is 0.1 torr
in our example. This is the result when calculating the graphite yield after equation 2.2 for this example:
Graphite yield =

3.1torr 0.1torr
= 1 = 100%.
3 1torr

(2.3)

Two things are different when water samples are graphitised. The one is the water trap through which
the sample is transferred. It has a temperature of about -110 C instead of -72 to -80 C. The second is the
catalyst: Instead of 0.8 mg, 1 mg cobalt is used and additionally, a small strip of silver foil is inserted into the
reactor. Both modifications are due to the high water vapor concentration that is left in CO2 extracted from
water samples. At a lower temperature, the water trap freezes water vapor more efficiently. As water vapor
that all the same reaches the reactor slows down the reaction with covering catalyst surface, the catalyst
amount is enlarged to provide reaction surface enough. Silver is used because it can react with hydrogen
sulphide H2 S to water and silver sulphide and so remove the hydrogen sulphide from the reaction tube:
4Ag + 2H2 S + O2 2Ag2 S + 2H2 O.

(2.4)

The water originating from this reaction is frozen in the Peltier cooler in the same way as the water originating
from the graphitisation reaction, CO2 + H2 C + H2 O.
There are two factors which have to be optimized in the graphitisation process to obtain best conditions for
reliable dating: The reaction time has to be as short as possible to minimize the risk of contamination through
air leaks and the reaction has to be as complete as possible in order to reduce the risk of fractionation (Smith,
34

Petrenko, Hua, Southon, and Brailsford 2007) and to get maximize the graphite yield, i.e. the amount of
carbon from the sample that can be used for dating.
In our laboratory, there are two graphitisation systems, called system 1 and system 2. System 1 comprises
10 reactors, R10 to R17, R19, and R110 (read R1-0, R1-1, to R1-10). Eight of them, R10 to R17, are normalsized (4.5 cm3 ) and the remaining two, R19 and R110, are small (0.8 cm3 ). It is planned to set up four
small reactors on system 1 that will be called R18 to R111. Because of lacking fittings, only two of the small
reactors could be completed. That is the reason for the incomplete numeration of the existing reactors. In
figure 2.1, four normal-sized reactors are shown. On the picture, Peltier coolers are already attached to
them. Figure 2.2 shows the part of the graphitisation system where the two small reactors are installed.
Figure 2.2b shows the reaction volume. In figure 2.2c, the Peltier cooler is attached. In figure 2.2d, also
the oven is placed on the reaction volume. System 2 comprises 8 normal-sized reactors, R20 to R27. In the
following, system 1 has been used almost exclusively.

2.2.1

Experiments with the existing graphitisation system

For testing how small samples can be graphitised with the old system, graphite samples of different sizes
were combusted after the standard procedure (see page 48) and graphitised again. They were then compared
to the original graphite via measurements in the mass spectrometer to see if the 13 C-content changes during
the combustion/graphitisation and if these changes are dependent on the sample size.
After combusting the samples in that way, the CO2 was transferred to the graphitisation system and
the amount of carbon was determined via measuring the CO2 pressure in a calibrated volume. The amount
of carbon before and after combustion for the graphite samples BP1 to BP8 is given in table 2.1. Small
differences in the amount of carbon are due to measurement uncertainties and loss during transfer. The
combustion was apparently not complete for the small samples BP7 and BP8, so that further investigation
is needed for the combustion of <0.3 mg samples.
The CO2 was reduced to carbon using hydrogen as reduction agent and cobalt as catalyst at 700 C.
From the graphite-cobalt compound, a fraction containing approximately 0.1 mg of carbon was put into
tin cups to be measured at the mass spectrometer (the mass spectrometer works best with this amount of
carbon). From BP1 to BP6, where a sufficient amount of cobalt + graphite was obtained, 2 fractions were
measured. The fraction put into tin cups is given in table 2.1. The 13 C-values are given in per mil with
respect to the standard Vienna Pee Dee Belemnite (VPDB). As a reference, also 3 samples of untreated
graphite were measured in the mass spectrometer. The mean values for the sample size and for the 13 Ccontent are given in the bottom line of table 2.1. As a first result, one can say that fractionation takes place
during combustion and graphitisation, and that the fractionation effect grows with decreasing sample size.
For BP8, no 13 C value is given, because the mass spectrometer reported a carbon mass of 0.001 mg for this
sample. 0.001 mg carbon correspond to only 1.1% of the initial sample mass. BP2 seems to have gained
mass through the combustion/graphitisation process, but this is not necessarily a sign for CO2 coming into
the sample from outside. It is probably only due to measurement uncertanties: MC after combustion is
measured via CO2 pressure, while MC before combustion weighed with scales. The table shows that the
combustion/graphitisation process always introduces fractionation. As a general rule, one can say that the
fractionation effect grows with decreasing sample size. BP4 seems to be an exception from that rule because
it has very high fractionation but average sample size. An explanation for the unusually high fractionation
could be the big difference in carbon mass before and after combustion: all processes that do not reach
completion bear a risk for fractionation.
Another problem with the smaller samples is apparently the incomplete combustion. From samples BP7
and BP8, only an amount of CO2 that corresponds to respectively 38% and 15% could be gained, although
all samples BP1 to BP8 were combusted in the same way. These problems could be connected with the bad
combustion characteristics of pure graphite. One attempt to enhance the combustion was to lengthen the
combustion time. Therefore, two sets of samples from the standard material GelA (a laboratory working
standard for 13 C and 15 N that has been calibrated against several international standards) in different sizes
were combusted. The combustion time was one hour for set 1 (odd sample IDs) and three hours for set 2
(even sample IDs; see table 2.2).
35

(a) Small reactors

(b) Small reactor

(c) Small reactor with Peltier cooling element

(d) Small reactor with Peltier cooling element and oven

Figure 2.2: The part of the graphitisation system with small reactors.

36

Table 2.1: Combustion and graphitisation of graphite

ID

MC [ mg]

MC [ mg]

before

after

MCo [ mg]

combustion

MCo+C [ g]

13 C [h]

Into

VPDB

MassSpec

BP1

1.05

0.85

0.79

BP2

0.81

0.82

0.75

BP3

0.60

0.52

0.84

BP4

0.48

0.31

0.89

BP5

0.42

0.40

0.85

BP6

0.31

0.27

0.82

BP7
BP8
Graphite

0.21
0.09

0.08
0.01

0.75
0.90

183
175
200
189
244
247
277
273
293
304
364
358
464
421
97

-27.02
-27.07
-27.06
-27.08
-27.82
-27.80
-29.86
-29.55
-27.83
-27.94
-29.17
-29.98
-34.37

-25.92

Table 2.2: Combustion and graphitisation of Gel A

1 hour combustion
ID
Mass (mg) Yield (%)
BP9
0.33
47.7
BP11 0.68
43.7
BP13 0.87
43.4
BP15 1.16
43.6
BP17 1.49
38.0
Average
43.31.7

3 hours
ID
Mass (mg)
BP10 0.30
BP12 0.62
BP14 0.92
BP16 1.16
BP18 1.54
Average

combustion
Combustion yield (%)
46.9
35.1
40.8
44.4
37.3
40.92.2

As can be seen from table 2.2, the average yield does not change significantly with longer combustion
time. Therefore, the normal combustion time of one hour could be applied to all following samples.
It is assumed that if the combustion process would introduce fractionation, it would affect small samples
more than bigger ones. To test this, normally combusted samples have been compared with samples that
were made by combusting the double sample size and then splitting up the CO2 gas into two samples. With
this procedure, it is possible to examine only the size-dependent fractionation from combustion. Graphitised
samples of the same size are compared, where some of them came from combusted doublets and some from
single combustion. The graphitisation took place with cobalt as catalyst. In table 2.3 the delta13 C values of
the singly combusted samples are compared with those of the doublets. This examination is important for
the choice of standard material preparation. If there is no difference between single and doublet combustion,
standards can be combusted in great amounts and split up for graphitisation to produce small standards
which are needed for the measurement of small samples. If there is a difference, then the combustion
of standards of the same size as the samples is necessary. The 13 C values for the graphitisation doublets

37

BP23/24, BP25/26 and BP27/28 and thus the fractionation does not differ significantly between the aliquots
of one doublet. It can be seen, though, that there is a big difference in the 13 C values between the doublets.
Varying fractionation is thus suspected to originate from the combustion process. If the graphitisation was
the cause for random fractionation, the 13 C values of two samples of a doublet would not agree as they
do here. When comparing the 13 C values of the doublets with those of the single-combustion samples,
a tendency towards bigger fractionation can be seen with the single combustion samples, but only if the
doublet BP25/26 and the two last results from BP21/22 are regarded as outliers. Because a clear tendency
can not be observed, further tests are necessary to decide whether the combustion really is the biggest source
of contamination and fractionation and whether standards can be combusted in big amounts and split up
for graphitisation. Tests are planned using not only doublets, but also quartets, and these tests are planned
to be repeated several times to find a statistically significant answer.
Table 2.3: Single and double combustion and graphitisation of GelA. Samples with similar carbon mass that
are to be compared are grouped by horizontal lines.
Single combustion
ID
Mass
(mg GelA)
BP21/22 0.79

Combustion
yield (%)
50.1

BP23/24

0.60

40.1

BP25/26

0.43

46.1

BP27/28

0.21

43.9

13 C
(VPDB)
-30.73
-26.71
-26.80
-27.95
-28.53

-30.14
-31.00
-26.52
-27.36

Double combustion
ID
Mass
(mg GelA)
BP29
0.43

Combustion
yield (%)

13 C
(VPDB)
-27.32

BP9
BP43
BP30
BP10
BP39
BP35
BP41
BP36
BP42

47.7
52.4
43.2
46.8
47.1
57.2
51.0
64.5
67.8

-28.28
-29.51
-30.43
-30.80
-27.53
-27.38
-34.56
-24.49
-30.83

(Fe)
(Fe)
(Fe)
(Fe)
(Fe)

0.33
0.33
0.30
0.30
0.28
0.21
0.16
0.09
0.06

Santos, Southon, Griffin, Beaupre, and Druffel (2007) developed some improvements in the sample preparation process for reducing the sample size. As for the dating of small samples, also small standards are
needed, they compared the combustion of small standards with the combustion of big standards which were
devided into smaller samples for graphitisation. Because there were no differences between standards prepared in the two different ways and because it is almost impossible to weigh out so small amounts of standard
material, they decided to use big amounts for combustion and to devide them for graphitisation.
After these first tests it was examined if iron is a better catalyst for small samples. Now, cobalt is used
as a catalyst for graphitisation. Several tests have now been done to compare the cobalt with iron and
to decide which catalyst is best suited for the graphitisation of small samples. The cobalt powder used in
the laboratory is a spherical cobalt powder, -325 mesh (<45 microns), from Johnson Matthey GmbH Alfa
Products (article no. 00739, manufacturing ceased). The iron I tested is iron reduced, grain size 10 micron,
from Merck KGaA (article no. 3819).
The purity, in terms of absence of carbon contamination, as well as the behaviour of a catalyst have to
be tested. Santos, Mazon, Southon, Rifai, and Moore (2007) give 5 criteria for testing catalysts:
1. 12 C+ current from pure catalyst in target (that indicates the amount of carbon contamination)
2. blank values for coal (measurements of the 14 C amount in 14 C-dead charcoal targets indicate the
amount of modern carbon contamination)
3. conversion time CO2 to graphite
38

(a) Pressure in reaction tube

(b) Pressure in reaction tube in % of start pressure

Figure 2.3: Graphitisation of two identically sized samples with cobalt and iron as catalyst.
4. homogeneity and lack of sintering
5. 12 C+ beam current intensity produced from the graphite targets
Testing the first criterion is difficult because it is hard to see the difference between carbon ions that come
from the catalyst itself and carbon ions originating from the target holder or the ion source (pers. comment
Klaus Bahner 2007). Due to several problems with ion source and accelerator, the second and fifth criterion
could neither be tested. The samples are prepared and ready for measurement, but unfortunately, the new
ion source was not ready for routine measurements before this thesis had to be finished.A first assessment
of catalyst has thus to be based solely on graphitisation ratio and catalyst / graphite structure.
The graphitisation process has been monitored with reading out the pressure sensors. The pressure
sensors of the normal-sized reactors are not connected to a computer so that the pressures had to be written
down manually. Therefore, not the whole nighttime-process could be monitored. Anyway, the first three
hours of graphitisation show interesting differences between cobalt and iron catalysts.
In general, it can be concluded that iron is the better catalyst in terms of reaction speed. Normally, the
reaction with iron starts soon after the ovens have been switched on, whereas it takes some time for a reaction
with cobalt to begin. Santos, Mazon, Southon, Rifai, and Moore (2007) even observe graphitisation times as
small as 120 minutes for some iron catalysts and sample sizes around 1 mg. In figure 2.3, the graphitisation of
two samples with the same size, 1.17 mgC, in normal-sized reactors is shown. It can be seen that the reaction
for the sample graphitised on iron is finished after about three hours. At that time, the total pressure for
the reaction with cobalt is only reduced to the half. The final graphite yield after equation 2.2 is 1.03 for the
sample graphitised on iron and 0.99 for the sample graphitised on cobalt (SSID 24100). For another sample
of equal size which also was graphitised on cobalt (SSID 24101), the graphite yield is 1.04. A difference in
yield for normal-sized samples can therefore not been found.
Figure 2.4 shows the start of a reaction more precisely. It can clearly be seen that the reaction starts
immediately for the two samples graphitised on iron (in R14 and R15). The pressure in the reaction tubes
filled with cobalt, though, rises during the first 10 to 15 minutes of the reaction. After that, the beginning
graphitisation can be seen, but the pressure decreases with a slower rate than in the case of iron catalyst.
Because a fast reaction reduces the risk of contamination, iron was used for the graphitisation of some of
the samples from Schlamersdorf and Kayhude (see section 4). Because they are normalized using standards
and backgrounds of the same size that were also graphitised using iron, no significant differences are expected
between the 14 C age measurements of the samples graphitised with cobalt and those graphitised with iron.
Therefore, the results remain comparable.
A mass-dependence of the reaction ratio and graphite yield could be observed for graphitisations with
iron (see figure 2.5).
39

Figure 2.4: The beginning graphitisation of normal-sized samples. In R10 to R13, Co was used as a catalyst,
whereas Fe was used in R14 and R15. Pressures in fraction of the maximum pressure.

Figure 2.5: Graphitisation of samples of different sizes with iron. Pressures as fraction of maximum pressure.

40

The catalyst amount also seems to play a role in the graphitisation process. Smith, Petrenko, Hua,
Southon, and Brailsford (2007) observed that increasing the catalyst amount from 1 mg to 4 mg improved
either yield or reaction rate, but not both. With a bigger catalyst amount, the life time of the sample in
the ion source is bigger but the current is smaller. They also examined the influence of the method of water
removal. They conclude that water removal is critical for graphitisation of small samples, but does not affect
larger samples. The reason why water vapor removal is critical for small samples is the following: For a
small sample, there is always a fresh catalyst surface available so that also the reverse action of graphitisation
comes into play (from the right-hand side to the left-hand side in the two following reactions).
CO2 + H2 CO + H2 O

(2.5)

CO + H2 C + H2 O

(2.6)

When the water vapor is efficiently removed, then these reactions are forced to the right-hand side.
An effective water vapor removal depends strongly on the temperature of the water trap if the water
vapor is meant to be frozen to ice. The reason for this is the strong dependence of the vapor pressure of ice
on temperature: 12.84 Pa at -40 C and only 0.06 Pa at -80 C. It could therefore be interesting to exchange
the existing peltier elements which cool down to about -40 C with a mixture of dry ice and ethanol which has
a temperature of approximately -80 C. Another possibility of water vapor removal which is worth trying is
the use of a dessicant like magnesium perchlorate (Mg(ClO4 )2 ). The aqueous vapor pressure over water-free
(anhydrous) magnesium perchlorate is <0.075 Pa (Smith, Petrenko, Hua, Southon, and Brailsford 2007).
With the small amounts of water that are formed during the graphitisation it is fair to assume that the
water vapor pressure not rises above approximately 1 Pa. This method of water vapor removal was also used
by Santos, Southon, Griffin, Beaupre, and Druffel (2007) who achieved graphitisation times under 2 hours
and were able to graphitise and reliably date samples as small as 0.002 mgC using magnesium perchlorate
water traps.
One exception from the general rule that iron is better suited as catalyst is the graphitisation of water
samples. It is well known that it is harder to convert the CO2 extracted from water samples to graphite
than is the case for other types of samples. With water samples, it could be observed, that cobalt is a
better catalyst than iron. The reason for this could be that iron, which is more reactive with regard to
CO2 , is also more reactive with regard to the other gases which accompany the CO2 extracted from water
samples. When so the surface of the iron is covered with those other gases, there is less surface left on which
the CO2 could react. In contrast to this, the surface of the less reactive cobalt stays free longer until the
reaction temperature is reached and the CO2 starts being reduced to graphite. Another reason could be the
higher content of water vapor that still accompanies the CO2 sample so that it is harder to force the above
reactions to the right-hand side. Figure 2.6 shows the graphitisation of water samples. The samples in the
normal-sized reactor R13 and in the small reactor R110 were graphitised on iron.
SEM microscope pictures of catalyst and graphite
For comparing the catalysing properties of both iron and cobalt, graphitisations with these two materials were
done and the end products compared under the SEM (scanning electron microscope) with a magnification of
up to 20,000. The magnetic properties of the examined material made further magnification impossible: The
strong magnetic field at the lens would have attracted the sample material so that it would have adhered to
the lens.
On samples BP31, BP32, BP 37 and BP38, both stable isotope measurements and scanning electron
microscopy were conducted. Figure 2.7 shows them 20,000 times magnified. BP31 and BP32 had been
graphitised with cobalt whereas iron had been used for BP37 and BP38. As the material (graphite + catalyst)
was not completely homogenous, it was not clear which carbon concentrations stayed on the catalyst that
was put in a tin cup for EA C/N measurements or on the catalyst that was used for scanning electron
microscopy. Therefore, the carbon content of the C/N samples varies a lot: from 38.3% for sample BP31a
to 4.7% for sample BP38 (see table 2.4). This difference in graphite content can also be seen on the SEM
pictures as will be explained later.
41

Figure 2.6: Graphitisation of water samples with cobalt and iron as catalysts. Pressures in % of the maximum
pressure.
When taking the SEM pictures, it was paid attention to choosing a representative part of the sample.
Figure 2.7 shows SEM pictures of the four above mentioned samples. The difference between cobalt (2.7a and
b) and graphite (2.7c and d) can clearly be seen. Cobalt consists of smaller, irregular pieces with no visible
surface structure. Iron consists of bigger, spherical parts with spiral-like surface patterns. The spheres often
are connected with each other and form longer chains. This observation fits well to the laboratory experience
with cobalt and iron as catalysts for graphitisation. When the sample (catalyst + adhering graphite) is being
pressed into a cathode, it can be felt that cobalt has a loose, powderlike structure while iron tends to be
harder to form and often sticks together as one piece.
In figure 2.7a, almost only the pure cobalt is visible. In 2.7b, little flakes of graphite have developed on
the cobalt grains. 2.7c shows iron catalysts with a lot of graphite. Note that graphite filaments are visible
around the graphite flakes that developed on the iron powder. The slightly lighter parts which are visible
on the tips of the graphite filaments are interpreted by Santos, Mazon, Southon, Rifai, and Moore (2007) as
small catalyst particles. In figure 2.7d, only a little bit of graphite has developed on the iron. It is believed
that the surface of catalyst particles is transformed to iron carbide (Fe3 C) before graphite filaments grow.
It is therefore possible that the sample sizes were not big enough for some samples to allow the beginning of
filament growth and that instead most of the carbon was taken up by the catalyst to form iron carbide.
The observed inhomogeneity of the samples shows that it is necessary to be careful to press the whole
sample into a cathode. If a little bit of the sample is not pressed into a cathode, it could be that the part
with most graphite gets lost.

2.2.2

Establishing a new graphitisation system with smaller reactors

In order to reduce the reaction volume, thinner quartz tubes and smaller fittings have been installed. The
total reaction volume for normal-sized samples is 4.5 cm3 while the new design provides a reaction volume
of 0.8 cm3 , which is only about 18 % of the volume for normal-sized samples. It is expected that reaction
rates for small samples are better in the smaller volumes, because the pressure is 5.6 times as high as in the

42

(a) BP31 (cobalt)

(b) BP32 (cobalt)

(c) BP37 (iron)

(d) BP38 (iron)

Figure 2.7: SEM pictures of graphitised samples. Note that all pictures are taken with the same magnification.

43

Table 2.4: Graphitised samples for C/N measurements and SEM

Sample
BP31a
BP31b
BP32
BP37
BP38

Sample material
0.2 mg Graphite

0.48 mg GelA
0.91 mg GelA
0.36 mg GelA

Catalyst
0.9 mg Co

0.8 mg Co
0.8 mg Fe
1.9 mg Fe

mgC
0.13
0.07
0.09
0.146
0.044

C%
38.3
17.3
16.9
25.3
4.7

13 C [h]
-16.16
-31.06
-26.77
-23.18
-22.36

SEM picture
2.7a

2.7b
2.7c
2.7d

normal volumes after the ideal gas law

p=

nRT
with the amount of substance n and the gas constant R.
V

(2.7)

That augments the collision rate between CO2 and H2 and so the reaction probability. A shorter reaction
time reduces the risk of contamination, as for example through air leaks (Smith, Petrenko, Hua, Southon, and
Brailsford 2007). Small reactors make it possible to graphitise samples which are too small to be graphitised
in the big reactors. When the sample size is too small, a reaction does not start because of the low pressure.
Santos, Southon, Griffin, Beaupre, and Druffel (2007) could reduce the minimum sample size from 0.006
to 0.002 mgC with reducing the reactor volume from 3.1 to 1.6 cm3 . They also noted that fractionation
is smaller when small samples are graphitised in the small reactors. Because of the smaller volume, the
maximum sample size for samples being graphitised in the small reactors is 0.2 mgC. Bigger samples would
cause higher pressures (note that H2 is added with at least 2.1 times the pressure of the CO2 in the reactor)
which could cause the reactors to crack, especially when the ovens start heating and expand the gases. For
comparing the reaction time of small samples graphitised in small and normal-sized reactors, seven samples
with sizes between 0.09 and 0.18 mgC were graphitised. In figure 2.8, the pressures monitored during the
graphitisation are shown. They are only given as fraction of maximum pressure because the pressure for the
same amount of gas is bigger in the smaller than in the normal reactors so that a comparison only is possible
with the relative pressure changes. All samples were graphitised using iron catalyst. The reactions were
finished after not more than two hours. The graphitisation yields for this reaction are given in table 2.5.

Table 2.5: Graphitisation yield of small samples

Reactor
R11
R12
R13
R16
R17
R19
R110

Sub sample ID
24089
24094
24095
24096
24097
24098
24099

mgC
0.18
0.07
0.18
0.18
0.15
0.09
0.17

Graphite yield (after equation 2.2)

0.97
0.93
0.97
0.98
0.97
1.27
1.15

The calculated graphitisation yield for R19 and R110 is surprisingly high, but this is due to a measurement
error. The pressure transducers for R19 and R110 could not be zeroed so that an offset had to be substracted
by hand. Additionally, the zero point changed with time. The changing offset is the reason for incorrect
pressure measurements. Still it was possible to monitor the reaction with these pressure transducers because
the offset changed slowly enough. It can be seen from the pressures in figure 2.8, though, that the completion
grade of the reaction in the small reactors 19 and 110 is bigger than in the normal-sized reactors.
44

Figure 2.8: Graphitisation of small samples in normal-sized (R11-R17) and small (R19 and R110) reactors
As was pointed out before, iron is the better catalyst in terms of reaction ratio and graphite yield. For
testing if the reaction ratio and graphite yield also prove satisfactory for a graphitisation on cobalt under
the same circumstances, two small samples (0.13 and 0.17 mgC) have been graphitised with cobalt in the
small reactors.
It can be seen in figure 2.9 that the reaction time is around
four hours, which is the double time as for a graphitisation with
iron. Smaller reactors alone do thus not shorten the reaction
time so much as does the choice of another catalyst. The catalyst plays the stronger role. The graphite yield, though, is the
same for this reaction with cobalt as for the reaction with iron
(see above). It is 1.03 for R19 (SSID 24958) and 1.05 for R110
(SSID 24958). In figure 2.10, a graphitisation of small samples
is shown for comparing the graphitisation ratio in the big and
small reactors. It can clearly be seen that the reaction of the
same sample mass (about 0.2 mgC) is faster in a small reactor
(R110) than in a big one (R13). But also here, as the samples
were graphitised using cobalt, the reaction time is quite high: Figure 2.10: Small sample graphitisation
more than four hours for the sample in the small reactor. The on cobalt.
reaction ratio in the normal-sized reactor is even slower: after more than four and a half hours, the pressure
is not yet reduced to 50% of the initial pressure. In figure 2.11, the graphitisation yield is shown both for the
big and the small reactors as a function of sample carbon mass. It is clearly visible that the graphite yield
decreases for smaller samples in the big reactors. In small reactors, the graphite yield varies a lot (this is
due to the shifting offset of the measurement apparatus), but appears to be fairly constant and independent
of sample mass. The higher yield for smaller sample masses is expected to be an effect of measurement

45

(a) Pressure in torr

(b) Pressure as fraction of maximum pressure

Figure 2.9: Graphitisation of two small samples in small reactors on cobalt

uncertainty, due to the shifting offset of the pressure transducers.
Hua, Jacobsen, Zoppi, Lawson, Williams, Smith, and McGann (2001) also observed a mass-dependence
of yield for samples graphitised with hydrogen in reactors with 3.5 ml using iron as catalyst. The reaction
time was 4 to 8 hours. The yield in their case began to decrease for samples with less than 100 gC
and showed a strong mass-dependence for samples with less than 50 gC. They observed that for samples
<50 gC, the 13 C value also is mass-dependent. The maximum isotopic fractionation was 14h for samples
of 21 gC. It has to be kept in mind that fractionation occurs during graphitisation when the reaction does
not reach completion. A similar mass-dependence for the stable isotope values as for the graphite yield
is therefore expected. Hua, Jacobsen, Zoppi, Lawson, Williams, Smith, and McGann (2001) report that
isotopic fractionation only becomes important for samples <100 gC. They also measured 14 C ratios of the

(a) Big reactors

(b) Small reactors

Figure 2.11: Graphitisation yield as a function of sample size for graphitisation on iron and cobalt
processed samples (oxalic acid standards). Even the 13 C-corrrected 14 C ratios show a mass-dependence for
samples <50 gC. For the smallest samples, the 14 C ratio is only 96% of that of normal sized samples . That
fact is hard to explain because the measurements were already corrected for fractionation occuring during

46

graphitisation, so that it could either be fractionation in the ion source or contamination with 14 C depleted
carbon (less than 100 pmC), or a combination of both.
Three effects have to be examined when using the small reactors for routine graphitisation and 14 Cdating. The first is the extent of fractionation and is checked by combusting a stable isotope standard
material (GelA in this case) and graphitising it in the small reactors. The difference of the 13 C values of the
graphite produced in that way and pure untreated GelA indicates the extent of fractionation. The other two
effects are contaminations with modern and dead carbon. As the contamination can come from different
sources with different 14 C ages, the total effect is the average of 14 C ages of the contaminants, weighted with
their relative amount. For practical reasons, contaminants are treated mathematically as if coming from
only two sources: modern and infinitely old carbon. The contribution of the first is estimated by measuring
14
C-free samples (background samples). The 14 C that is measured in a background sample indicates the
amount of modern contamination. For estimating the amount of 14 C-dead carbon contamination, it is
assumed that a constant amount of this type of contamination enters the sample. Samples of a standard
material in different sizes have to be measured. The differences in 14 C ratio between these samples indicate
the amount of 14 C-dead carbon contamination.
In table 2.6, some results for tests of the extent of fractionation are given. Both big and small reactors
were used, and both Fe and Co were taken as catalyst. The fractionation is defined as the deviation from the
13 C value of untreated GelA, which is -21.81h VPDB. It can clearly be seen that the biggest fractionation
is introduced from the graphitisation of a GelA sample in a big reactor on cobalt. The fractionation in
this case is -6.36h. Compared to that, the other two graphitisations with cobalt that took place in small
reactors, introduced less fractionation (-1.120.48h in average). The fractionation from graphitisation in
big reactors using iron as catalyst is -2.221.72h, so that in this case, the graphitisation with iron introduces
less fractionation than the graphitisation with cobalt. The graphitisation with iron in small reactors shows
something completely different: Here, the average fractionation is 0.470.88. It is remarkable that the
deviation is positive in this case. A negative deviation from the true value means that the heavier isotopes
are depleted in the sample so that its 13 C value is more negative than that of the original material. A
depletion in heavier isotopes can easily be explained with incomplete reactions. As it is easier to break
12
C-O2 bonds than 13 C-O2 or 14 C-O2 bonds, the lighter isotopes react more readily. It is thus expected that
after a certain amount of time, a bigger portion of the 12 C-O2 is reduced compared to the portion of 13 C-O2
or 14 C-O2 that is reduced after the same time.

Table 2.6: Quartz tube combustion and graphitisation of GelA samples

Reactor
normal
small
small
normal
normal
normal
normal
normal
small
small

Catalyst
Co
Co
Co
Fe
Fe
Fe
Fe
Fe
Fe
Fe

Sub sample ID
24149
24150
24151
24152
24153
24154
24155
24156
24157
24158

mgC
0.20
0.08
0.10
0.18
0.07
0.18
0.18
0.15
0.05
0.09

13 C (VPDB)
-28.17
-23.27
-22.59
-22.72
-25.70
-22.09
-23.72
-25.91
-21.97
-20.72

Fractionation
-6.36
-1.46
-0.78
-0.91
-3.89
-0.28
-1.91
-4.1
-0.16
1.09

A positive deviation indicates an enrichment in heavier isotopes. This could happen during the graphitisation process when CO is formed (also the dissociation CO2 to produce CO is easier for the lighter carbon
isotopes). It is hard to explain, though, why just the graphitisation with iron in small reactors causes enrichment in heavier isotopes. It was expected that the same kind of fractionation (enrichment or depletion)
47

occured for all reactors and catalyst types and that only the degree of fractionation varied. As the enrichment in heavier isotopes only happened for one sample, a measurement error can not be ruled out. This one
possible outlier and the quite high standard deviations suggest a repetition of these experiments. A bigger
number of samples is desired to ascertain that the type and extent of fractionation really depend on the
graphitisation settings. Although the number of samples was too small to understand the conditions that
influence fractionation, a general advice for future sample preparation can be given. The iron catalyst should
be preferred, and the samples should be graphitised in small reactors, if the sample size is below 0.2 mgC.
As can be seen from the following table, both choices reduce the extent of fractionation:
13 C mean value of graphite. . .
. . . from graphitisation on Co
. . . from graphitisation on Fe
. . . from graphitisation in normal-sized reactors
. . . from graphitisation in small reactors

Average fractionation
-2.91.8h
-1.50.7h
-2.90.9h
-0.30.5h

It has been shown that using iron as a catalyst and reducing the reaction volume both lead to faster
graphitisation ratios and possibly reduce fractionation. Another possibility of shortening the reaction time
would be another activation method for the catalyst. The standard procedure is 1 hour H2 at 400 C, but
with a preceding oxygen treatment for 30 minutes, Hua, Zoppi, Williams, and Smith (2004) report to have
reduced the graphitisation time to one third. The oxygen step enlarges the surface area of the catalyst and
so speeds up the reaction. This method has not yet been applied in our laboratory because the usage of
hydrogen and oxygen in the same system can be dangerous because hydrogen and oxygen together form the
explosive gas oxyhydrogen.
Concluding, a recommendation can be given to use iron instead of cobalt as a catalyst. The most
important reason for this choice is the faster reaction ratio of the graphitisation with iron. Another recommendation is the use of reactor volumes that are adequate to the sample sizes. The smallest possible reaction
volume should be chosen as this has the potential to reduce fractionation, i.e. leads to better completion of
the graphitisation reaction.

2.2.3

On-line combustion with EA measurements

After a short description of the existing methods of sample combustion for 14 C dating and stable isotope
analysis, I will explain why development in the existing sample combustion for 14 C dating is necessary.
The sample combustion at the elemental analyzer for stable isotope measurements will be combined with a
trapping device that can trap a fraction of the samples CO2 . The advantages of this system will be pointed
out below. Finally, the results of first tests of this device will be presented.
The AMS 14 C laboratory uses a mass spectrometer for 13 C measurements because it is more precise than
AMS, and for 18 O, 15 N, D (2 H), and 34 S measurements. 13 C and 18 O measurements are done via a dual
inlet (DI) system which uses a Gilson 220XL sampling robot which transfers the CO2 gas from vials in a 50
position manifold bed to the mass spectrometer. 13 C measurements for correcting fractionation effects for
14
C datings are also done with this system.
For 15 N and 13 C measurements, small fractions of sample material (corresponding to 200gC) are weighed
out into tin capsules and combusted at a continuous flow elemental analyzer (CF-EA) which is shown in
figure 2.12. The standard combustion of the samples for graphitisation and AMS 14 C measurements takes
place in quartz tubes filled with 200 mg copper oxide, which is heated at 900 C for one hour to burn off
possible contamination. The samples are filled into the prepared quartz tubes, which are then evacuated
and sealed by melting the glass. The samples are combusted for one hour at 900 C: At temperatures above
500 C, the CuO undergoes pyrolytic decomposition and provides O2 for oxidation (Kirner, Taylor, and
Southon 1995) so that the carbon from the sample has O2 available to react to CO2 . The CO2 is then
manually transferred to the graphitisation system where a fraction corresponding to 1.1 mgC is graphitised
and a small aliquot is saved for 13 C analysis and transferred to the mass spectrometer via the DI. If stable
isotope analysis (13 C and 15 N) is desired, another piece of sample has to be weighed out into a tin capsule
48

Figure 2.12: The continuous flow elemental analyzer (CF-EA). The sample is combusted in the combustion
tube, crosses the chromatograph column and then enters the tube leading to the trapping device and the
mass spectrometer. After J. Olsen, unpublished PhD thesis, Aarhus University.

and seperately combusted in an continuous flow elemental analyzer (CF-EA). Continuous flow means that
a constant flow of helium transports the sample from combustion to mass spectrometer.
Several groups have found out that the combustion process brings the biggest fractionation and contamination in the AMS sample preparation process. Vandeputte, Moens, Dams, and van der Plicht (1998)
examined the contamination potential of both the copper oxide and the iron they used as a catalyst for graphitisation. Although the catalyst may have a higher carbon content than the copper oxide, the contamination
contribution of the last one prevails. The amount of copper oxide needed for one combustion/graphitisation
is about 100 times as big as the amount of catalyst. Pearson, McNichol, Schneider, and von Reden (1998)
also report that the biggest contamination, about 1 gC, is being introduced during the combustion. This
constant amount of contamination affects small samples in particular. Additionally, it has been observed
that some kinds of samples are not combusted completely and that it sometimes is hard to place the sample
at the bottom of the glass: often, the samples are electrostatically charged and stick to the walls of the glass
tube so that the sample might be affected by the melting process when it is sticking to the upper parts of
the tube. This also is a problem especially for very small samples where the sample is hardly visible. These
observations necessitate developments in the combustion process if smaller samples are to be dated reliably.
The existing combustion system for stable isotope measurements at the continuous flow elemental analyser
(CF-EA, see figure 2.12) uses combustion at ca. 1000 C in an oxygen-enriched atmosphere, where the
samples are burned in tin capsules. The high temperature and oxygen-enriched atmosphere provide for
flash combustion of the sample. Through a GC (gas chromatography) column, the nitrogen and other
combustion products are separated from the CO2 and the gases are introduced into the mass spectrometer.
The introduction to the mass spectrometer takes place through an open split that reduces the sample size
to an amount tolerable by the mass spectrometer.
The objective is now to add a device for CO2 trapping to that system so that the CO2 from the sample
combusted in the EA can be transferred to the graphitisation system. The combustion of the sample in
a quartz tube is in this case not needed any longer. Such an automatic gas handling system has already
been developed by Jesper Olsen (Olsen, Heinemeier, Bahner, Graney, and Phillips 2007). It is a cryogenic
trapping device added in such a way that it is possible to shift between DI applications and CF-EA-AMS

49

applications of the Gilson robot. CF-EA-AMS denotes the sample combustion at the EA and the trapping
of CO2 for AMS measurements with simultanous stable isotope measurements.
Now instead of two combustions on two aliquots of the same sample material, one for stable isotope
measurement and one for graphitisation for radiocarbon dating, only one combustion is needed. The timeconsuming process of weighing out the sample into a quartz tube, flame-sealing the tube and combustion
over night is now not longer necessary. Online combustion combined with stable isotope measurements has
not only the potential to save time during the preparation process. It can also minimize contamination as
each step in the sample preparation can introduce contamination so that a minimization of preparation steps
is favoured.
The advantage of that combustion method is, besides the reduction of preparation steps, the pureness
of the trapped CO2 which makes its transfer to the graphitisation reaction tube easier and which has
the potential to react faster to graphite than samples combusted in quartz tubes. A combination of that
combustion system with a gas ion source has been designed at the Oxford Radiocarbon Accelerator Unit,
but the limited precision restricts its use to biomedical samples, samples where high precision is not needed
or to very small samples (between 30 and 150 gC) where high precision is not achievable (Bronk Ramsey
and Humm 2000).
In some laboratories, the tin capsules are cleaned for example with cyclohexane and acetone in order
to remove any traces of hydrocarbons. Olsen, Heinemeier, Bahner, Graney, and Phillips (2007) combusted
0, 1, or 5 empty tin capsules in a quartz tube together with anthracite coal. This process can add about
0.2 g modern carbon to the sample which results in a 0.024 higher pmC. They conclude that for very small
samples or very old 14 C samples a tin cup cleaning procedure may be successfully adopted. It was concluded
that a cleaning procedure is not necessary for our first experiments with the new gas handling system. It is
expected that a contamination corresponding to more than 0.2 g modern carbon is introduced in the first
test runs with background samples through leaks in the system or similar sources, so that it would make no
difference to clean the tin capsules before use.
After combustion, the sample is transported on with the continuous helium flow. A small fraction of
the sample CO2 reaches the mass spectrometer while a bigger fraction passes a quite thick tube which is
cooled down with liquid nitrogen. This cooled-down part of the tube is the trap. It can be sealed with
computer-controlled valves after the whole sample gas has passed and the sample is completely frozen.
Before unfreezing the sample, Helium or other gasses that might be present in the trap, but not frozen, are
pumped away. After sealing the trap, it is warmed up again so that the CO2 becomes gaseous again. Now
the pressure in the closed volume can be measured. Once the closed volume is calibrated, the pressure can
be taken as a measure of sample mass.
A Gilson 220XL sampling robot is routinely used for the transfer of CO2 gas from samples that have
been combusted elsewhere. They are transported in manifold tubes to the mass spectrometer for 13 C and
18
O measurements. This system is for example used for 13 C analysis on the CO2 that was combusted for
graphitisation. It is shown in figure 2.13. Now, the same Gilson robot can be used the other way round
for trapping the samples that were combusted in the EA and transferring the CO2 into manifold tubes to
transport it to the graphitisation system. The system designed by J. Olsen used a movable dewar that was
attached to the Gilson robot arm and could be filled automatically with liquid nitrogen. It should therefore
have been possible to run the system automatically. The glas vials that can be used with this automatical
dewar are smaller that the ones normally used for 13 C sample transfer. They have a rubber septum and can
only be used one because the septum gets broken when transferring the sample. For transfer of the sample,
the needle has to be moved to the respective vial. Then the needle is lowered just so much that it enters
the septum but not penetrates it. It is so possible to pump out the air in the needle and transfer line, as air
enters the needle and transfer line when the needle moves. Afterwords the needle can be lowered completely
so that the vial can be evacuated and is ready for sample transfer. The dewar is so moved to the glass vial
and filled with liquid nitrogen so that the sample can be frozen into the glass vial. The rubber septum of
the vial is subject to high stress when the needle is moving through the septum. The septum is therefore
deformed quite a lot. The seal height, that is, the position of the needle when it enters the septum without
penetrating it, is 2mm deeper for a septum that already was used than for a new, unused one. It is therefore

50

(a) The manifold bed and the Gilson 220XL sampling robot

(b) Sample transfer from a manifold through the

needle to the mass spectrometer

Figure 2.13: Sample transfer for 13 C dual inlet (DI) measurements

assumed that such a vial only can be used for one sample preparation process. During transfer of the trapped
CO2 sample to the graphitisation system, the septum is again subject to strong deformation forces. Another
disadvantage with these rubber septa is that rubber can get stucked in the opening of the needle so that the
needle is blocked after some trapping runs. A possible solution could be another needle with a side hole.
It is therefore planned for the future to find a suitable needle that has a side hole but is sharp enough to
penetrate the rubber septum without deforming it too much. For the tests described here, the same manifold
tubes that are used for dual inlet 13 C measurements were utilised. The advantage of them is that they have
a valve instead of a rubber septum so that they can be used numerous times without the danger of leaks. It
is furthermore easier to transfer the samples from these manifold tubes to the graphitisation system.
Olsen, Heinemeier, Bahner, Graney, and Phillips (2007) report a trapping efficiency of 38% to 84% when
the system is running automatically, but 97% when dewar and needle are moved by hand. Their measurement
results are promising: The elemental composition of carbon and nitrogen and the stable isotope analysis
of 13 C and 15 N perfectly match the result expected for normal CF-EA analysis and the 13 C values
determined by the CF-EA-AMS and the DI method on the same CO2 gas all mutually agree, indicating that
isotopic fractionation by splitting of the CO2 gas is insignificant.
There was one disadvantage with the system described above. That is that the amount of CO2 trapped in
the glass vials was totally unknown. Besides trapping, it is also important to measure the amount of trapped
CO2 . Therefore further developments of the gas handling system had to be done. The system developed
by J. Olsen was therefore modified for making it possible to check the trapped amount of CO2 . A trap
was constructed and built in so that the sample after combustion could be trapped and its amount could be
measured before it was transferred to the graphitisation system (see figure 2.14). Air-actuated valves that
are controlled by the mass spectrometer computer are used for realizing this trapping system, see figure 2.15.
The 4 port valve can switch between two positions. In the first one, the gas from the EA passes through the
trap. In the second position, the trap is isolated so that gas coming from the EA is directly lead to vent.
The physical realisation of the trap is a small copper tank that can be filled with liquid nitrogen using a

51

Figure 2.14: A sketch of the device for trapping CO2 from EA combustion. After the amount of CO2 is
meausered, the CO2 is via the existing parts of the dual inlet / Gilson transferred to a manifold tube.

pressure air pump. This pump is also controlled by the mass spectrometer computer. The actual trap is a
stainless steel tube that is wrapped around this tank. For heating the trap after trapping, a heating wire is
also wrapped around the copper tank. The trapping yield for the modified system is given in table 2.7.
As the object is to trap samples for 14 C dating, the fractionation and contamination introduced during
the trapping procedure have to be estimated. The fractionation can be examined with the combustion and
trapping of isotopic standards. In this case, the laboratory standard GelA is used. It has a carbon content
of 46% and its 13 C value is -21.81h. The difference in 13 C between the obtained graphite and the original
material indicates the extent of fractionation. This extent of fractionation has to be compared with the
fractionation that is introduced during the normal sample combustion in quartz tubes. The new combustion
and trapping method can be used for routine sample preparation if it does not induce a higher degree of
fractionation than the traditional method. The extent of modern, that is 14 C containing, contamination is
assessed by the preparation of 14 C-free samples. If those background samples have a 14 C age comparable to
that of other background samples prepared with other methods, then the trapping procedure is good enough
to be used for the preparation of old samples. For estimating the amount of old, 14 C-free, contamination, 14 Ccontaining samples of different sizes are dated. From the observed mass-dependence of 14 C concentration,
the amount of 14 C-free contamination can be estimated.
Some GelA and background anthracite coal samples were combusted in the EA and trapped in the
modified trapping device. Both groups of samples were graphitised. The graphite-catalyst mixture obtained
from GelA was placed into tin capsules for EA measurement. The difference between the measured 13 C
value for pure GelA samples and the 13 C value for combusted and graphitised GelA samples defined as
the fractionation. The graphite-catalyst mixture obtained from 14 C-dead anthracite coal was pressed into
cathodes for 14 C dating. For comparison, some GelA samples were converted to graphite in the traditional
way, i.e. combusted in quartz tubes and graphitised. The results of the traditional combustion are given
in table 2.6 Figure 2.16 shows the 13 C values for these GelA graphite samples. They were combusted in
quartz tubes, graphitised and then 13 C-measured using CF-EA mass spectrometry. 2.16a and b shows the
13 C values of 10 GelA samples as a function of sample mass (in mgC). The GelA samples were combusted in
qartz tubes and graphitised with iron or cobalt in big (4.5 cm3 ) or small (0.8 cm3 ) reactors. In figure 2.16a,
52

Figure 2.15: The valves that control the trapping process

big reactors are marked with red and small reactors with blue squares. In figure 2.16b, samples that were
graphitised using cobalt as catalyst are marked with red and those graphitised with iron with blue squares.
The valves we used for the first tests of the trapping device were not vacuum-tight enough for the
low pressures in the system. Therefore, new valves were installed and the volume of the tubes and fittings
around the trap was reduced. Unfortunately, it took a long time until tight connections to the valves were
finished in the workshop. When this finally was achieved, one of the new valves itself proved to have a leak.
The long delivery time of these valves made it impossible to rebuild and test the trapping device completely.
The tests above the horizontal line in table 2.7 were done with the setup shown above, with the valves that
were not vacuum tight. The tests under the horizontal line were done after the new valves were installed
and the volume of the tubes and fittings was reduced.

As can be seen from this table, the trapping efficiency varies a lot. This is partly due to different problems
that occured during trapping tests and necessitated modifications of the system, as for example valves that
were not completely vacuum-tight. Here, the 13 C measurement results for some GelA samples that were
combusted in the EA, trapped, and graphitised, are given.

53

(a) Quartz tube combustion - comparison big and small

reactors

(b) Quartz tube combustion - comparison cobalt and iron

catalyst

Figure 2.16: Combustion and graphitisation of GelA - comparison between different graphitisation parameters after traditionel combustion in quartz tubes

Table 2.7: CO2 trapping tests. The sample is filled into a tin capsule and combusted at the EA. The sample
size in mgC is calculated from the sample size and the carbon content of the respective sample type: 90% for
the background material Anthracite charcoal and 46% for the stable isotope working standard GelA. The
trapped amount of CO2 was obtained by measuring the pressure of the CO2 in a calibrated volume.
Sample material
Anthracite
Anthracite
Anthracite
Anthracite
GelA
GelA
GelA
GelA
GelA
Anthracite
Anthracite
GelA
Anthracite
Anthracite
GelA
GelA
GelA
GelA
GelA
GelA

Sample size (mg)

0.23
0.39
0.80
1.34
2.40
2.70
1.41
2.07
0.86
0.49
1.04
1.12
0.49
1.04
1.12
1.02
0.75
0.41
1.02
0.86

Sample size (mgC)

0.21
0.35
0.72
1.21
1.10
1.24
0.65
0.95
0.40
0.44
0.94
0.52
0.44
0.94
0.52
0.47
0.35
0.19
0.47
0.40

54

Trapped (mgC)
0.20
0.30
0.50
0.63
0.36
0.28
0.16
0.15
0.09
0.28
0.29
0.45
0.28
0.29
0.45
0.23
0.19
0.08
0.27
0.27

Trapping efficiency
95%
86%
69%
52%
35%
23%
25%
16%
23%
64%
31%
87%
64%
31%
87%
49%
54%
42%
57%
68%

SSID

trap yield

27520
27521
27522
27523
27524
27525
27526

87%
87%
49%
54%
42%
57%
68%

trapped
CO2 (mgC)
0.45
0.45
0.23
0.19
0.08
0.27
0.27

reactor
type
big
big
big
small
small
big
big

13 C
(hVPDB)
-23.110.10
-23.180.10
-22.820.10
-21.620.10
-22.910.10
-34.780.10
-35.880.10

fractionation
(hVPDB)
-1.30
-1.37
-1.01
0.19
-1.10
-12.97
-14.07

Apparently, the CO2 gas that was trapped and graphitised originates from GelA. Otherwise, it would
have totally different 13 C values. The fractionation, which is the deviation from the 13 C value -21.81hof
untreated GelA, is now compared between the samples combusted and trapped at the EA and the samples
combusted traditionally. The 13 C values of the samples from traditional combustion can be found in
table2.6. It is striking that the fractionation value is smaller for the trapped samples than for the traditionally
combusted ones. For better comparison, the results already presented in table 2.2.2 are given here again.
13 C mean value of graphite. . .
. . . from graphitisation on Co
. . . from graphitisation on Fe
. . . from graphitisation in normal-sized reactors
. . . from graphitisation in small reactors

Average fractionation
-2.91.8h
-1.50.7h
-2.90.9h
-0.30.5h

It can be seen that even the biggest fractionation in a trapped sample, a deviation of -1.37hfrom the
GelA value, is smaller than the fractionation in most cases of traditional combustion and graphitisation.
The trap test samples were graphitised on iron and according to their size in big or small reactors.
The contamination with modern carbon was planned to be tested with the EA combustion, trapping,
graphitisation and 14 C dating of anthracite samples. The anthracite is assumed to be 14 C-free. For finding
out how big the amount of modern carbon is that is introduced during AMS measurement, 14 C-dead
samples are routinely dated between the dating of unknown samples. The amount of modern carbon that
is introduced during the combustion and trapping procedure is calculated with substracting the normal
AMS background pmC from the anthracite samples pmC. Unfortunately, the results of this test are not yet
available. It was planned that the samples should be measured in the new ion source. Therefore, also small
sample sizes and iron as catalyst were used. Unfortunately, the new ion source was not yet runnning. Due
to different practical problems, it was neither possible to test the last aspect, that is, the contamination with
old carbon from the EA and trapping device. For estimating the amount of 14 C-dead carbon introduced
during the trapping procedure, one had to combust and 14 C-date standard samples of different sizes which
have a 14 C activity well above background level, as mentioned above. The pmC-difference between normalsized and small samples is an indicator for the amount of 14 C-dead carbon that enters all the samples,
assuming that the amount of old carbon introduced in the trapping procedure is independent of sample size.
This test is planned to be made in the future after several problem have delayed the assembling and testing of
the trapping device. It is also planned for future tests to measure the 13 C value of the combusted or trapped
gas via dual inlet mass spectronomy. This would enable us to estimate the influence of the graphitisation,
when the 13 C of the gas are compared to those of the graphite. The limited time and limited amount of
samples made it impossible to measure 13 C with both methods. Therefore, only the graphite was examined,
as the intention to develop such a trapping system is the preparation of CO2 samples for graphitisation and
AMS measurements.

55

Chapter 3

The sites
The aim of this thesis is, as mentioned before, dating the first occurrence of pottery in Northern Germany
which at that time was inhabited by the Late Mesolithic Erteblle culture, a culture of hunters and gatherers.
The emergence of pottery in Northern Germany is on the one hand an important indicator for contacts to
other European groups already using pottery. On the other hand, pottery is one of the characteristics of the
Neolithic, thus indicating the beginning transition from a hunter-gatherer to an agricultural society.
Erteblle inland sites in Schleswig-Holstein play an important role in archaeology because most coastal
sites are inaccessible due to the rising of sea levels (Hartz (1997); see section 3.3.2). Two inland sites next to
hardwater rivers were chosen for further examination: Schlamersdorf and Kayhude. The radiocarbon dates
of foodcrusts on pottery from these sites showed higher ages than those from coastal sites, although the same
age for both categories of settlements had been expected. The food crusts were dated to 5400 BC for Kayhude
and 5200 BC for Schlamersdorf (pers. comment Hartz 2007), see figure 3.1 on page 57. The pottery dates
are the oldest evidence for pottery in Schleswig-Holstein. Pottery from coastal sites in Schleswig-Holstein
is not older than 4750 BC (Hartz and L
ubke 2006). In Denmark, pottery does not occur before 4600 BC
although Denmark was inhabited by the people of the same culture (Hartz 1996). One possible explanation
if it should not be the hardwater effect is the close contact between southern Schleswig-Holstein and the
Neolithic regions south of the river Elbe.
The two sites regarded here have been shortly occupied hunting sites from the Erteblle culture. A short
occupation time of a settlement site can be derived from different findings, including the presence of flint
artefacts while there is no indication for flint knapping or the absence of pollen of settlement indicators like
ribwort plantain or sorrel.
In this chapter, I will describe the two sites from which samples have been taken for radiocarbon analysis. I will explain the archaeological background in some detail to facilitate the later interpretation of the
experimental results. A description of the sites and their archaeological classification follows as well as a
portrayal of the culture of that time. First, the geography and research history will be described. After
that, the geology of the sites will be addressed and the probablility of a hardwater effect will be estimated.
Therafter, the archaeological culture that is concerned here will be characterized by the natural environment
to which it was adapted to by its economy (i.e. substistence strategies) and artefacts. An assessment of the
existing theories regarding the transition from a hunter-gatherer to a farming society will be presented in
section 3.3.5.

3.1

Geography and research history

The site at Schlamersdorf (district Stormarn, see figure 3.2) is located about 7 km north west of Bad Oldesloe
in the valley of the river Trave, in a valley section which is 2 km long and 700 m wide and narrows to the
north and south to 200 m. The site regarded here, with the official name Schlamersdorf LA 5 (in the following
simply called Schlamersdorf), is situated on a low spit of land about 7.5 m above sea level (Hartz 1997) that

56

Figure 3.1: Map of Kayhude, Schlamersdorf and other EBK sites with appendant food crust datings.

reached into the former lake or river system. The Trave is the biggest river of Schleswig-Holstein that flows
into the baltic sea (Ministerium f
ur Umwelt, Naturschutz und Landwirtschaft des Landes Schleswig-Holstein
2003).
Already in the 1930s, stone age artefacts were found 3 km northwest of Schlamersdorf when the Trave was
straightened on a stretch of 350 m. The straightened part of the river with the bayou west of it can be seen
on figure 3.2. The finds, different antler and flint artefacts and potsherds, belonged to the Erteblle culture.
In 1985, K. Bokelman and S. Hartz tried to find the settlement site where these finds came from, and in
1986-1989, a total area of 400 m2 was excavated, not only for reconstructing the situation at the settlement,
but also for reconstructing the development of the lake/river which now is the Trave (Hartz 1997).
At Schlamersdorf, there are two sites called LA5 and LA15 (LA as abbreviation of Landesaufnahme)
which were excavated in 1986-1990 in the course of the project Neolithisation in Schleswig-Holstein of the
DFG (Deutsche Forschungsgemeinschaft, German Research Association). About 3,500 flint artefacts were
excavated, furthermore 800 potsherds, 400 unworked bones and antler fragments, three antler tools, one
sandstone axe, some wooden stakes that were rammed in the lake ground, and a lot of burnt flint and pot
boilers (Hartz 1996).
Kayhude (district Segeberg, see figure 3.3) is situated 15 km north of Hamburg next to the river Alster
that flows into the river Elbe in Hamburg. The site is situated in a narrow flood plain (about 50 m wide)
with geest ridges on both sides of the Alster. North of the site there is the fen Wakendorfer Moor, to the

57

Figure 3.2: A map of the site Schlamersdorf LA 5 (upper left) and its surroundings

south the Niendorfer Moor. Both fens are likely to be former lakes.
During river regulation works, a big amount of organic finds was dug up from the fluvial sediments. The
site was characterized by a lot of mesolithic surface finds (Clausen 2007). It was excavated in 2005/2006 by
Schleswig-Holsteins state office for archaeology (Archaologisches Landesamt) on an area of 80 m2 . 1500
finds could be excavated of which about 70 were potsherds. All find material came from the waste zone in
open water. Pollen analysis showed that the site was in a shallow water region which slowly sedimented.
The Alster at that time was about 50 m wide and often changed its riverbed (pers. comment Ingo Clausen
2007). A 8 m long row of wooden poles with a length of up to 70 cm can be interpreted as a fish weir.
According to 14 C datings, it was constructed around 5000 BC. Other finds were antler axes (among them
several T-axes), typical Erteblle pottery, wooden tools, a stone mace head, pot boilers and several bone
and antler remains from wild animals (Clausen 2007). One date of a foodcrust on a potsherd gave the age
5400 BC, which is 400 years older than the fish weir and almost 800 years older than pottery from coastal
sites (Clausen 2007).
Layers of sand and detritus were washed ashore and had influence on the finds of the upper layers. Some
of the finds are positioned diagonally or upright in the sand so it can be concluded that they have been moved
by the water. Because of the different layers which were washed ashore, it is hard to draw a stratigraphy.
It is thus hard to conclude which of the artefacts were associated. Therefore, only finds from a stone layer
at the bottom of all the layers were taken. This stone layer seemed to be undisturbed and contained two

58

Figure 3.3: A map of the site Kayhude LA8 (marked with yellow in the center of the map) and its surroundings

T-axes, a mace head and many ceramic and flint artefacts (pers. comment Ingo Clausen 2007).

3.2

Geology

As explained in section 1.2.3, the water hardness is an indicator for the carbonate concentration in the water
and thus an indicator for the hardwater effect. We assume that the water hardness as we measure it now
has not much changed from the water hardness during the time of the Erteblle culture. There are processes
which can alter the water hardness of a river. The one is changes in the course of the river or decalcification
of the underground. The other is man-made changes of water hardness, for example marling of the fields
next to the river so that carbonate from the marl can be washed out into the river. We now have to estimate
the probability of these processes for the rivers Alster and Trave.
Both rivers are supposed to have been fluvial systems with hard water already during the time of the
food crust formation, the Erteblle period in the late Atlantic pollen zone, and the course of the rivers is
expected to have changed only to a very limited extent. Anthropogenic changes have as well taken place only
to a limited amount on these rivers: The Trave and Oberalster [the upper Alster] are two of the few nearnatural brooks and rivers in Schleswig-Holstein and Hamburg (http://www.uni-kiel.de/Geographie/lehrvonline/GeoVis2000/InternetGIS/Ergebnis/att/Texte.html from 12. July 2007, authors translation).
There is another possible man-made change of water hardness: the marling of the fields next to the rivers.
59

Marl is a loose or crumbling earthy deposit (as of sand, silt, or clay) that contains a substantial amount of
calcium carbonate (Merriam-Webster Online Dictionary on September 11, 2007) which is applied to muddy,
acidic soils. The sand or clay is used to make the ground more compact and the calcium carbonate can
neutralize acid to improve conditions for agriculture. So there is a danger that the water hardness increased
during historical times because the calcium carbonate from the marl could have been washed out into the
river. For the Alster, there is a low possibility for this effect, because people in that region were poor
and could probably not afford the marl. Additionally, they mainly lived on selling peat and clay bricks to
Hamburg, and not on agriculture. For the moderate agriculture in this region, the land did not need to
be used intensively. It is therefore unlikely that expensive marl was used for improving the wet fields next
to the river (pers. comment Ingo Clausen 2007). The region at the Trave around Schlamersdorf was more
prosperous. It has therfore been suspected that great land owners used marl to improve the quality of their
fields. However, there is no reason for that concern: The Trave valley between Bad Oldesloe and Schwissel,
including Schlamersdorf, has been thoroughly examined by U. Cimiotti and he excludes this possible source
of carbonate contamination: The lowlands next to the river have been agriculturally so unattractive that
they have not even been examined before Cimiottis work (Cimiotti 1983). The underground of the present
Trave could have changed since the Mesolithic/Neolithic, because it consists mainly of sediments. Still it
can be expected that the Trave had hard water also in former times because the Trave valley is called one
of the best-preserved examples of subglacial meltwater tunnel valley with mostly undisturbed landscape
(Ministerium f
ur Umwelt, Naturschutz und Landwirtschaft des Landes Schleswig-Holstein 2003). During
the Atlantic period, there was a large body of water in the Trave valley with a slow current. Probably the
Trave already ran through this lake system during the Boreal (Cimiotti 1983). In the Atlantic, a strong
aggradation of the lake basin started that led to a lowland with fens through which the river Trave was
flowing, surrounded by wetlands. Through the dry phase of the Sub-Boreal, the water level sank and forests
spread along the river, resulting in the formation of peat (Bruchwaldtorf) but were drowned again during
the cool and humid Sub-Atlantic, leading to fens and the formation of fen peat. Today, the Trave valley
would still be dominated by fens if there had not been changes of the landscape through straightening of the
river, drainage and pasturing (Cimiotti 1983). The natural vegetation and appearance of the Trave valley
today is therefore similar to the situation during the late Atlantic.

3.2.1

Water hardness and

14

C in the Trave and Alster

Both rivers show a quite high carbonate content: The Trave downriver of the Wardersee at Warderbr
uck (ca.
25 km upriver of Schlamersdorf) has an average calcium concentration of 87.6212.29 mg/l and a magnesium
concentration of 7.190.69 mg/l so that the total water hardness, when neglecting other alkaline earth metal
ions, is 94.8112.59 mg/l. That corresponds to 13.31.8 German degrees ( dH (0-8.4 dH: soft, 8.4-14 dH:
medium, >14 dH: hard)), the unit which is common both in Denmark and in Germany to state the
hardness of water. The Alster at the tide gauge Wulksfelde (5 km downriver of Kayhude) has 61.519.17 mg/l
Ca and 5.190.57 mg/l Mg. The total water hardness 66.719.58 mg/l corresponds to 9.31.3 dH, which is
still a medium hardness. The Ca and Mg concentrations were mean values of the monthly measurements from
the State Agency for Nature and Environment of Schleswig-Holstein, Germany. For the Trave, measurements
have been done in 1998 and from 1/2001 to 12/2006. The Ca and Mg concentrations of the Alster have
been measured from 1/1997 to 12/1998 and from 12/2000 to 12/2006 (LANU, pers. comm. 2007). See
section 1.2.2 for a definition of water hardness and its implications for 14 C dating. The water hardness of
the water samples Trave 1.1 and Alster 1.1 was measured. These were the water samples which were taken
closest to the sites Schlamersdorf and Kayhude, respectively. The Trave water had a hardness of about
13 dH, the Alster water about 10.5 dH. These values are consistent with the measurement of the State
Agency for Nature and Environment (see above). The relatively high water hardness makes a hardwater
effect on pottery plausible, if people from that time had cooked freshwater fish in the pots. The effect is
expected to be greater at Schlamersdorf, Trave, than at Kayhude, Alster, but the radiocarbon dates now
available seem to indicate the opposite (see section 4.2.1 and 4.2.3).

60

3.3

Erteblle and Funnel Beaker culture

The Erteblle culture (EBK) is named after the classic kitchenmidden at Erteblle, a Late Mesolithic coastal
site (Andersen and Johansen 1986). It is a Mesolithic hunter-gatherer culture with some neolithic habits in
Southern Sweden, Denmark and Northern Germany. Although the coastal kitchenmiddens are a well-known
characteristic of the Erteblle culture, there are also many Erteblle sites without kitchenmiddens as well as
inland sites.
Instead of some neolithic culture specific elements, such as ceramics
or polished axes (Hartz and L
ubke 2006), a classification of the EBK into
the Mesolithic stands to reason because the most important criterion for the
classification is the producing way of life (Hartz and L
ubke 2006). However,
Erteblle culture has to be differentiated as Nordic Terminal Mesolithic period
from the Late Mesolithic, as it was exposed to an acculturation process through
the neighbouring Central European Neolithic cultures like Linear pottery and
Post-Linear pottery cultures. Subsistence economy and settlement types of
the Nordic Terminal Mesolithic are based on the Late Mesolithic tradition.
Only the artefact assemblages allow an archaeo-typological differentiation from
the Late Mesolithic (Hartz and L
ubke 2006). The Erteblle culture can be Figure 3.4: Funnel beaker
subdivided into two phases: the aceramic (before the introduction of pottery) and the ceramic phase.
Only recent research has assured that the aceramic Erteblle was present in Northern Germany, while this
phase has been known for a long time in Denmark (Hartz 2005). The Funnel Beaker culture (TRB, the
abbreviation for German Trichterbecher) is the first completely neolithic culture of the North German
Plain in the sense of a society whose economy is based on agriculture. The Funnel Beaker culture is named
after a typical kind of pottery, the funnel beaker (see figure 3.4) and follows the EBK. The sites which are
examined in this thesis belong to the EBK and have probably the oldest pottery in Schleswig-Holstein.

3.3.1

EBK research history and Kkkenmddinger

In this section, I will describe how the Erteblle culture was discovered. A description of the site next to
Erteblle at the Limfjord in Denmark, the locus classicus which is eponymous for the culture, will explain
its main features, along with a description of the characteristic kitchenmiddens, the kkkenmddinger,
because it was the investigation of kitchenmiddens that started the interest for the Danish/Northern German
Mesolithic: the big kitchenmiddens are found more easily than the small layers of other deposits which are
characteristic for other settlements. Denmark is one of the classic areas for prehistoric studies of shell
middens and has a long archaeological tradition for investigations of kitchenmiddens or Kkkenmddinger
(Andersen and Johansen 1986). Kitchenmiddens are accumulations of waste (at Danish coastal sites mostly
shells) from human settlements. The first excavations on kitchenmiddens took place in 1837. In 1851 it was
shown that the investigated kitchenmiddens were not a natural accumulation of shells, although it is also
possible that there is a natural accumulation of shells when a kitchenmidden is inundated (Richter 1986). In
the same year, the name kkkenmddinger was introduced (Andersen and Johansen 1986). This name is
still in use, synonymous with kitchenmidden, and not restricted to the Danish literature. It was found out
that the kitchenmiddens represented an earlier kind of stone age than the phase in which the well-known
megalithic graves and polished axes emerged (which is now known as the Neolithic), and this earlier culture
was called Erteblle. It is now often called Mesolithic, but because of some neolithic aspects like pottery,
sedentariness and the beginning of the transition to farming, in the past the term proto-neolithic was
sometimes preferred (Schwabedissen 1959). A newer name proposal for the time of the EBK is Nordic
Terminal Mesolithic. Hartz and L
ubke (2006) differentiate so between the Late Mesolithic with typical
Mesolithic tool assemblages and the EBK, whose economy is based on Mesolithic subsistence strategies,
but whose material culture shows a different flint tool spectrum and the use of pottery, which connects
them with the following fully Neolithic, culture, the TRB. Although they are a very special feature of that
culture, shell middens are not necessarily situated at Erteblle sites. Even within small areas, one may
find contemporary coastal settlements with an associated Kkkenmdding and/or without (Andersen and
61

Johansen 1986). The Erteblle site itself had been repeatedly inhabited for several hundred years before the
accumulation of the midden started(Andersen and Johansen 1986).
The shell midden at Erteblle - one of the
largest middens in Denmark - was excavated in
1893-1897 for the first time. It can be regarded as
a typical Danish kkkenmdding. It consists of
marine molluscs (mainly oysters), charcoal, flint
debitage, animal bone, ceramics, and stones of
varying size. There are also fireplaces, layers of
ash and flintknapping and food-processing areas
(indicated by flint debitage and bones / fishbones
respectively) in the midden (Andersen and Johansen 1986). Very thick-walled pottery occurs
around 3700 BC. Like other kitchenmiddens, it
has been accumulated over 700 years: the oldest 14 C-date from the bottom of the midden is
3,800 95 BC, the youngest from the top layer is
3,120 90 BC, so that all dates are of a Mesolithic
age (Andersen and Johansen 1986). Accumula- Figure 3.5: The reconstructed Erteblle settlement
tion rates vary over the years, and the middens Photograph by Peter Marling/Scanpix Nordfoto
grow also horizontally, not only vertically. The
Erteblle midden, for example, grew from north to south. The locus classicus Erteblle will also provide
some examples for the economy of that culture in section 3.3.3. A similar culture, showing the same economy
and pottery, but lacking kkkenmddinger, was discovered in Northern Germany and termed Ellerbekkultur after the site Ellerbek, where during dredging works in the Kiel fjord many finds from former fresh water
lakes could be found in the years 1876-1903. After the insight that kitchenmiddens are not a necessary part
of EBK settlements, and because there were no differences in the artefacts, if was concluded that Ellerbek
and Erteblle in fact are parts of the same culture. In Northern Germany, the Erteblle culture is sometimes
referred to as Erteblle/Ellerbek-Kultur.

3.3.2

The environment of the Erteblle culture

After the last ice age, the climate became rapidly warmer until it reached the high Atlantic climatic optimum
(L
uth, Maarleveld, and Rieck 2004). The inland ice of Scandinavia melted already in the Boreal. During
the Atlantic, the North American ice sheet collapsed and caused a rising of the sea level (Dellbr
ugge 2002).
The North Sea developed in 8000 to 6000 BC, and the coast line moved in average 100m per year, so that
people in that time often had to move their settlements (L
uth, Maarleveld, and Rieck 2004). The rising of
the sea levels resulted since 7000 BC in the formation of the Baltic Sea, which before had no connection to
salt water and was called Ancylus Lake. The river Trave flowed in that time into the Ancylus lake (Hartz
and L
ubke 2006). The new sea is also called Litorina Sea after the salt water snail Littorina Littorea, and
it was mainly formed during four big transgressions, the early atlantic, high atlantic, late atlantic and early
sub-boreal transgressions (Dellbr
ugge 2002). The formation of the Baltic Sea had a wide variety of habitats
as result, with estuarine systems being the most stable and diversified ones (Mahler 1981). The exploitation
possibilities of the different habitats will be described in section 3.3.3. At the end of the EBK, the climate
deteriorated which resulted in a scarcity of food resources, especially in winter. Oysters, which could bridge
the food resource gap in late winter, were available only in the warmer periods in Northern Denmark. This
climate deterioration is one possible reason for the development of farming, as will be explained in detail in
section 3.3.5.

62

3.3.3

The Erteblle economy

The Terminal Mesolithic Erteblle culture, though belonging to the Mesolithic, already shows some traits of
the Neolithic. Besides sedentariness at places where marine resources could be exploited without the need
for nomadism and the first occurrences of pottery, the first domesticated animal, the dog, appears in the
archaeological record of the site Erteblle (Andersen and Johansen 1986). Since the time of the Erteblle
culture, coastal settlements became important or at least for the first time visible in the archaeological
record (Brinch Petersen 1993). Molluscs, fish (both marine and freshwater) and sea mammals, game like roe
deer, red deer and wild boar are represented at Erteblle sites. Bones of animals that were killed for their
fur were also found (Andersen and Johansen 1986). Big mammals were hunted with bow and arrow which
is documented by fragments of flint arrow heads that were found in bones (Hartz 1997). Carnivores and
rodents like marten, wildcat, otter, beaver and squirrel could also be caught in traps (Hartz 1997). Big fish
were killed with spears with fine-toothed bone points, with harpoons or nets of bast fibres while eel was also
caught in fish traps or with wooden eel spears (Hartz 1997). Although fresh water fish provided a big part
of the diet, there is evidence from some Danish sites that even if salt-water fish contributed to diet only in
a minor way, yet line-fishing from boats in a considerable depth of water must already have begun (Clark
1948). The evidence is bones of large, mature specimens of haddock and coal fish, since both are habitable
to depths from 40 to 100 metres and imply line-fishing as the Danish coastal waters are too shallow (Clark
1948).
One example for the exploitation of fish is the locus classicus, the site Erteblle: Most of the fish bones
at the site Erteblle are from freshwater fish with cyprinids and eel as the most prominent representatives
(Enghoff 1986). Most likely, they were caught in two nearby lakes, which now have disappeared. The number
of fishbones of the different species can not be taken as a proxy for the importance of each species, because
of the different number of bones per fish. Eel (Anguilla) has ca. 115 vertebrae, whereas cod (Gadus) only
has ca. 50. The preservation probability also varies for bones of different species. Bones from some kinds
of fish contain more fat than others and are therefore preferred by foxes and dogs. Because of the different
structure and composition, some bones disintegrate more easily than others (Enghoff 1986). The range
of marine species and their sizes indicate that they were caught in shallow water near the shore, so it is
probable that they have been caught with fish traps (Enghoff 1986). There have been no remains of fish
traps at the Erteblle site, but use-wear analysis on flint tools suggests the production of traps. At some
other sites, though, equipment like eel prongs and fish traps were preserved.
Another example is the site Grube-Rosenfelde LA 83 which was excavated in 2001 and 2003. In the
marine coastal sediments at the former shore, remains of big animal bones in their anatomical position and
rests of fish prongs were found. Additionally, large amounts of eel bones (Anguilla anguilla) were associated
with a fireplace. This site can be interpreted as a temporarily used station for catching eel. Fresh, but
otherwise useless, parts of prey could have been placed in the shallow water to attract eel (Hartz 2005). The
eel was then processed at the fireplace and the waste came into the fire and was so preserved (Hartz 2005).
Eel seemed to play an important nutritional role throughout the whole EBK, as indicated by remains of eel
bones, eel prongs, fish traps and weirs (Hartz 2005).
In the environment described above, three different types of adaptation, concerning the settlement pattern, are possible after (Mikkelsen 1978)):
1. permanent settlement at one biotope with storage to cover periods of food scarcity
2. permanent base camps between different biotopes with small task groups temporarily exploiting the
biotopes
3. non-sedentary, with an annual migration cycle
Although a hunter-gatherer community, the Erteblle settlement pattern was quite stable. 13 C measurements
have shown that people from coastal sites lived mainly on marine food, and that people from inland sites
lived mainly on terrestrial food. We may probably speak of large base camps occupied most of the year,
with a radial exploitation pattern of the surrounding area by the help of specialized satellite extraction
camps (Madsen 1986). There are only few hut remnants found at excavations (Andersen 1993) but larger

63

accumulations of findings and the presence of some graves give hints to settlements (Kannegaard Nielsen
and Brinch Petersen 1993).
Paludan-M
uller (1978) investigated the ecological conditions and their influence on hunter-gatherer subsistence chances of different ecosystems in Northern Zealand, and his results are applicable to the whole area
of the EBK culture. Depending on their productivity, seasonality, stability and diversity, some ecosystems
are better suited for keeping a stable, sedentary population of hunter-gatherers whereas others only can be
exploited by limited groups and not year-round. Estuarine systems seem to have the best conditions, because
a high productivity and diversity here results in high stability. Furthermore, the exploitation of different
resources is possible: marine and freshwater fish, molluscs and mammals, terrestrial and water plants as well
as terrestrial mammals and different kinds of birds. The seasonality in estuarine systems is small enough to
allow a population of hunter-gatherers nutrition during all seasons. Fresh water systems are almost equally
good, but show a higher degree of seasonality, due to a lack of marine resources. Fishing at the open coast
or on the sea would have been less effective than that at estuarine and freshwater systems, where the use
of fish traps minimized the effort, and is therefore expected to have given a negligible contribution to the
EBK nutrition. On small islands in the Baltic sea, there were peak occurrences of seal during the winter,
their breeding season, so the exploitation of this resource by small task groups and in limited intervals could
have provided the EBK society with meat, fur, fat and oil for the lamps during winter, when other resources
were not easlily exploitable. Forest areas are expected to have been less attractive. The forests at the time
of the EBK culture had a dense canopy with few light entering the soil and therefore little undergrowth.
This kind of forest is also called the High Atlantic climax forest after the climatic period during that time,
the High Atlantic climatic optimum. Food resources as edible plants (e.g. hazelnut or raspberry) and big
deer were therefore mainly found at the edge of the forest, except only for mushrooms, roots and wild boar
(Paludan-M
uller 1978). Pollen diagrams show changes in the forest landscape during the Erteblle culture
which indicates a limited forestry with clearings and cultivation of grain, but with marginal economic importance (Schirren 1997). Clearing of the dense forests may also have had another cause than cultivation of
grain: felling big trees and so letting more light entering the forest could have been a method to ameliorate
the conditions for edible plants and deer in order to enlarge their population.

3.3.4

Erteblle pottery and tools

The Erteblle culture was the first North European culture that produced pottery. Normally, pottery is
associated with the introduction of agriculture, but it is now known that pottery production preceded
agriculture in several instances. Instead, the basic requirement for the production of pottery is sufficiently
long periods of sedentism, spent close to appropriate clay sources and under suitable climatic conditions, to
allow time for collecting raw materials and for forming, drying and firing the vessels (Tite 2003b). The
most characteristic kind of pottery is the Spitzboden, the pointed base vessel or point-butted vessel. As
a second type flat bowls in boat form, called lamps, are found (figure 3.7). The pointed base vessels
have apparently been used for cooking food, because charred food crusts can often be found on them. Our
experiments also show that they are well suited for cooking food (see section 4.1.3). They are in most cases
built up from coils which have been smoothed in a certain way so that the side of a sherd shows U-shaped
lines (see figure 3.6).
The lamps are expected to have been filled with blubber or oil that was cooked out of blubber, therefore
they are also sometimes called blubber lamps. Experiments showed that the EBK pots are good for
cooking oil out of blubber and that the lamps can be used for different purposes, depending on the wick:
a small wick gives a small and very quiet, non-sooting flame, good for indoor use, whereas a thick wick
produces a very bright light that is stable under windy conditions and could for example have been used to
attract fish during night-fishing or to illuminate the outdoor areas of the settlement (pers. comment Hartz
2007).
A comprehensive description of the flint tool inventories of the different phases of the northern German
EBK can be found in Hartz and L
ubke (2006). In general it can be said that in the EBK, the micro-blade
flint technique of the Late Mesolithic disappears. Macro-blades produced in punch technique, transverse
arrowheads and trapezoidal, flat trimmed flake adzes become the most common artefacts. Transverse arrow64

(a) Mixing clay and temper (granite chippings)

(b) The pointed base

(c) Building up the pot in Utechnique

Figure 3.6: Rebuilding a pointed-base vessel in the so-called U-technique

heads may not seem to be so efficient at first view, but they are in fact very useful for hunting in the forest.
The arrow rotates after being shot off and so drills through the fur and skin of the deer, causing a heavily
bleeding wound. It is not possible to kill a deer with that arrow with a single shot, but it is easy to follow
it after the blood it loses. Borers and burins were made out of flint stone flakes, but also ground stone tools
such as round-pecked axes can be found.

3.3.5

Transition to farming: From Mesolithic to Neolithic or from Erteblle to

Funnel Beaker culture

The introduction of agriculture and animal husbandry marks the transition from the Mesolithic, the middle
stone age, to the Neolithic, the younger stone age. This process is called neolithisation and is the most
extensive change in human life conditions that happened in Europe until today. In the course of few
generations, not only the way of food production changed, but also the type of society, beliefs and technology
(Andersen 1989). For some regions, it is therefore also called neolithic revolution. In Southern Scandinavia,
where the change happened gradually, this term is maybe not appropriate. In 4700 BC, the first pottery
came to southern Scandinavia, but a real farming culture did not occur before 4000 BC (Andersen 1989). At
3900 BC, the culture change was completed and the Funnel Beaker Culture (TRB) established (Andersen
1989). In Northern Germany, the oldest pottery was produced around 4750 BC, if we exclude the pottery
with uncertain ages because of a possible reservoir effect (Hartz and L
ubke 2006). The introduction of pottery
in Northern Germany and Denmark can therefore be characterized as being happened contemporarily. The
new way of producing food necessitated also new technologies, so that there was a big change in the tool
inventory (Andersen 1989). A consistent chronology of the whole Neolithic in Europe is hard to achieve
because of the cultural diversity during that time. Some parts of Europe were inhabited by hunter-gatherers
while elsewhere, farming societies had lasted for a course of many generations. Anyway, the chronology
needs a stable framework that is independent of cultural groups. Cultural groups that are found or defined
in the future can so fit into that framework (Fischer 1976).
The transition was not only economical, but also social and religious: from the egalitarian hunter and
gatherer society to the ranked farmer society, with a completely different perspective towards its territory.
Storage of harvested goods caused the division of production and consumption and necessitated a controlling
factor which finally ended with a hierarchical society. Also the attitude towards the land changed: agriculture
requires fields which belong to the people who work on these fields, so the protection of the territory suddenly
was a very important task (Mahler 1981). As the transition to farming took place at the end of the EBK
and as pottery is one of the aspects of neolithic cultures, the dating of EBK pottery will provide information
about the process of neolithisation in Northern Germany. Therefore, I will now describe possible theories
about the transition from Mesolithic to Neolithic in some detail, because the results of the datings and
65

(a) Pointed-base vessels (unfired)

(b) Pointed-base vessels and lamp

(fired)

Figure 3.7: Erteblle pottery (copies). Photographs by Aikaterini Glykou.

isotope measurements have to be interpreted in terms of culture change and contacts to other cultures.
Why is it hard to explain this transition?
Normally, the transition from a hunter-gatherer to an agricultural society is regarded as natural because it is
a form of progress. Farmers are regarded to have a higher security regarding the availability of food resources.
An agricultural, stratified society with division of labour is also able to make bigger cultural achievements.
In the area north of the lower Elbe, the EBK area, the question why people gave up hunting and gathering
to start farming is hard to answer, because the life of a farmer is harsher than that of a hunter-gatherer
in that region. The neolithisation, which proceeded from the Eastern Mediterranean throughout Europe
with a speed of approximately 1 km annually, reached central and northwestern Europe around 6000 BC
(Andersen 1989) and stopped from 5000 BC on at the lower Elbe for 1000 years (Fischer 1974), because the
introduction of agriculture was not necessary north of that region: The productive coastal zones provided
enough food for the whole population so that the Mesolithic economy with its low labour demands could
exist there for a long time. This is called the Garden of Eden argument (Madsen 1986). The work effort
of a hunter-gatherer community for example consisted of only 2-3 days per week, while farmers had to work
much longer to achieve the same amount of food (Fischer 1974). The higher mobility makes it furthermore
possible for hunter-gatherer communities to move to richer regions in case of food scarcity, while farmers are
bound to their settlements with their fields and crop. There is even archaeological evidence for the flexibility
of the EBK community: The number of Erteblle sites increased strongly when the sea level rose and marine
resources came into the Danish baltic sea which points to a flexible, fast reaction (Rowley-Conwy 1985). The
hunter-gatherer subsistence strategies provided sufficient nutrition as can be seen on skeletons from EBK
graves. Furthermore, the absence of caries and chronic diseases, apart from gout with aged individuals, is
a sign for the balanced nourishment of the Mesolithic population (Kannegaard Nielsen and Brinch Petersen
1993). In the past, the introduction of agriculture was, as most big changes in society and economy, explained
by immigration of groups that already used all these new techniques. But the archaeological record gives
another result, for example in the area examined here, the south-eastern part of Schleswig-Holstein. Here,
the mixed Mesolithic and neolithic material of some sites indicates a site continuity. The preferred settling
regions of the Mesolithic and the Early Neolithic correspond for example in the range of the rivers Trave
66

and Alster. Theses areas probably kept their economic importance as fishing and hunting stations until the
beginning of the bronze age (Schirren 1997).
Different phases in the transition
The adaptation of agriculture and the development to a neolithic society takes place in a process which can be
divided into different phases. There is one advantage when examining this process in Southern Scandinavia:
The transition to farming in the European part of the boreal zone was a far more gradual process
than elsewhere in Europe. This makes it possible for archaeologists to trace the transition to
farming at a finer level of resolution and to isolate discrete phases in the decelerated evolution of
settled farming communities (Zwelebil and Rowley-Conwy 1984).
One can divide the process of adaptation of farming into three phases, from a phase of availability to
substitution and finally consolidation.
How these phases are reflected in the archaeological material from Schleswig-Holstein
The Erteblle culture existed at the same time as the Central European Early Neolithic sedentary Linear
pottery and Post-Linear pottery cultures (Hartz and L
ubke 2006). Around 3400 BC, at a former bay on
the Baltic sea coast of Schleswig Holstein, the Dahmer Bucht, a strong influence from southern cultures
is visible. Parallels to the Neolithic Michelsberg culture show the close cultural contacts which now link
Northern Germany closer with the Central European development (Meurers-Balke 1983). The eastern parts
of Holstein seem to have been a center of commerce between Eastern Denmark and the neolithic settlement
areas at the Elbe, as for example Danubian axes on the sites Grube-Rosenhof and Neustadt show (Hartz
2005). Hartz and L
ubke (2006), though, warn that not every innovation is a sign of contact to neolithic
culture groups: Certain elements in the artefactual record, such as pottery or T-shaped antler axes, which
have always been interpreted as Neolithic influences, could originally have come from other Mesolithic groups
in northwestern Europe or the Baltic. But one artefact group clearly is an indicator of contacts to Neolithic
cultures: Findings of shoe last axes show contacts to central Europe or in fact even to the Balkans; in
Denmark (Fischer 1993) as well as in Schleswig-Holstein (Schwabedissen 1979). So, in the case of EBK to
TRB, the availability named by Rowley-Conwy (1984) was provided through contacts to the Michelsberg
culture and further south (Fischer 1993).
Nevertheless, the EBK phase of Rosenhof at the Dahmer Bucht can not be regarded as fully Neolithic.
Some of the first proofs for a beginning neolithisation have been argued against: There are only two bone
fragments of domestic cattle, which does not indicate that stock-keeping was an important food source,
especially not because the cattle could have come (donated or traded) from the Michelsberg culture. Traces
of cereal pollen could have been spuriously identified, while a potsherd with a grain impression is also
probably a Michelsberg import, like other imported pots from Michelsberg and Baalberge (Zwelebil and
Rowley-Conwy 1984). The uncalibrated 14 C age for the finds of domestic cattle is 5960 65 BP (Heinrich
1993).
New excavations at Rosenhof in 2001 and 2002 showed a closed find inventory from the time between
4800 and 4500 BC (calibrated age) with a lot of Erteblle tools but no signs of agriculture or stock-keeping
(Hartz and Schm
olcke 2006).
The availability phase ends with the adoption of at least some elements of farming by the foragers, or
with the settlement of farmers in the territory hereto exploited by hunter-gatherers (Zwelebil and RowleyConwy 1984). Thus, the availability phase comprises the early and classic Erteblle and lasted for more than
1000 years (Zwelebil and Rowley-Conwy 1984). Pottery and more or less strongly developed sedentariness
for example have been adopted very early.
In former times it was believed that the EBK and the Funnel Beaker culture (TRB) ran parallel for a
considerable amount of time (Madsen 1986). But since the 1970s, when 14 C dates from EBK and TRB
became available, it was known that they were not contemporaneous but followed each other, which is also
visible at some sites with both EBK and TRB finds (Andersen 1989). Hunting, fishing and gathering was
67

the main form of subsistence on all northern German and southern Scandinavian Erteblle sites (Hartz and
L
ubke 2006). Even in the full Neolithic, in the Funnel Beaker culture, hunting, fishing and gathering still
played an important role. The strong links and a possible continuity from Erteblle to Funnel Beaker can
for example be seen on neighbouring sites on the former Dahmer Bucht: Siggeneben S
ud and Rosenhof,
as well as Wangels, 15 km west of Rosenhof.
On the former coastal site Siggeneben S
ud, for example, hints for farming and cattle have been found,
but there were also rests of hunting and fishing equipment (eel prongs, spears). The findings propose that
Mesolithic and Neolithic economy were equally important on that site. Siggeneben S
ud has been radiocarbon dated to 3200-3000 BC (Meurers-Balke 1983).
On the neighbouring site Rosenhof, whose main layer consists of Erteblle remains, the economic situation
was approximately the same, but hunting, gathering and fishing played a more important role while there
were only small beginnings of agriculture and cattle. When comparing these two sites, one finds a continuity
from Erteblle to Funnel Beaker. On the bottom layer of Rosenhof, there are pointed base vessels and
lamps. Its younger pottery shows a strong influence of the Michelsberg culture and leads to the Funnel
Beaker culture. In the following phase, which is situated at Siggeneben S
ud, there is a broad spectrum
of funnel beakers and flasks. The strong links to the Erteblle culture are proved by the occurrence of
lamps in the early Funnel Beaker culture. Although these differences in the pottery define the two different
cultures, the inventory of stone, wooden and bone tools from the two sites is morphological and quantitatively
comparable. There are only some tendencies that would show a technological change, like the changes in
pottery and in stone tool technology (blade technology decreases in importance, the first polished axes are
produced). As a conclusion, there must have been comparable activities during Erteblle and Funnel Beaker.
Wangels has been excavated from 1996 until 1999 and contains elements both from the late EBK as
well as from the early TRB. Pointed base vessels and lamps have been food-crust dated and belong to
the time before 4100 BC. A completely different type of ceramics was dated to 4100-3800 BC: decorated
funnel beakers, flasks, beakers with ears, thin-walled bowls and pots with round bottom which represent the
repertoire of the earliest TRB. There are also changes in the stone tool industry: polished axes, made from
imported stone, occur for the first time, as well as core axes with specialised cutting edges. The rest of the
stone tool spectrum remains unchanged and continues EBK traditions. In contrast to Rosenhof, there are
hints for a developed crop-keeping in Wangels, as the archaeo-zoologist Dirk Heinrich has found out: Two
thirds of all mammal bones are from domesticated animals, with cattle as the biggest group (two thirds of
all domesticated animal bones). Sheep/goat1 bones already occur 4200 BC, before the culture change from
EBK to TRB, whereas cow bones date only back to 4100 BC, the time of the culture change. There are
also signs for agriculture: pollen of emmer wheat, one charred emmer grain in a potsherd, imprints of grain
spikes on a sherd and fragments of mill stones (Hartz and Schmolcke 2006).
The substitution phase is therefore visible already in the late EBK layers, as in Wangels, where for
example sheep/goat is found. The consolidation phase is the beginning of a new fully Neolithic culture, the
TRB, in Denmark for example in 3900 BC (Andersen 1989). It developed on the basis of a EBK that already
began using some Neolithic techniques.
Different models
For the explanation of the Mesolithic-Neolithic transition, different scientists focused on different aspects.
This resulted in a number of different models.
Climate change caused a shortage in food resources The transition from atlantic to subboreal
climate brought about some major changes: summer temperatures which were 2 C lower as well as lower
salinity, temperature and nutrient content of the sea water. The adoption of farming has been explained at
least for the Erteblle kitchenmidden sites in western Denmark where a lower salinity once led to a lower
content of oysters in the fjords. The oysters were bridging a food gap in late winter/spring, and when they
1 Sheep and goat bones are hardly distinguishable. Therefore, in most cases they are stated as sheep/goat instead of
deciding for one denotation.

68

disappeared, something else was needed to bridge that gap. Because farming was done by communities in
the south and because there were contacts between these different groups, it was likely that farming was
adopted to have something to eat in the times when there were no other matching resources available. Deer,
for example, has a very low fat content at the end of the winter (Rowley-Conwy 1984). The gap after the
decline of oyster could have been filled with the cultivation of cereals. But then, there was a competition
for labour during autumn, which is the most labour-intensive season for both hunter-gatherer and farming
communities. If some of the hunter-gatherer activities were displaced by farming activities, it would be
logical to expand the farming sector still further to compensate (Zwelebil and Rowley-Conwy 1984). But
for the inland and for the coastal sites without kitchenmiddens, that is, for sites where oysters were not an
important resource, there must be another explanation.
Catastrophe theory While in former times abrupt changes in the prehistorical societies have been
explained with immigration of other people, many researchers now prefer to use models of catastrophe
theory, i.e. that abrupt breaks in the archaeological record can be caused by slow, ordinary, everyday
changes in local society. The archaeological record does not represent all the possible choices available in a
society, but only the chosen ones, so that the knowledge for agriculture can have been available for a long
time without being used. The claim is that hunter-gatherers live a secure life, and that stable equilibrium
is the hallmark of their cultural system, but is has to be considered that many systems cannot be stable
unless they change, and that a constant change is possible without being reflected in the archaeological
record. Only when all the small changes sum up and cross a threshold, one sees an abrupt change (Madsen
1986). Because of this abrupt change without visible cause, this theory is called catastrophe theory. Small
changes in the EBK daily life could for example be
growing knowledge of agriculture due to contacts with farming communities
growing sedentariness at places with high productivity such as estuarine systems
storage of hunted and/or gathered food for times with lower productivity , which both is a result of
and a cause for a higher degree of sedentariness
changing the natural environment for increasing its productivity, for example clearing the dense forest
to make better conditions for fruit-bearing trees and wild game
Storage of food and systematic changes of the natural environment already lead to a different social model:
The production and consumption of food are separated and division of labour has to be planned. Therefore a
controlling entity is needed (Mahler 1981). These small changes which are hardly visible in the archaeological
record result in a sedentary society with a broad knowledge on agricultural and storage techniques which is
already used to influencing the environment according to its demands. In this society, it is only a small step
towards the adaptation of agriculture, which could be caused even by minor changes in the environment at
the end of the Atlantic period: A population whose subsistence is partly based on storage can be destabilised
more easily than a fully Mesolithic society. Agriculture could therefore be used to substitute food shortages
(Mahler 1981).
Progress Model and Evolutionary Model The progress models say that farming is progress and therefore automatically adopted when the environmental conditions are appropriate. To the contrary, farming
techniques were available for 1000 years but still not adopted in Southern Scandinavia, although the population lived on the right soils light, but fertile and in the right climate for farming. Therefore, progress
models are of no use for the EBK situation (Rowley-Conwy 1985). Close to the progress models is the
evolutionary model that assumes processes like cultural evolution, for example a growing social structuring,
to be the cause for changes in food production techniques.

69

Population Growth Population growth or population press models say that the growing population led
to a more extended exploitation of the Mesolithic resources, increasing the number of working hours needed
for one unit of food. Finally, more working hours per food unit are needed in a Mesolithic than in a Neolithic
economy. At this point, assuming the contact to Neolithic groups, agriculture is introduced (Fischer 1974).
The longterm population growth models assume that there is always a population growth and that this was
the reason for introducing agriculture. However, the population is fluctuating regionally much stronger than
globally so that there is no constant population growth in a certain area. Therefore is it not an explanation
for the adoption of agriculture (Rowley-Conwy 1985). It can often be observed that population growth takes
place after the introduction of agriculture. A growing population is in fact one of the characteristics of the
Neolithic. This is also the case in the region examined here. First in the advanced Early Neolithic of the
Funnel Beaker culture there are more findings / bigger concentration of findings in most regions. Assuming
population growth to be a reason for the adaptation of farming would mean mixing cause and consequence.
In opposition to the longterm population growth model, many people assume population size to be
a factor that is fully controlled by homeostatic mechanisms in the system (Madsen 1986). In agreement
with the New Archaeology since Binford, [s]ome unexpected change in the equilibrium level of the system
has to take place (Madsen 1986) to cause a population pressure. Therefore, the arguments stating that
agriculture was adopted because of a growth in population do not refer to the direct cause. Another, somehow
more marxist model also stresses the importance of population growth, but it takes the reasons for that
population growth into account and acts on the assumption that
an imbalance between population level and food resources created a growing sedentism based
on seasonal resources (fish) that could be stored. The sedentism, then, resulted in a growing
population, whose demands for food led to a perfection of the catching and storing technology,
so that more fish could be harvested. Subsequently, this development led to a depletion (overfishing) of resources. The only possible answer to this was to adopt agriculture ((Madsen 1986),
summarizing (Mahler, Paludan-M
uller, and Hansen 1983)).
As it is now known that there was a decline in temperature and therefore a change in the environment at
the end of the EBK, over-fishing is now not longer needed as an explanation for the beginning scarcity of
resources.
The fertile gift Another model that does not need population pressure as explanation is that of Kristina
Jennbert who proposes to regard grains and cattle as prestige goods that were in the beginning not used for
nutrition, but mainly as signs of prestige after contacts with agricultural societies. She bases her argument
on sites in Scania where there is continuity between Erteblle and Early Funnel Beaker, but no indication for
a decline in food resources (Jennbert 1985). Some single findings point to contacts between fully Neolithic
groups and the Late Mesolithic. So the exchange of prestige goods as gifts between different cultures is
conceivable.

70

Chapter 4

The samples from Schlamersdorf and

Kayhude
Here, I will explain the different kinds of samples I have taken as well as the way of sampling and pretreatment.
Measurements and results will also be given.

4.1

Selection and pretreatment of samples

To ascertain a hardwater effect, both modern and old samples were chosen. Firstly, water samples from
the rivers next to the sites were taken, because the radiocarbon age of them can give a hint on a possible
hardwater effect. Secondly, recent fish and mollusc was chosen, in order to show that the hardwater effect
is passed on from the water through water plants and finally fish. For finding out if the age of the fish also
affects the age of a food crust, food crusts both from fresh terrestrial as well as freshwater material were
produced and pretreated in the same way as the old food crusts. As one could doubt that the carbonate
content of the rivers as it is measured now is the same as in the Mesolithic/Neolithic, also old samples had
to be taken. First of all of course food crusts were dated because samples of this type were taken before
to date the first occurrence of pottery in Schleswig-Holstein and showed surprisingly high ages. In order to
discover a hardwater effect in the archaeological material, associated samples of terrestrial origin on the one
hand and freshwater origin on the other hand had to be dated. Therefore fishbone, bone, charcoal and wood
samples from the same layers and not too far away from each other were chosen.

4.1.1

Water samples

On each site, three water samples have been taken. One directly next to the site, on upriver and one
downriver of the site. Dissolved inorganic carbon was extracted from the samples that were taken directly
next to the sites (called Trave 1.1 and Alster 1.1) and converted into graphite samples. The other two
samples from each river were kept for the case that Trave 1.1 and Alster 1.1 got lost during preparation
or measurement. They can now be used for further examinations, for example chemical analyses or the
extraction of DOC which might be necessary to explain some of the dating results (see section 4.2.1 and
4.2.3).
On the same day on which the water samples were prepared, a background sample was also prepared
to get an idea of the background contamination that enters the samples in the CO2 -extraction process and
following graphitisation. For the preparation of a water background sample, a half-liter bottle is filled with
demineralized water and 30 mg Iceland spar, in Danish dobbeltspat. It is a variety of crystallized calcium
carbonate, CaCO3 . 30 mg Iceland spar correspond to 3.7 mgC. 4 ml 85%H3 PO4 (phosphoric acid) are added
to dissolve the carbonate over night at 80 C. After cooling down for one day, the background sample was
processed in the same way as the other water samples.
71

In our laboratory, in most cases only DIC is extracted from the water (see section 1.2.3). Water samples
are taken with half-liter amber glass bottles which were rinsed with acid and deionized water and dried. When
the water samples are taken from the river, it is paid attention to closing the cap under water or shortly after
filling the bottle so that no atmospheric air can enter the sample. Three to four drops Mercury(II) chloride
solution, also known as mercuric chloride, HgCl2 , are added to prevent algae growth. The concentration
of this solution is 3.5 g HgCl2 / 50 ml water. Mercuric chloride is used because it is one of the forms of
mercury that is most soluble in water and because of its high toxicity that prevents all forms of biologic
activity in the water sample. This preservation is necessary if the sample can not be kept cool all the time
between collection and measurement and if the measurement takes place later that a few days after collection
(Clark and Fritz 1997). In the laboratory, the samples are stored in a fridge until the DIC is extracted. For
transferring the sample to the DIC extraction system (in the following called water system), the samples is
pumped from the bottle to an evacuated flask that is connected to the extraction system. If one would pour
the sample into the flask instead of pumping it through a rubber tube, it would have too much contact with
atmospheric air. 223.6 g water were taken from the background sample, 216.2 from Trave 1.1 and 216.5 from
Alster 1.1 for DIC extraction. In figure 4.1, the DIC extraction from water samples at the water system is
shown. The water system is filled with about 600 torr nitrogen gas (N2 (g)). 4 ml 85%H3 PO4 (phosphoric
acid) are filled into the flask with the sample (figure 4.1a). The N2 (g) is pumped through the sample in
a closed circuit, bubbling out the CO2 that formed from the DIC when phosphoric acid was added to
the sample (figure 4.1b). The CO2 is frozen at two freeze traps (figure 4.1c and d). After 15 minutes, the
nitrogen is pumped away and the CO2 is defrozen and its pressure is measured in a calibrated volume. For
transfer to the graphitisation system, the CO2 is frozen into evacuated glass tubes which are flame-sealed
after the sample is filled in. From the 216.2 mg Trave water, 3.5 mgC could be extracted. That corresponds
to a carbon yield of 1.6%. The Alster water sample with 216.5 mg water yielded 7.18 mgC. That corresponds
to a carbon yield of 3.3%. The amount of DIC extracted from the Alster water is thus twice the amount
extracted from the Trave water. This result is strange because the Trave water had a hardness of about
13 dH, the Alster water about 10.5 dH, as was explained in section 3.2.1. As the water hardness is the
concentration of the alkaline earth metal ions, predominantly Ca and Mg, it is an indicator for the amount
of dissolved carbonate in the river water. The carbon yields from these two samples show that other sources
of DIC than carbonate mineral dissolution must be taken into account for the Alster.
Some graphitisation parameters are changed when water samples are graphitised. The first is that the
water trap the samples have to pass at the graphitisation system has a temperature of -110 C instead of the
normally used -80 C. The reason for this is the higher water vapour content of the samples that necessitates
a more efficient removal of water. The laboratory experience shows that the graphitisation rate of water
samples is lower than that of other types of samples. A possible reason is that the surface of the catalyst
is covered with contamination from the water sample so that the reaction surface for CO2 is reduced. For
enhancing the graphitisation conditions for water samples, the catalyst amount is enlarged from 0.8 to 1.1 mg
cobalt. Furthermore, a small stripe of silver foil is placed in the reaction tube to absorb contaminants like
sulphur compounds.

4.1.2

Recent fish and molluscs

Richter (1986) found out in experiments on recent fishbone (vertebrae) that collagen degrades when heated:
Thermal denaturation of the bone at 60 C caused melting of the collagen in local areas both at the ends
and along the fibril. Melting progresses with higher temperature and a decreasing fraction of the fibrils is
native collagen so that at 80 C only small fragments of collagen fibrils with melted (swollen) ends can be
seen. Vertebrae heated to 100 C showed no signs of any fibers which could be identified as collagen, neither
when it was heated with nor without tissue attached. She uses the degradation of the collagen as a hint if
fishbones have been heated (and so form an anthropogenic deposit) or not. Exceptions are of course bigger
fish that were boned before usage.
When the bones are prepared in our laboratory, they are sometimes ultrafiltered, because contaminants
are likely to consist of smaller molecules while the original bone material consists of bigger molecules. Because
of the above-mentioned degradation of collagen, it was suspected that cooked bones give a smaller yield after
72

(a) Flask with sample

(b) Bubbling N2 (g) through the sample

(c) Freeze-trapping of CO2

(d) The frozen CO2

Figure 4.1: The preparation of water samples (DIC extraction)

73

ultrafiltration than uncooked bones, because the degraded collagen molecules could be too small to stay in
the filter. To test this, cooked as well as uncooked fresh fishbones from the river Trave have been prepared
and the preparation yields have been compared. The fish was cooked in water in a pointed base vessel,
standing on three stones and heated by a small fire which mainly consisted of glowing charcoal. After only
15 Minutes, at a water temperature of 77 C, the fish was already done and taken out of the pot. It can be
expected that the temperature in the bones did not rise above 70 C and maybe even stayed under 60 C,
so that a degradation of the collagen, as Richter (1986) experienced, possibly did not take place in our
case. This fits well to the result that there is no significant difference in the preparation yields (extracted
collagen weight compared to sample weight), and the yield of the cooked bones is even a little bit bigger.
Therefore, ultrafiltration can also be applied to fishbones that are likely to have been heated, because it is
unlikely that a stone age fish meal was heated much longer than to that point where the fish was done and
ready to be consumed. The bones were chosen to be dated, and not the flesh, because the results should be
comparative to the archaeological material, which only provides bones of the fish.
The recent fish bones from the river Trave were prepared after the following method: They were put
into a glass with demineralised water and cleaned (i.e. the remaining tissue was removed) with tweezers
and scalpel. The cooked fish bone was clean and white after this procedure, but there was a lot of tissue
remaining on the uncooked fishbones. Therefore, they were additionally cleaned with demineralised water
in an ultrasonic bath, first for 10 minutes, then for 30 and finally for 60 minutes. Because there was still
tissue adhering to the bones, another cleaning step with ultrasound and acetone for one hour was performed
before the samples were dried overnight at 56 C. The recent fish bones from the river Alster only needed
the following cleaning procedure: Two times ultrasonic bath (with demineralised water) and cleaning with
tweezers and scalpel in between before they were dried like the Trave fish bones. The chemical pretreatment
of the bones with ultrafiltration is described in section 4.1.5. The fresh fish bones were pretreated in the same
way as archaeological bones and fish bones to provide comparable results. Additionally, one snail-shell from
the Alster was dated. It was cleaned in demineralized water in the ultrasonic bath for about two minutes.
Thereafter it was dried and weighed. The outer parts of the shell were etched with 40 L 1M HCl per 10 mg
shell in demineralized water. A treatment with 7 to 8 drops 0.25M KMnO4 in 25 mL demineralized water
followed. This was done for 16 to 20 hours at 80 C. Figure 4.2 comprises the recent fish and shell samples
from both rivers.

4.1.3

Recent food crusts

Experiments with the formation of food crusts were conducted to get answers to problems like formation
time and probability as well as alteration of chemical composition and isotopic values during the process of
cooking and food crust formation. Experiments like these never reflect the complete prehistorical situation
and are not suited as a definite proof for a certain theory of prehistoric mans behaviour, but at least they
can show possibilities - and impossibilities. As Charlton (1981) remarks,
In considering the applicability of data from experimental archaeology it is necessary to keep
in mind the probabilistic nature of inductive argument by analogy and the importance of the
relevance of the claimed similarities and differences. Among those who have examined this aspect
of experimental archaeology there is general agreement that such studies serve to strengthen the
bases for inference via analogy by eliminating irrelevant alternatives for a given phenomenon.
In the experiment, two types of food crust were produced: Recent fish (roach) from the Trave and recent
wild boar meat were cooked in Trave water until the water was boiled away and the food burnt and formed
a crust on the pot. To copy the prehistorical situation best possible, copies of pointed base vessels were
formed by Harm Paulsen, experimental archaeologist in Schleswig. The pots were tempered with crushed
red granite (see picture 3.6a on page 65). It is relatively easy to crush the granite stones when they have
previously been heated, as is the case for pot boilers or stones that formed a fire place. The finished pots
(figure 4.3) were then dried for 15 days at room temperature.
The firing also was done copying the prehistorical conditions. First, a spot of soil was cleaned of grass
and levelled. This place was dried and warmed by a fire, because firing the pots directly on the cool soil could
74

(a) Fresh fishbone (Trave), SID 12060

(b) Fresh cooked fishbone (Trave), SID 12097

(c) Fresh fishbone (Alster)

(d) Snail-shell (Alster)

Figure 4.2: Photographs of the modern fish and shell samples.

75

cause them to break, due to the temperature differences between soil and fire (pers. comm. H. Paulsen 2007).
When this first fire was almost completely burnt down, it was pulled apart (figure 4.4a) and the pots were
placed in the middle, with the top facing down (figure 4.4b). Now, the ring of embers surrounding the pots
was fed with more firewood and slowly brought closer to the pots, so they heated up slowly (figure 4.4c). The
slow heating process is necessary because the thick walls crack easily when there are too high temperature
differences between to places on the pot. Especially the thick pointed bases are very fragile. We could also
see the that two of the pointed bases cracked away from the pots, one pot therefore having a hole and being
useless, another one only missing the pointed base (and so showing the silhouette of a funnel beaker).
When the fire finally covered the pots, ca. 30 minutes after the pots
had been placed onto the firing site, it was heated up and a more wood
was put on the fire little by little, so that a big fire was burning for ca.
20 minutes (figure 4.4d). After that, the fire was left to burn down to
ashes (figure 4.4e), which took two hours, and the pots were carefully
rolled away from the firing site (figure 4.4f).
These conditions are comparable to the assumed prehistorical open
firing, described by Tite (2003b): The bonfire reaches the maximum
temperature in 20-30 minutes, while the maximum temperature is maintained only for a few minutes (in our case: when all the wood was put
on the fire, the fire had its maximum temperature, before it was left for
burning down). After 20 minutes of cooling, the pots still had a temperature of more than 90 C. As the sand on the firing site was coloured
Figure 4.3: Finishing a pointed- red and the pots clinked when one knocked at them, a firing temperature of 600-700 C could be assumed (because of a broken device, we
base vessel
were not able to measure the firing temperature directly). This is again
comparable to the archaeological experiences: in an open firing, maximum temperatures reach from 500 to
900 C, in most cases between 600 and 800 C. The firing atmosphere in an open fire can change rapidly
from reducing to oxidising, and fully oxidising conditions are reached very seldom, because the pottery is in
intimate contact with smoky and sooty fuel (Tite 2003b). The latter description also fits to our pots: They
have an irregular colour, partly reddish and partly dark, so the firing was a mixture of oxidized firing and
firing in oxido-reducing atmosphere (figure 4.4f).
One pot was filled approximately half full with fish (without head and fins, but still with bones) and a
little water so that the fish pieces were covered. The water was taken from the Trave and still contained
some plant pieces, both terrestrial and water plants (as the river had high tide and was flooding surrounding
fields), which is likely to reflect the prehistorical situation (some plant material might have been used as
spice, for example). A second pot with wild boar meat was prepared in the same way. It could be seen that
after a short while, the meals were done, with most of the water still being in the pots and not crusts on
the inner surface of the pots. Therefore, the small hearth fires were enlarged and kept burning for a long
time in order to make food crusts. It took almost two hours until the water of the fish soup was boiled
away, and from the heating of the wild boar meat until a food crust was formed, it took almost three hours.
Therefore, we can say that the formation of a food crust is a very unusual event which requires a lot of time
and energy, assuming the use of some water in the preparation of stone age food. Another observation is
the very unpleasant smell of the crusts, which makes further use of the pots after the formation of a crust
improbable, taking into account the refined sense of taste of a population that had no access to strong spices
or artificial flavours, but depended on the sense of taste to chose between edible and poisonous plants. The
little work that is required to build a pointed base vessel is another argument for the discarding of pots as
soon as a crust was on it. These observations now necessitate an explanation for the large number of food
crusts that can be found on EBK sites.
The fish food crust was coloured light brown to black. Some fishbones were visible on the surface, while
other fishbones were charred and only visible as imprints. The boar food crust was a homogenous viscous
black mass. After cooling down, it divided into two crusts: one part firmly adhering to the pot under another
brittle and easily removable crust with air bubbles. The food crusts were pretreated in the same way as old

76

(a) Preparing the firing site

(b) Placing the pots on the prepared ground

(c) Bringing the fire closer to the pots

(d) Firing

(e) The fire burns down

(f) The pots after firing

Figure 4.4: Firing of the pointed-base vessels. Photographs by Aikaterini Glykou

77

(a) Fish soup gets heated

(b) The water of the fish soup is completely boiled away

(c) Fish food crust

(d) Meat soup gets heated

(e) The meat soup is boiling

(f) Meat food crust

Figure 4.5: Food crust production from fish (roach, a-c) and meat (wild boar, d-f).
ones (see the following section, 4.1.4), to give comparable results.
Later, the team of archaeologists from Schleswig was able to get blubber from a beached whale (porpoise)
on the west coast of Schleswig-Holstein. They cooked blubber in a pointed-base vessel and also scorched
some of it in the pot. This makes it now possible to examine the difference between original material and
crust also for a marine sample. The oil that was cooked out of the blubber was then used for filling a copy
of the typical EBK lamp (pers. comment Sonke Hartz 2007). See sectionrefsec: ertebolle-pottery-and-tools
for a description of the lamp.

4.1.4

Old food crusts

At Schlamersdorf, two different pottery wares could be found. One of them is thick-walled, tempered with
reddish granite chippings and made in U-technique. The other is thin-walled, contains fine temper particles
and is made in U-technique and Schrgaufbau. Most of the food crusts were pretreated according to the
laboratorys standard pretreatment procedure for plant rests, food crusts and charcoal: The food crusts were
examined under the microscope and visible contamination such as rootlets were removed. Then the crusts
were scraped off the sherd with great care, so that no clay material was abraded. When available, both the
inner and outer crust of a sherd were used. Without a hardwater effect it is expected that the outer crust
has the same or a higher age than the inner crust: The inner crust is expected to have formed from charred
food whereas the outer crust can consist of food that boiled over or of soot from the hearth fire. Soot from
the hearth fire can have a higher age than the charred food remains if old wood was used (old wood effect).

78

In two cases, plant remains were found inside the sherds, and one of these sherds also had an outer crust so
that it will be possible to compare dates of three fractions from the same sherd (see table 4.1). It is hard
to say if the plant remains entered the clay during the production of the pot or if they stem from rootlets
that grew through the sherds during their deposition in the soil. As the clay was tempered with granite
chippings, organic temper can be excluded as a source of plant remains. If the plant remains were originally
mixed into the clay, they are expected to have the same 14 C age as a food crust from terrestrial material.
Otherwise, a much younger age is expected.
Table 4.1: Pottery sherd samples from Kayhude and Schlamersdorf: sample type, NaOH concentration
applied in the pretreatment procedure, and pretreatment yield.
SID

Find No.

Sample
material

12047

KAY8-432,01

12048

KAY8-168,01

12053

N-629

12054
12055

N-629.1
SL1

12056

SL2

12057
12058

SL3
SL4

12345
12347

KAY8-412,01
SLA5-1713

12348
12349

SLA5-2707
SLA5-2742

Food crust
Humic
Food crust
Humic
Food crust
Humic
Food crust
Modern food crust
Humic
Modern food crust
Humic
Modern food crust
Modern food crust
Humic
Food crust
Food crust
Outer crust
Plant remains
Food crust
Food crust
Plant remains

Sample size
(mg) before
pretreatment

NaOH
conc.

Sample size
(mg) after
pretreatment

Yield
(mg/
mg)

Cathode
number

68.9
68.9
40.2
40.2
42.8
42.8
32.8
83.2
83.2
40.1
40.1
61.6
65.2
65.2
43.6
29.3
14.2
0.6
17.9
26.9
3.6

1M

50
0.4
27.7
2.2
22.3
4.0
18.7
0
35.6
0
14.8
40.4
15.8
10.8
31.7
20.4
9.8
0.3
13.3
18.8
2.0

0.726
0.006
0.689
0.055
0.521
0.093
0.570
0
0.428
0
0.369
0.656
0.242
0.166
0.727
0.696
0.690
0.500
0.743
0.699
0.555

19899
19900
19901
19902
19904
19905
19906
...
19925
...
...
...
19926
19927
19928
19979
19974
20502
19980
19981
19977

1M
1M
1M
1M
1M
1M
1M
1M
1M
0.5M
0.2M
0.5M
1M
0.2M

First, the food crusts were treated with HCl at 80 C for 1 hour to remove any carbonate. After rinsing
with demineralized water to remove the dissolved material, humic substances were dissolved in NaOH and
thereafter washed away with demineralized water. The samples were then acidified with 1M HCl over night
to remove any CO2 absorbed during the NaOH treatment (Olsson 1976a). The usual NaOH concentration
for food crust pretreatment is 1M, but for very small samples, less concentrated solutions were used. When
the NaOH solution was coloured very dark after the first NaOH step, the solution was not poured away but
safed in a glass beaker and acidified with HCl and heated so that the humic substances precipitated. The
precipitated humic substances were rinsed with demineralized water and dried. As described in section 2.1,
humic acid precipitates at pH < 2 whereas fulvic acid is soluble at all pH values. The precipitated substance
from the sample is therefore expected to be a mixture of acids present in the food crust, for example fatty
acids, and humic acids. The fulvic acids which is present at all pH values should have been removed already
in the first rinsing procedure. The NaOH step was repeated until the solution was clear. The samples
of modern food crust from wild boar meat dissolved completely under NaOH treatment. Therefore, only

79

the precipitated humic substances could be dated. In this case, as the food crusts were not buried after
formation, the base-soluble fraction is of course not soil-derived humic substance. Instead of this, it consists
probably of fatty acids. The solubility of the wild boar food crust in NaOH points to incomplete carbonisation
of the sample. In future experiments, the time for letting the crust char should therefore be longer to check
if this increases the fraction which is not base-soluble. The table shows that there is no significant difference
in the pretreatment yield of the archaeological and modern samples. This is an indicator for the reliability
of food crusts as sample material. Apparently, the food crusts only disintegrate to a limited extent in the
soil. Later, for some of the food crusts, the same method as for bones was tried (protein-extraction), but the
yield was too small: From 534.5 mg food crust of sample SID 12056 (wild boar), only 2.6 mg protein could
be obtained. That is a pretreatment yield of 5 mg per g original sample mass. Only half of it, 1.3 mg, could
be taken out of the glass. The fish food crust SID 12058 yielded approximately the same protein ratio. From
282.2 mg sample, 1.7 mg proteins could be extracted. This corresponds to a yield of 6 mg per g original
sample. Here, only 0.3 mg could be taken out of the glass after pretreatment, as the rest of the extracted
material was adhering to firmly to the glass. Pretreated food crusts consists usually of about 50% carbon
so that the yield can also be expressed as around 3 mgC per gram sample. These yields are only slightly
higher than the protein yields that were reported for archaeological food crusts that were extracted with the
Lowry-method (see section 1.4. With that method, 1 mg carbon could be obtained from 1 g of food crust.
Assuming that the collagen yield is smaller for archaeological than for modern samples, protein extraction
is not the right method of pretreatment for radiocarbon dating. For obtaining sufficient carbon masses with
the protein extraction method, big food crust samples are needed. However, only few sides provide food
crust samples with masses of several hundred mg. For radiocarbon dating, other methods have to be applied
that give a higher carbon yield.For stable isotope analysis, though, where the required sample masses are
smaller, one could assume to use this method of protein extraction. Further research on the recent food
crusts is planned to test several methods of food crust pretreatment and to compare the 13 C and 15 N values
that are obtained after these different pretreatments.
Some authors prefer not to pretreat food crusts for 13 C and 15 N measurements at all because the
pretreatment has no influence on for example the 13 C value whereas it is possible that part of the food
crust dissolves under pretreatment (Craig, Forster, Andersen, Koch, Crombe, Milner, Stern, Bailey, and
Heron 2007). For radiocarbon dating, though, I chose to pretreat the food crusts as already minor amounts
of modern contamination can alter the age of the sample significantly. Hallgren and Possnert (1997) report
that the chemical pretreatment of organic remains on neolithic potsherds yielded almost no insoluble fraction.
This means that the degree of carbonisation (particle content) was small and that the biggest part of the
organic remains is connected to alkalisoluble compounds, probably lipids. It has been shown that the alkalisoluble and alkali-insoluble fraction of a food crust have about the same age (Segerberg, Possnert, Arrhenius,
and Liden 1991).
Instead of scraping off the food crusts from the sherd, it is also possible to crush the whole sherd and
place it in deionized water so that the minerals sink to the bottom and the organic remains float on the
surface (Johnson, Stipp, Tamers, Bonani, Suter, and Wolfli 1986). This method has not been applied in this
case, because it makes only an analysis of the whole organic material from the sherd possible: the total of
animal fats, plant fibres, charcoal used in the tempering process (Johnson, Stipp, Tamers, Bonani, Suter,
and Wolfli 1986), and soot deposits in the pores. In this case, specific analyses of food crusts were desired
so that the crust alone had to be removed carefully from the sherd. Another disadvantage of crushing the
sherd to extract the organic material is that the sherds are completely destroyed in that way.

4.1.5

Bone

Before describing the chemical pretreatment that is applied to bones in our laboratory, I will explain which
substances are present in the bone and how they are affected during burial. The chemical pretreatment
procedure will be described and methods of quality control will be presented, for examining the reliability
of the bones as sample material for radiocarbon dating and stable isotope analysis. My samples will then
be tested using these quality criteria. A short paragraph about the zoological appraisal of the find material
from Schlamersdorf will round off this section. A similar examination for the find material from Kayhude
80

has not yet been done.

Bone and antler consist to approximately one third of organical primary substance (ossein and fat)
and to two thirds of inorganical material (85% of it calcium phosphate, furthermore calcium carbonate
and calcium fluoride). On the soil surface and in well-aerated/ventilated soils (like sand or gravel), bones
are not preserved: microbiological processes degrade organical substances and the silicid acid in the sand
dissolves mineral substances. In contrast to that, the preservation conditions for bone are excellent in humid
sediments from lakes and bogs or in submarine settlements. Only in high moors the high acidity (pH up
to 2) dissolves the mineral substances (Dellbr
ugge 2002). It is expected that the organical substance of
the bone changes least during deposition in the soil. Therefore, the bone pretreatment method is protein
extraction, or gelatinisation. The extracted substance (proteins) is often referred to as collagen, although
it is well known that the degraded bone material is different from the original collagen (Kanstrup 2008). As
bone substance consists in the average of bigger molecules than contaminants from the soil, the extracted
dissolved collagen is ultra-filtered to exclude the small-molecular contaminants. The >30 kDa (Da =
Dalton) fraction is used for dating and isotope analysis.
If the bone pieces are big enough, bone powder is drilled out of the bones after rinsing the surface of the
drilling area. Between 200 and 300 mg powder are normally used. If the bones are too small to allow drilling,
for example fish bones or small bone fragments, they are cleaned in demineralized water and ultrasound.
After that, they are either cut into small pieces, smashed with a hammer or mortared. The first step in the
chemical bone pretreatment procedure is the decalcification, that is the removal of inorganic material. The
bone powder is cooled down to 5 C and 1M HCl, also cooled down, is added. The bone powder - acid mixture
is stirred regularly and kept in a fridge at 5 C until the bubbling stops. After the bubbling has stopped
(usually after 15-20 minutes), pH is controlled. If the pH is >0.5, more acid is added. When the bubbling
has stopped again, the pH is controlled and if necessary, more acid is added. This has to be repeated until
the pH is <0.5 when the bubbling has stopped. The low temperatures are needed to prevent the proteins
from dissolving. After 3 to 5 minutes in the centrifuge at 2000 rounds per minute (rpm), the solution is
poured off and the sample is rinsed with demineralized water. 0.2M NaOH is added at room temperature
to dissolve humic acids that entered the samples from the soil. After 15 minutes, the colour of the solution
is controlled. When it is very dark, new NaOH is applied to the sample. This is repeated until the solution
is almost clear. After pouring off the NaOH solution and rinsing with demineralized water, 102 M HCl is
added to the samples so that the pH is between 2.0 and 2.5. The pH is controlled after 30 minutes and
HCl or demineralized water is added, if needed, until the pH is stable at 2.0 - 2.5. Then the samples are
placed in a heating cabinet at 58 C over night to extract the collagen. The ultrafilters Amicon Ultra 4mL,
>30 kDa, LOT-number R4JN69709 were used for the samples discussed in this thesis. They are cleaned
first with filling them with water and centrifuging them two times with fresh demineralized water, then
with demineralized water in the ultrasonic bath and again centrifuging three times with fresh demineralized
water. On the next day, the gelatin solution is poured into the ultrafilters. Insoluble residues on the bottom
of the reaction tubes are kept down using centrifugation and 5-8 m Ezee mesh filters (Elkay Laboratory
Products) which have been cleaned with ultrasound and demineralized water. The gelatin solution is now
ultrafiltered (7 minutes at 3500 rpm) to remove small molecules. After ultrafiltration, the gelatin solution is
poured into new, weighed glasses. They are cooled down, frozen with liquid nitrogen and finally freeze-dried,
which takes one to two days. The glasses containing the collagen are weighed to calculate the collagen
mass and estimate the collagen yield.
To determine the chemical integrity of the extracted gelatin, the C:N ratio, the mass ratio of carbon versus
nitrogen, can be used. Bonsall, Cook, Hedges, Higham, Pickard, and Radovanovic (2004) define a range of
acceptability between 2.9 and 3.6. This range can be refined to between 3.1 and 3.5 for radiocarbon dating
(Kanstrup (2008), and references therein). Also the gelatin (collagen) yield can be used as a criterion of
the samples quality. Bonsall, Cook, Hedges, Higham, Pickard, and Radovanovic (2004) for example do not
routinely date yields below 10 mg collagen per g sample. The demands on collagen yield were reduced in
newer literature, so that a yield of 1 mg g1 is sufficient for some groups (Kanstrup 2008). For samples
prepared without ultrafiltration, yields above 3.5% (35 mg g1 ) are required. In table 4.2, the gelatin yield
and C:N ratio for all pretreated samples is shown. There was not enough material from some of the samples

81

for both 14 C dating and stable isotope measurements. Some of the samples were kept to be combusted in
the EA for 13 C and 15 N measurements with additional CO2 trapping for graphitisation and 14 C dating when
the new trapping device is tested well enough to allow the processing of archaeological samples. Some of the
samples were only graphitised for 14 C dating.
Table 4.2: Quality of extracted collagen. For samples without C:N ratio: not enough material for EA,
only cathode for 14 C dating; ? material kept for on-line combustion at EA with CO2 trapping.
SID

Find
number

Sample material

12060
12097
12099
12100
12101
12102
12154
12167
12342
12343
12344
12392
12393
12606
12608
505
505

(Trave)
(Trave)
SLA5-2784
SLA5-2761
SLA5-2883
SLA5-2913
(Alster)
SLA5-2869
SLA5-2786
KAY8-815,0
SLA5-2874
(Kayhude)
(Kayhude)
SLA5-2912
SLA5-2906

Fresh fishbone
Fresh fishbone
Bone (wild cat)
Bone (beaver)
Bone (wild boar)
Fishbone
Fresh fishbone
Fishbone
Tooth (red deer)
Bone
Tooth (aurochs)
Fishbone (pike)
Fishbone (pike)
Fishbone
Fishbone
Background bone
Background bone

Sample size (mg)

before
after
pretreatment
108.4
11
94.9
12.3
296
7.2
220.1
2.1
299.3
5.3
373.4
1.5
341.4
18.3
406.2
5.8
226
6
616
6.3
509
4.3
254.9
2.8
146.2
0.13
145.2
3.7
103.0
3.1
183.1
7.9
180.5
6.3

Pretreatment yield
(mg collagen
per g sample)
102
130
24
9
18
4
54
14
27
10
8
11
10
25
30
43
35

C:N
ratio
3.1
3.1
3.2
3.6
3.2
?
3.2
?

...
...

From the two background bone samples, no collagen was taken for stable isotope measurements, but
the C:N ratio for other samples of the same background bone material is about 3.3. The two background
bone samples were pretreated with different methods: the first with ultrafiltration and the second without.
Apparantly, the collagen yield for the background bone sample prepared with ultrafiltration is bigger than
that for the sample without ultrafiltration. This fact is hard to explain because one would expect that the
yield is smaller for those samples where a fraction of the molecules is removed (ultrafiltration removes small
molecules). As these are only two samples and as the difference is not very big, statistical errors could be the
reason. While being weighed, the samples can uptake water from the air, depending on the time they are
exposed to air and on air humidity. It could therefore be that the one sample has incorporated more water
and so became heavier than the other. All samples for which C/N measurements were available lie in the
range of acceptability Bonsall, Cook, Hedges, Higham, Pickard, and Radovanovic (2004) defined for C:N
values. The collagen yield varies a lot between the different samples. Modern samples yield most collagen:
between 54 and 130 mg collagen per g sample. This was expected because no collagen degradation could
take place in those samples. The high yield of background bone samples (35 and 43 mg/g) is consistent with
laboratory experience. The background bone samples are taken from well-preserved whale bones and always
have quite high collagen yields, compared to other archaeological bone samples. The collagen yield from
archaeological samples ranges from 4 to 24 mg/g. Three of the samples, a bone (beaver), a tooth (aurochs)
and a fishbone sample from Schlamersdorf, had a collagen yield that was defined as not sufficient by Bonsall,
Cook, Hedges, Higham, Pickard, and Radovanovic (2004). For the tooth sample, a low collagen yield was
expected because it was not clear how much of the material drilled out from the tooth contained collagen
and how much was tooth enamel, for example. For the other tooth sample, it was possible to use only the

82

collagen containing parts, so that the collagen yield is quite high. The low collagen yields of the beaver
bone and fishbone samples can be explained by the advanced decomposition of these bones. Because of the
limited amount of bone samples from the sites and because the C:N ratios are in the range of acceptability
for all samples with C/N measurements, it was decided to use all the samples listed in the table above for
dating, although the collagen yield for some of them is quite low.
Bone from Schlamersdorf
For the bones from Schlamersdorf, a detailed zoological analysis is available. Some of the bone findings from
Schlamersdorf have a dark colour because of humic acid. They are not very well preserved and especially
most of the fish bones are porous and crumbly. All bones were found in the former littoral, i.e. in the waste
zone of the settlement. This is certainly caused by the different preservation conditions: in the shallow
water, the bones were better preserved than on the well-ariated soils of the settlement site. There is a large
number of species, but only a small number of individuals per species. Of the 389 bone findings, 288 could
be determined and belonged to 33 species. But not all of these have been hunted by humans. Especially
small mammals and very small fish did probably not belong to the range of prey species of prehistoric man
but were washed ashore. With the species that might have belonged to the human prey spectrum, one
also has to be careful because also they can be natural depositions. The small number of bone findings of
anthropogenic origin leads to the conclusion that this site has only been inhabited temporarily. Also the
transportation of the prey to a probable main settlement a bit further away could be the reason. There have
also been flint tools but no evidence for the production of these flint tools (Heinrich 1993), which also points
to the existence of a bigger settlement nearby, so that the production of flint tools was not necessary in this
camp.
The species that probably were fished/hunted by humans are the following: Northern pike (Esox lucius)
gave most fish bone findings: 111 from at least 5 individuals. There are also 38 findings of cyprinids
(Cyprinidae), with at least 5 individuals, and 38 of European perch (Perca fluviatilis), with at least 7
individuals. The comparatively high number of cyprinids is consistent with their availability in the river
(Heinrich 1993). Also the Northern pike has been important for prehistoric fishing in middle and northern
Europe, although it can be expected that it is overrepresented in the archaeological record because of the
high resistance of its bones (Heinrich 1993). The same effect can be expected for perch bones, because they
are also more resistant than some other bones. Especially the very small ones could be taphocoenotic. There
were bones from at least 11 individuals of waterfowl and 1 wild boar, 2 red deer and one aurochs that also
may have been hunted for meat. Some smaller mammals like wildcat, European otter, European beaver and
red squirrel may have been hunted for their fur. A quite big number of different mice can best be explained
with the ideal life conditions for these species in the surroundings of the site (Heinrich 1993).

4.2

Dating and stable isotope measurement results

First, a wide selection of recent material has been dated in order to ascertain the hardwater effect and to
study the changes in age when going from water samples to fish and molluscs and finally to food crusts. The
latter examinations have mainly been conducted on material from the river Trave. Samples from the river
Alster have only been examined to see if a hardwater effect is existent in that river. It is assumed that the
water and fish from one river have too high ages that can also be found on food crusts from this material. This
leads to the conclusion that also food crusts from material from another river show too high ages, if its water
and fish show the high ages. Therefore, it is not necessary to make food crust experiments with material from
both rivers. Although both sites are described as shortly-occupied hunting stations, it can not be concluded
that all the material found there was contemporaneous. There is a possibility that the hunting stations were
used several times within intervals of some centuries. For being sure that only contemporaneous material is
compared, groups of associated finds were chosen. These are fish bones compared with bones of terrestrial
animals to find out if the hardwater effect was existent in the archaeological material. Furthermore, food
crusts are compared with terrestrial material such as wood, charcoal or bones of terrestrial animals. In the

83

case of Kayhude, these are finds from one stone layer which seems to be undisturbed by fluvial processes like
inundation or sedimentation. In the case of Schlamersdorf, the coordinates of the samples were compared
and samples from the same layer and similar position were grouped.
The results of the 14 C measurement are given in percent modern Carbon pmC and in 14 C age, in years
BP. The 14 C age is calculated from the pmC in the following way:
14

4.2.1

C age = 8033 ln

pmC
100

(4.1)

Recent samples from the river Trave

The first datings on samples from the river Trave were conducted on four modern samples: One water
sample, one fresh fishbone, one food crust made from fresh fish from the Trave and one food crust made of
fresh wild boar meat.

Table 4.3: Trave - modern samples

pmC

14

Sample ID

Sample material

12504

water

86.540.57

C age
(years BP)
117055

12060

fresh fish bone

96.510.38

28432

12097

fresh fish bone

(cooked)

97.000.34

24428

12058
12055

food crust (fresh fish)

food crust
(fresh boar meat)

96.110.31
106.870.45

37123
-53734

Date cal. AD
(95.4% interval)
695-698 (0.3%),
708-747 (6.0%),
766-987 (89.1)
1492-1603 (60.9%),
1614-1665 (33.4%),
1785-1793 (1.1%)
1525-1558 (6.9%),
1631-1680 (56.4%),
1763-1801 (26.1%),
1938-1955 (6.0%)
1487-1645 (95.4%)
1956-1957 (4.0%),
2002-2008 (91.4%)

In table 4.3, the 14 C content is given in percent modern carbon (pmC) as well as the calibrated AD-ages.
The data was calibrated with OxCal 4.0, using the calibration curve IntCal04. The development and use of
a calibration curve is described in section 1.1.3.
It can be seen from the data that the fresh fish bone has nearly the same age as the food crust which was
prepared from the meat of the same fish. It can therefore be concluded that in the archaeological material,
food crusts and fishbones should show approximately the same age, if the food crust was made exclusively
from fish. It is noticeable that the age of the water is much higher than that of the fish and the fish food
crust. The fish should show the same age as the water if the fish feeds on water plants and water animals. It
is known that roach also eat insects, but their diet consists mainly of freshwater organisms. The nutrition of
the roach is therefore not a sufficient explanation for the difference in ages between water and fish. Another
reason could be that there are water plants in the river that take carbon not only from the river water
but also from the atmosphere so that their 14 C concentration is not so depleted as that of the river water.
The most probable reason, though, is that only dissolved inorganic carbon (DIC; see section 1.2.3) but not
dissolved organic carbon (DOC) is dated with the method I applied while fish and other water animals
uptake carbon from both sources. It would therefore be interesting to also date DOC, which should have a
younger radiocarbon age if the above reasons really can explain the age difference between water and fish.
84

It is desirable that in the future, both fractions of dissolved carbon are dated and not only the dissolved
inorganic carbon. As DOC is not routinely dated in our laboratory, the efforts of extracting the DOC from
the water samples would have been too big for examining the DOC in this work, as the DOC extraction is
described in the literature as being complicated and time-consuming (see section 1.2.3). For future work,
DOC extraction of the already collected water samples from both rivers is planned. It is expected that the
average age of DIC and DOC corresponds to the radiocarbon age of the fish.
Furthermore, the seasonal changes of the water hardness and of the DICs and DOCs 14 C concentration
have to be taken into account, although the effect is expected to be smaller in rivers than in lakes. As
explained in section1.2.3, biologic activity removes CO2 from the original DIC reservoir so that more exchange
with atmospheric CO2 can take place. This increases the 14 C value of the DIC as dissolved CO2 is one of
the DIC species. Seasonal changes of the exchange ratio with atmospheric CO2 can thus not explain the
difference between the 14 C ages of the fish and the DIC. For future examinations of the hardwater effect,
several water samples should be taken throughout the year. Both DIC and DOC from these samples should
be dated and compared with the 14 C age of water plants and fish. The 13 C value for the Trave water sample
is -13.590.01hwhich is a normal value for groundwater DIC. The 13 C value for the Trave water is thus
reasonable as rivers usually originate from groundwater (see section 1.2.3). The surprisingly high DIC age
of the Trave water could be due to the precipitation of secondary calcite, a process which dilutes the 14 C
without being visible in the 13 C value (Clark and Fritz 1997).
The age of the wild boar food crust is out of the range of the calibration curve: it is too young to appear
on the curve. For a calibration of the wild boar food crust, the calibration curve has to be extended to
present using an exponential decay curve, as the 14 C concentration from H-bomb testing in the atmosphere
decreases exponentially (see page 4). Therefore, an exponential decay curve has been fitted to the data of
the bomb pulse calibration curve Kueppers04 used by OxCal. Kueppers04 was obtained by 14 C dating
of tree-rings from 1890 to 2001. The 14 C data in calibration curve data is given as 14 C and 14 C age in
years BP. 14 C is defined byStuiver and Polach (1977) as


ASN
1 1000h.
(4.2)
14 C =
AABS
AABS is the 14 C activity of the standard material oxalic acid, corrected for decay since the time of the first
measurement of this standard (see also section 1.2.1):
AABS = AON e(y1950)

(4.3)

with the standard oxalic acid activity AON and the year of measurement y. denotes in this case the real
1
radiocarbon decay constant of 8267
a which belongs to the half-life of 5730 a (Stuiver and Polach 1977). The
radiocarbon age of a sample is given as


ASN
t = 8033 ln
(4.4)
AON
where 8033 a is Libbys radiocarbon mean life. The curve has been fitted to the data given in 14 C from
1985 to 2001 because there the exponential decrease was most pronounced. The calibration programme uses
the data given in radiocarbon ages (t) so that the radiocarbon age had to be calculated from the 14 C values
in the following way:


  14
1
C
+1 +
(y 1950)
(4.5)
t = 8033 ln
1000h
8267a
The data obtained in this way was merged with the data of the Kueppers04 calibration curve to form a new
bomb pulse calibration curve reaching to the present. In figure 4.2.1, the data from Kueppers04 and the
exponential decrease fit are shown.
The obtained calendar age in the 95.4% probability range is 1956 to 1957 (4.0%) and 2002 to 2008
(91.4%). This fits well with the assumption that the wild boar meat was, although frozen, quite fresh when
we bought it in summer 2007. The exponential function fitted to the Kueppers04 calibration curve is only
85

Figure 4.6: The bomb pulse is extended via fitting an exponential decrease function to the data.

86

an approximation. We set the offset of the 14 C exponential curve to zero and this is not totally correct.
As a first approximation, one could assume that when the effect of the bomb pulse is totally faded out, the
14 C, which is the difference of the samples 14 C activity and the 14 C activity of the standard oxalic acid,
would be zero for contemporary samples. The activity of the oxalic acid standard was determined in a year
in which the effect of the bomb pulse already began and the Suess effect depletes the 14 C activity of samples
in the near future to an unknown extent, depending on the amount of fossil fuel that then will be burnt.
Therefore, it is impossible to exactly define an appropriate offset.
Because of the influence of the bomb peak, it is hard to directly calculate modern reservoir ages. When
calibrating the measured 14 C age, the calibrated age would underestimate the reservoir effect. Therefore,
the age difference is calculated from the 14 C ratio in percent modern carbon and from this difference the
reservoir age is calculated. With the 14 C ratio F (pmC) of the riverine sample, the 14 C ratio F0 of the
terrestrial sample and the mean life of 14 C =8033 a or 8267 a, the reservoir age t can be calculated as
t = (ln F0 ln F) = ln

F0
F

(4.6)

Two different reservoir ages can be calculated, depending on which mean life of 14 C is taken. If the reservoir
age is to be expressed in 14 C years, the mean life 8033 a belonging to Libbys radiocarbon half-life has to
be taken. For an estimation of the reservoir effect in kalender years, the mean-life of 8267 a belonging to
the real half-life of radiocarbon, 5730 a, is used. In the case of recent samples, F0 is the pmC of the
atmosphere at the moment of taking the samples from the river (that is, summer of 2007). The atmospheric
14
C content is constantly monitored on the mountain Schauinsland in the Black Forest near Freiburg im
Breisgau, Germany, and in the high Alpine research station Jungfraujoch in Switzerland. In summer 2007,
the atmospheric 14 C concentration measured at these two sites was between 105 and 105.5 pmC.

Table 4.4: Trave - reservoir ages of modern samples

Sample ID
12504
12060
12097
12058

4.2.2

Sample material
water
fresh fish bone
fresh fish bone (cooked)
food crust (fresh fish)

Reservoir age (14 C years)

158562
70146
66040
73440

Reservoir age (years)

163163
72247
67941
75641

Archaeological samples from Schlamersdorf (Trave)

Associated samples of both fluvial and terrestrial origin have been dated. The difference in radiocarbon age
of paired samples is the reservoir age. Only one food crust sample, SID 12349 from Schlamersdorf yielded
enough carbon to be dated using the old ion source. Unfortunately, the graphite of this sample fell out in
the ion source and could thus not be measured. Therefore, only the date for a plant rest that was found
inside the sherd is available. This plant rest could have entered the sherd during the production process of
the pot. In that case, it would almost be contemporaneous with the formation of the food crust. It could
also be a rootlet that grew through the sherd during its deposition in the soil. In that case, the plant rest
would be a terminus ante quem for the formation of the food crust. It was originally planned to date both
samples from the same sherd, the food crust and the plant rest. With the loss of this food crust sample,
the only food crust sample that was datable with the old ion source was lost. The other food crust samples
can first be dated when the new ion source is tested and running fine, so that they can not be considered in
this thesis. Of the three sherd samples that are left, one had both an outer and an inner crust as well as a
plant rest inside the sherd. This is another possibility of comparing different samples from the same sherd.
87

They are expected to be contemporaneous if the plant rest was incorporated during the pottery production
process. The outer crust may show a higher age: It could consist of soot that derived from old wood in the
hearth fire. Stable isotope measuerements were done for a number of food crust samples from Schlamersdorf.
The results of these measurements will be presented in section 4.3 where they are compared to the stable
isotope measurements of samples from Kayhude, Neustadt (see section 4.2.5), and modern samples.

Table 4.5: Trave - archaeological samples

Sample ID
12099
12101
12051
12051
12051
12100
12349
12342
12606
12608

Sample material
Wildcat
Wild boar
Burnt wood (1)
Burnt wood (2)
Burnt wood (3)
Beaver
Plant rest from sherd
Red deer
Fish
Fish

pmC
49.280.19
47.180.34
48.890.56
46.150.29
46.180.36
44.610.50
47.470.31
45.790.38
38.640.38
38.730.56

14

C age (years BP)

567531
603158
574792
621151
620662
648490
598252
627066
763880
7617115

Date cal. BC (95.4% interval)

4601-4454
5205-4781
4796-4370
5306-5036
5309-5004
5617-5306
4999-4729
5463-5050
6646-6372
6697-6227

In figure 4.2.2, the samples dated so far are shown. Please notice that there are three datings from the
wood sample SID12051. This sample is burnt wood from the find layer. The first date was obtained with
the old ion source and a normal sample size. The two other dates were made with the new ion source. The
sample sizes were small, and the graphitisation took place in small reactors. These two samples were test
samples for the new ion source. The results from these samples are not reliable and are therefore excluded
from further discussion. Figure 4.2.2 shows that the results of the two small samples match perfectly. There
is a significant difference, though, between the dates of the smaller samples and the date of the normal-sized
sample.
When interpreting the result of SID 12100, beaver bone, one has to keep in mind that the pretreatment
yield of this sample was very low. It is therefore less probable that the accurate age of this sample is
measured. This could explain why the age of the beaver is much higher than for example of the wood sample
SID 12051 of the wildcat SID12099. A few of the samples were clearly associated when excavated. When
chosing the samples for dating, it has been paid attention to grouping food crusts with terrestrial samples
or fluvial with terrestrial samples. All food crusts and all but two fishbone samples could not be dated.
Therefore, only few pairs are left for interpretation. Samples were regarded associated when they came
from the same depth level and the horizontal distance between them was small enough, in most cases a few
centimeters. Two samples that were clearly associated are SID 12099 wildcat and SID 12051 burnt wood.
Figure 4.2.2 and table 4.5 show that these two samples are contemporaneous in the range of errors. The
two dated fishbone samples SID 12606 and SID 12608 were found closely next to each other. They have
accordingly an equal age as can be seen in figure 4.2.2. These two fishbone sampels were found associated
with a plant rest from the sherd SID 12349 and with the red deer tooth SID 12342. The age difference
between the fish bones and the red deer tooth is probably due to the reservoir effect. Two dual inlet 13 C
measurements of the red deer tooth are available: 13 C = -23.630.01 and 13 C = -23.540.01. As these
two 13 C values were obtained from samples that were pretreated and combusted independently and as the
13 C values are terrestrial, the samples 14 C value is also being regarded as reliable. The fish bone SID
12606 has a 13 C value of -26.780.01, measured with dual inlet. In section 1.3.1, 13 C values for freshwater
systems were given: At the end of freshwater food chains, 13 C values in bone collagen are expected to be
between -24h in lowland rivers and -20h in lakes and canals. The Trave is a lowland river so that 13 C

88

Figure 4.7: The calibration of the archaeological samples from Schlamersdorf.

89

values of about -24h are expected here for the end of the fooc chain. The 13 C value increases along the
food chain. The fish SID 12606 and SID 12608, the one being a member of the cyprinid family and the other
one unknown, but of similar size, are quite small and were thus not at the end of the food chain. The 13 C
value measured for SID 12606 fits thus well into the expectation: It is more negative than the 13 C value
one would expect for the end member of a food chain. Therefore, also the dating of SID 12606 is regarded
Unfortunately, there was not enough material to allow continuous flow carbon and nitrogen stable isotope
measurements of the red deer tooth and these two fishbones.

4.2.3

Recent samples from the river Alster

Three recent samples from the Alster have been dated: one water sample, one snail-shell from a water snail
that was collected alive in the river and bones from a fish that was caught in the river.

Table 4.6: Alster - modern samples

pmC

14

Sample ID

Sample material

C age

12503

water

78.280.32

196633

12154

fresh fish bone

97.270.35

22229

12153

snail-shell

94.750.37

43332

Date cal. BC/AD

(95.4% interval)
44BC-87AD (92.7%),
106AD-120AD (2.7%)
1641-1684 AD (38.9%),
1736-1805 AD (43.3%),
1935-1955 AD (13.2%)
1418-1498 AD (91.6%),
1601-1615 AD (3.8%)

The reservoir age of the river water from the Alster and the samples from this river is calculated after
equation 4.6. The reservoir age in 14 C years is calculated using Libbys radiocarbon mean life of 8033 years
while the reservoir age in years is calculated using the real radiocarbon mean life of 8267 years. When
comparing table 4.6 with table 4.7, one can see that the calibration of the measured data leads to wrong
estimates of the reservoir age. The water sample, for instance, has after calibration an age of a little less
than 2000 years, whereas the reservoir age for this sample is 2380 14 C years or about 2450 calendar years.

Table 4.7: Alster - reservoir ages for modern samples

Sample ID
12503
12154
12153

Sample material
water
fresh fish bone
snail-shell

Reservoir age (14 C years)

238044
63546
84446

Reservoir age (years)

244945
65346
86847

Also in the Alster, the reservoir age of water and fish bone / shell differs significantly. A possible
explanation can also here be that the water is only dated using DIC while fish and snail could also incorporate
DOC.

90

4.2.4

Archaeological samples from Kayhude (Alster)

Unfortunately, two bone samples from Kayhude could not be dated. The size of these samples was too small
for measurements with the old ion source. Therefore is it only possible to compare the three food crust dates
with charcoal, as this was the only certainly terrestrical sample. The reservoir age t is calculated after
equation 4.6. This is the same as substracting the age of the terrestrial sample from the age of the fluvial
sample. Some samples from Kayhude have already been 14 C measured at the Leibnitz Laboratory for Age
Determination and Isotope Research, Christian Albrechts University Kiel. The results were kindly placed to
my disposal by Ingo Clausen,

Table 4.8: Alster - archaeological samples

Sample ID

Sample material

pmC

12047
12048
12345
12346
12392

Food crust
Food crust
Food crust
Charcoal
Fishbone

Sample ID (KIA)

Sample material

29523
29524
29525
29526
29527
29527 (humic)
29528
30079
30080
9906

Wooden pole (alder)

Wooden lance (hazel)
Wooden pole (alder)
Wooden pole (alder)
Food crust
Food crust
Wooden pole (hazel)
Wooden axe handle (hazel)
Wooden axe handle (ash)
T-axe (antler, red deer)

49.230.47
46.840.46
51.350.68
50.820.26
34.640.61
pmC
47.950.23
50.890.19
47.020.18
46.820.20
44.890.17
43.880.17
54.920.19
45.860.20
51.310.19
49.120.26

14

C age

569254
608856
5349106
543741
851483
14

C age

590540
542530
606030
609535
643530
661530
481530
626535
536030
571040

Date cal. BC
(95.4% interval)
4706-4367
5221-4799
4501-3800
4359-4177
8165-7177
Date cal. BC
(95.4% interval)
4893-4694
4341-4239
5053-4849
5207-4911
5476-5341
5620-5490
3654-3526
5320-5078
4327-4055
4684-4459

In this case, the fishbone, SID 12392, is about 3100 14 C years older than the charcoal sample, SID12346.
If assuming that they were deposited at the same time, the reservoir age for samples formed in the Alster is
about 3100 years during the Erteblle period. In figure 4.2.4, the calibrated samples both from our laboratory
and from Kiel are shown.
The figure shows that the food crust that was dated in Kiel is older than the three food crust samples that
were recently dated. The wood samples show a great variability. Two of them, KIA29524 and KIA30080 are
approximately contemporaneous with the charcoal sample. It should be kept in mind, though, that KIA30080
was reported to give a small pretreatment yield and that the result should be interpreted with caution. If
the wooden pole KIA29528 is regarded as an outlier (due to contamination or disturbed stratigraphy), all
other wooden poles are contemporaneous with or older than the charcoal sample. A possible scenario is
that the wooden structure of poles was constructed at the same time as the charcoal was used. The higher
ages of some of the wood samples may be the result of the usage of old wood for the wooden structure.
The fishbone sample is significantly older than all the other samples from Kayhude that were measured up
to now. If assuming that the fishbone sample and the food crusts were formed at about the same time,
it can be concluded that the food crusts were not exclusively made of fish. The experiment with recent
fishbones and food crusts made from the same fish showed that both samples yielded about the same age
91

Figure 4.8: The calibration of the archaeological samples from Kayhude. SID number: sample was measured
at the AMS 14 C Dating Centre, Aarhus University. KIA number: sample was measured at the Leibnitz
Labor for age determination and isotope research, Christian Albrechts University Kiel.

92

Table 4.9: C/N data of archaeological food crusts from Kayhude and modern food crusts
C:N
8.71
9.31
8.760.30
9.05
9.05

13 C
-28.880.10
-30.720.10

-28.700.10
-28.790.10

15 N
6.960.09
6.060.25

11.410.09
10.330.25

17.44
17.89

-26.440.10
-26.620.17

1.500.09
3.80.25

Wild boar (humic)

Wild boar (humic)
Wild boar (humic)
Wild boar (humic)
Fish
Fish
Fish
Fish
Fish (humic)
Fish (humic)

6.40
6.40
6.91
6.85
6.29
5.87
5.31
5.72
6.73
7.42

-17.880.10
-17.800.10
-18.000.10
-17.920.10
-27.210.10
-27.550.10
-28.140.10
-28.740.10
-123.250.10
-30.740.10

7.950.09
7.310.25
7.830.09
6.670.25
17.580.09
16.550.25
18.020.09
17.930.25
18.250.09
17.430.25

Archaeologic
Archaeologic (humic)

...
...

-28.860.22
-28.340.09

...
...

Sample ID
12047
12047
12047
12048
12048
12048
12345
12345

Material
Archaeologic
Archaeologic
Mean Value
Archaeologic
Archaeologic
Mean Value
Archaeologic
Archaeologic

12055
12055
12056
12056
12057
12057
12058
12058
12058
12058
KIA29527
KIA29527

(see section 4.2.1). As the food crust samples have about the same or a slightly higher age than the charcoal,
it can be concluded that they consist mainly of terrestrial ingredients with a little freshwater component.
Stable isotope measurements can shed more light on the composition of the food crusts. Unfortunately,
no stable isotope analysis was available for the food crust sample dated in Kiel. Only the result of a 13 C
measurement at the accelerator can be given. This result is only to a limited extent comparable with other
stable isotope measurements as it is influenced by fractionation during graphitisation and in the ion source.
The modern food crusts SID 12055 and 12056 dissolved completely in the NaOH step, so that only the
humic fraction was used. The similarity between the 13 C values of the archaeological food crusts to those
of the modern fish food crusts is striking.

4.2.5

Comparison with marine samples

To be able to give a short remark on marine samples, a pair of modern samples as well as one archaeological
sample, a food crust on pottery from the coastal site Neustadt (Holstein), have been examined. The blubber
of a porpoise that was found at the North Sea coast of Schleswig-Holstein was dated, as well as the crust
that was formed in a pot when the oil was cooked out of the blubber. These are the dating results:
Sample ID
12394
12395

Sample material
blubber
charred crust made of blubber

pmC
107.400.38
116.520.39

14

C age (years BP)

-57328
-122827

The pmC values of the porpoise are over 100% modern so that a calibration of the ages has to be done
with the bomb pulse. As the atmospheric bomb pulse is not directly reflected in the sea water, a marine
93

Figure 4.9: The bomb pulse in the atmosphere and different parts of the oceans. After C. R. Weidman,
unpublished PhD thesis 1995.
calibration curve has to be applied. There are different calibration curves for various zones of the oceans.
Some examples can be seen in figure 4.2.5 where also the two porpoise samples (fat and charred crust) are
plotted.
It is not possible to chose one curve for the calibration of the porpoise samples because it is not clear
where the porpoise lived and what it fed on. The calibration curves themselves were made from the 14 C
dating of shells which ideally reflect their environment because they are not as mobile as fish or, for example,
porpoises.
There is a remarkable difference in the 14 C ratios of both samples, although they were derived from
the same material. The difference corresponds to approximately 655 14 C years (after equation 4.6). As
can be seen from figure 4.2.5, a high pmC can be found some decades BP, while a pmC of 107 fits into
the extrapolation of the North Atlantic / North Sea calibration curves. Apparently, the 14 C content of the
blubber and the crust that was formed in the pot when the oil was cooked out of the blubber are different. A
possible explanation could be the following: Blubber consists of fat cells which are filled with oil. When the
oil is being cooked out of the blubber, the cell rests remain at the bottom of the pot and are likely to char
there while the liquid oil can be poured out of the pot. When now assuming different turnaround times for
the fat cells and their content, so that the cells have higher average ages, an age difference for the total fatty
tissue and the charred crust is probable. In future experiments with blubber, both the charred crust and
the oil should be dated to test this assumption. Unfortunately, no bones from the porpoise were available.

94

This would else be the ideal material for 14 C dating as it reflects the past 10 years of the porpoises life,
the turnover time for bone collagen being 10 years. Then it would also have been possible to compare the
13 C values of the bone collagen and the fat. The blubber has a 13 C value of -22.78h whereas the crust
from the pot has a 13 C value of -19.61h, both measured with dual inlet. The crust was also measured with
continuous flow and yielded a 13 C value of -19.4h. The 13 C value of the porpoise blubber is very negative
and unusual for a marine animal. But as was explained in section 1.3.1, different tissues of an animal can
have different 13 C values. The difference for fat and bones of an ungulate was for example 7.7h. If we
assume that a difference of the same order of magnitude also can be found in the porpoise, than its bones
would have a 13 C value of -15.1h. Bone collagen for Californian porpoises has a 13 C value of around
-12.6h(Chamberlain, Waldbauer, Fox-Dobbs, Newsome, Koch, Smith, Church, Chamberlain, Sorenson,
and Risebrough 2005), whereas bone collagen for Northern Pacific fur seals has values around -12hat the
Californian coast and -15hat the Western Aleutian Islands (Newsome, Etnier, Gifford-Gonzalez, Phillips,
van Tuinen, Hadly, Costa, Kennett, Guilderson, and Koch 2007). It can therefore not be ruled out that
porpoises living in the northern parts of the ocean have bone collagen values around -15h. This would then
well fit with the 13 C value of bone collagen calculated above for our example. However, these conclusions
are based on two assumptions and further investigations are therefore necessary. At least it could be shown
that a possible explanation for the unsusually low 13 C value of the porpoise blubber exists.
The food crust from a pot from a coastal site (Neustadt) has also been dated. As it was the only material
from that site that was dated in this thesis, it is not possible to make a statement about the marine reservoir
effect in food crusts from pottery. The Neustadt sherd has mainly been used for comparing stable isotope
analysis on different materials, als will be shown in section 4.3.

4.3

Comparison of the sites, discussion and conclustion

The 14 C ages of fresh water from both rivers differ significantly. The water from the Trave is 150664 14 C
years old whereas the water from the Alster has a 14 C age of 238044. The 14 C age of the Trave water is
thus only 63% of the 14 C age of the Alster water. The water hardness is the concentration of the alkaline
earth metal ions and is an indicator for the carbonate content of the water (see section 1.2.2). As the water
hardness in the Trave is higher than in the Alster (section 3.2.1), one can conclude that the water hardness
is not an indicator for the extent of the hardwater effect. The same observation was made by Fontes (1992)
who warned that carbonate dissolution should not automatically be considered as an index of 14 C dilution
(see section 1.2.3). The DIC amount, though, that could be extracted from the water samples, is much higher
for the Alster than for the Trave sample. The conclusion should thus rather be that the water hardness is
not a good indicator for the DIC content and age of a river water sample. As only two water samples were
measured here, more research taking multiple samples and testing several rivers is favourable. Fish samples
from the Trave have a mean 14 C age of 70146 and those from the Alster are about 63546 14 C years old,
which is about 91% of the 14 C age of the fish bones from the Trave. In figure 4.3 the 13 C and 15 N values
of the archaeological and modern food crust samples are mapped.
The 13 C values of the archaeological samples from Schlamersdorf and Kayhude (displayed in cyan and
red) are similar to those of modern food crusts made of freshwater fish (green). The 15 N values for the
archaeological samples are in general smaller than those of modern material. This is presumably caused by
the decomposition of the food crust during burial in the soil. The carbonized parts of the food crust are not
attractive for microbiological organisms, in contrast to protein-containing parts. Therefore, the 13 C values
are supposed to reflect the original composition of the food crust whereas the 15 N values are supposed to
have changed. The 13 C values of the food crust from Neustadt are widely spread, although all samples
were taken from the same sherd. This spread already can be found in the doublets that were measured
of the different fractions. First, a part of the food crust that already fell off the sherd during storage in
the museum was pretreated. From this part, both the base-soluble and isoluble fraction were measured in
doublets. Furthermore, some food crust that was adhering firmly to the sherd was scraped off, and a doublet
of the base-insoluble fraction of this sample was measured. These are the 13 C measurement results of the
different fractions:
95

Figure 4.10: 13 C (X-axis) and 15 N (Y-axis) values of food crusts.

96

Sample ID
12053
12053
12053
12053
12054
12054

Sample material
Food crust, fallen off
Food crust, fallen off
Food crust, fallen off (humic)
Food crust, fallen off (humic)
Food crust, scraped off
Food crust, scraped off

13 C
-20.100.10
-22.990.10
-22.110.10
-22.100.10
-20.580.10
-19.080.10

The food crust that was scraped off the sherd has less negative 13 C values than the food crust that fell
off. The measurement of the first doublet is not considered as reliable as the others as there is a big difference
in the 13 C values. Only the 13 C values of the second doublet, the humic fraction of the food crust that
was fallen off, are agreeing perfectly. The 13 C values of the pottery fit very well the expected origin. The
samples from Schlamersdorf and Kayhude, for example, are expected to consist at least partly of freshwater
fish. Their 13 C values are about the same as those of recent freshwater food crusts. The sample from the
coastal site Neustadt is expected to reflect the marine environment where it comes from. Accordingly, the
13 C values of this food crust and of a recent food crust made of porpoise match. A complete discussion of the
probability of a hardwater effect in the archaeological material is not yet possible. The few food crust that
could be dated up to now all come from the same site, Kayhude. The sample that were dated in this project,
SID 12047, 12048, 12345, 12346 and 12392, were all associated because they were found in an undisturbed
stone layer. As could be seen on figure 4.2.4 in section 4.2.4, the fishbone sample from these sample group
is significantly older than the charcoal sample. One food crust is approximately contemporaneous with the
charcoal, one is slightly, but not significantly older and one is significantly older. The age difference of the
oldest food crust and the charcoal sample is only 650 14 C years, whereas the age difference between the
fishbone and the charcoal is more than 3000 years. As was shown in 4.2.1, a food crust that only consists
of fish has the same 14 C age as the bones of a fish that was used for preparing the crust. It can therefore
be concluded that the food crusts from Kayhude not exclusively originate from fish. If they did, then they
should have the same age as the fish bones. It is remarkable, though, that the food crusts from Kayhude
had the same 13 C value as modern food crusts that were made of freshwater fish. It can thus not be ruled
out that the one fishbone that was dated so far really is older, not only in hardwater-caused 14 C years, but
also in real calendar years. In that case, it must have entered the find layer 3000 years after it had been
deposited elsewhere. As the reservoir age for modern Alster fish is about 650 years (see section 4.2.3), it is
unlikely that the reservoir age during the time of the Erteblle culture was 5 times as high. A final answer
to the question Hard water or high ages? is not possible until the remaining samples are dated. It can
only be concluded that a hardwater effect on food crusts from Schlamersdorf and Kayhude is probable, but
the extent of the hardwater effect can not yet be determined.
The experiments concerning the preparation of small samples are not terminated, but some general
tendencies could already be observed. Iron will be used instead of cobalt for graphitisation of small samples
because it improves the reaction ratio. Furthermore, it could be shown that a smaller reaction volume
reduces fractionation during graphitisation. Thus, the small reactors will in the future be used routinely for
samples below 0.2 mgC, and the normal-sized reactors will be exchanged with reactors that have a reduced
volume, but are still big enough for the graphitisation of about 1 mgC. These new reactors will also have
pressure transducers that are connected to a computer so that the pressure can be monitored automatically,
as is already is possible for the small reactors. It could be shown that the trapping device that combines
stable isotope measurements with the combustion of samples for AMS 14 C dating works in principle without
introducing more fractionation than the traditional combustion process. Only the trapping yield is not
sufficient. Further development will include the use of really vacuum-tight valves and automatisation of
the cryogenic transfer of the sample to a manifold tube for handling the sample over to the graphitisation
system.

97

Glossary
Activity
The activity of a radioactive substance is the number of disintegration per time unit. It can be measured
in Becquerel (1bc = 1 decay per second), in Curie (1Ci = 3.7*1010 decays per second = (3.7*1010 bc)
or in the case of very low activities in disintegrations per minute (dpm).
AMS
AMS, Accelerator Mass Spectrometry, is mass spectrometry using an accelerator. At high energies,
particles can be separated and counted that else would be indistinguishable. It is mainly used for the
measurement of long-lived cosmogenic radionuclides such as 14 C or 10Be.
Archaeometry
The application of scientific methods to archaeological problems.
Atlantic
Besides the ocean, the term Atlantic denotes a climatic period at the end of the Holocene. It lasted
from the 6th to the beginning of the 3rd millennium BC and was a period of warm and very moist
climate. Thermophilous species migrated north, and the Boreal mixed forest was replaced by the
climax forest, containing trees like oak, lime and elm.
Background correction
A background correction in 14 C dating is made by measuring a 14 C-dead sample. A 14 C ratio that is
measured although the sample does not contain any 14 C, is called background. The 14 C ratios of other
samples have to be corrected for that backgroung 14 C ratio.
Blubber
The fat of whales or other large marine animals.
Boreal
The Boreal is the climatic period that precedes the Atlantic. It came after the cold period Younger
Dryas, during which Europe was covered with Tundra and Taiga. Around 11,500 cal. BP the temperature rises quite sharply, which marks the beginning of the Boreal. The climate in that period varied,
but it was mostly like today. Forests began covering the European plains, and a raising of the sea level
resulted in the formation of numerous islands. The Boreal ended around 8,000 cal. BC when the even
warmer Atlantic began.
Dalton
One Dalton (Da) is one unified atomic mass unit (u), roughly equal to the mass of a proton or
neutron. In biochemistry and molecular biology literature (particularly in reference to proteins),
the term dalton is used, with the symbol Da. Because proteins are large molecules, they are
typically referred to in kilodaltons, or kDa, with one kilodalton being equal to 1000 daltons
(http://en.wikipedia.org/wiki/Atomic mass unit on March 13, 2008).

98

Decay constant
The decay constant of a radioactive substance is the inverse mean life,
Mean life.

1
.

See also Half-life and

Emmer
The pristine form of wheat that was used in the Early Neolithic
Estuary
An estuary is a body of water with one or more rivers flowing through it and with connection to the
open sea. It is often under tidal influence and the brackish water provides nutrients as a basis for rich
biological activity.
Flake adze
German name Scheibenbeil. An adze that was produced by knapping flint flakes from a nucleus.
Flint knapping
The process of flintstone tool production
Funnel Beaker culture
The Funnel Beaker culture is an early Neolithic culture that followed the Erteblle culture. It stretched
across the Netherlands, Northern Germany, Poland and Southern Scandinavia and lasted from c. 4200
to c. 2800 BC.
Geest
Geest or geestland denotes a landscape type in Northern Germany, Denmark and the Netherlands.
It consists of sandy glacial deposits and is often next to marshland. It lies normally higher than
marshlands and is slightly hilly.
Half-life
The half-life of a radioactive substance is the time after which half of the atoms are decayed. See also
Mean life.
High Atlantic Climatic Optimum
The High Atlantic Climatic Optimum is the climax, the warmest section, of the Atlantic.
Homeostatic
Being in a relatively stable state of equilibrium or having a tendency toward such a state between the
different but interdependent elements or groups of elements of an organism, population, or group (after
Merriam-Webster Online Dictionary, 28.01.2008).
Hunter-gatherers
People whose subsistence is mainly based on hunted game and collected plants. Sometimes, fishing is
also included.
ologische Landesaufnahme)
LA - Landesaufnahme (here: Archa
An Arch
aologische Landesaufnahme is an archaeological field survery where archaeological finds are
continuously registered and mapped. In Schleswig-Holstein, the Archaologische Landesaufnahme is
working since about 80 years. From the Landesaufnahme, sites get individual numbers to identify
them, in combination with the name of the region or village next to which the site was found. The
two sites regarded in this thesis have thus the names Schlamersdorf LA5 and Kayhude LA8.
Linear Pottery culture
The abbreviation for this culture is LBK, after its German name Linearbandkeramische Kultur. It
is one of the oldest Neolithic farming cultures in Central Europe. It ranged from Western Hungary,
Romania and the Ukraine over Western Slovakia, Poland and Germany up to Eastern France. It was
thus the biggest culture of the Neolithic, in terms of geographical spread.
99

Mean life
Symbol . Also mean lifetime. The mean life of a radioactive substance is the time after which
1
1
e = 2.718 of the atoms are decayed. See also Half-life and Decay constant.
Mesolithic
The Mesolithic is the younger phase of the older (hunter-gatherer) stone age. It is the time since the
last ice age until the beginning of farming ((Mikkelsen 1978)). In regions outside Northern Europe that
were not affected by the ice age, a division of the older stone age into Palaeolithic and Mesolithic is
irrelevant. In Northern Europe, though, the landscape changed drastically as the ice age ended. Open
grass plains were herds of big mammals were grazing were replaced by dense forest which required
different hunting strategies and so different tools, which is reflected in the archaeological record as a
transition from one culture to another.
Michelsberg culture
The Michelsberg culture (German: Michelsberger Kultur (MK)) is an important Neolithic culture in
Central Europe. Its conventional name is derived from the important excavated site on Michelsberg
(or Michaelsberg) hill near Untergrombach, between Karlsruhe and Heidelberg (Baden-W
urttemberg).
The Michelsberg culture is dated in the late 5th and the first half of the 4th millennium BC. Thus, it
belongs to the Central European Late Neolithic. Its distribution covered much of West Central Europe,
along both sides of the Rhine
Neolithic
The younger stone age, where stone still was the most important raw material and metal, if known,
only played a minor role. Agriculture and connected phenomena distinguish this phase from the older
stone age.
New Archaeology
Also processual archaeology. A movement beginning in the 1960s that places emphasis on scientific
methods and defines culture as means of adaptation, thus describing a cultural evolution. The aim of
new archaeology was to explore the people that made the artefacts found in archaeological excavations,
the society they lived in and their way of life. The American archaeologist Lewis Binford was one of
its main advocats, why it sometimes is called The new archaeology since Binford. This movement
can be seen as a reaction to the culture history approach that dominated in that time. In culture
history, emphasis lies on artefacts which are described and on the basis of which chronologies are built
up. The reconstruction of past human habits on the basis of artefacts is regarded infeasible in the
cultural-historical approach.
Peltier cooler
A Peltier cooler, heater, or thermoelectric heat pump is a solid-state active heat pump which transfers
heat from one side of the device to the other side against the temperature gradient (from cold to
hot), with consumption of electrical energy. Thermoelectric junctions are generally only around 510%
as efficient as the ideal refrigerator (Carnot cycle), compared with 4060% achieved by conventional
compression cycle systems (reverse Rankine systems like a compressor). Due to the relatively low
efficiency, thermoelectric cooling is generally only used in environments where the solid state nature
(no moving parts, maintenance-free) outweighs pure efficiency (http://en.wikipedia.org/w/index.php?title=Thermoelectric cooling&oldid=186367236) on Jan 24, 2008).
Phloem
Phloem is a transport tissue in plants. It transports mainly nutrients. The name is derived from the
Greek word for bark, as the inner layer of a trees bark consists of phloem.
Phosphoenolpyruvate (PEP) carboxylase
PEP carboxylase is an enzyme that catalyzes the addition of CO2 to phosphoenolpyruvate (PEP) to
form the four-carbon compound oxaloacetate.
100

Pot boiler
Pot boilers are stones which are heated in a fire and then used for heating liquids. This can be in a
clay pot, a skin container or a cooking pit.
Provenance studies
In provenance studies, chemical and other scientific methods are used for finding out, where an artefact
or raw material comes from. The basis for these methods is the fact, that for example clay or flint
deposits have a characteristic chemical composition. When the chemical composition of a sample is
measured, it can be compared to that of a range of possible raw material deposits.
Remote sensing
Remote sensing is the gathering of information about an object without having physical contact to
that object. Examples are satellite pictures, radar or magnetic resonance imaging. These techniques
can for example be used for the detection of buried building structures.
Ribwort plantain
Latin name Plantago lanceolata. A weed that is common on cultivated land and can therefore be used
as an indicator of agriculture or grazing. Originating from Europe, but now world-wide prevalent.
Roach
A small fish of the Cyprinid family, between 25 and 45 cm long, that is common in many rivers and
lakes throughout Europe
Rubisco enzyme
Rubisco, also written RuBisCO, is the abbreviation of Ribulose-1,5-bisphosphate carboxylase / oxygenase. It is an enzyme that catalyzes the first major step of carbon fixation in the Calvin cycle of
photosynthesis. It catalyzes either the carboxylation or oxygenation of ribulose-1,5-bisphosphate (also
known as RuBP) with carbon dioxide or oxygen. It is the most abundant protein in leaves and it may
be the most abundant protein on Earth (http://en.wikipedia.org/wiki/Rubisco on March 24, 2008).
Scanning electron microscope (SEM)
An electron microscope in which a beam of focused electrons moves across the object with the secondary
electrons produced by the object and the electrons scattered by the object being collected to form a
three-dimensional image on a display screen (www.merriam-webster.com on March 7, 2008)
Shoe last axe
Also shoe last celt. A long and thin stone tool whose form reminds of a shoe makers last. They were
produced by the early neolithic Linear Pottery culture which populated big parts of Europe. Shoe last
axes were mainly used as wood working tools. In the Erteblle culture, finds of shoe last axes indicate
trading connections to Neolithic cultures further south and the Linear Pottery culture.
Sorrel
Latin name Rumex acetosa. Sorrel is a perennial herb that is cultivated as a leaf vegetable
(http://en.wikipedia.org/wiki/Sorrel on March 18, 2008).
Sub sample ID (SSID)
The sub sample ID is used to identify different fractions and preparation steps of a sample in our
laboratory.
Terminus ante quem
Literally Limit before which. A terminus ante quem describes a point in time before which a certain
event happened. Example: When a letter describes a certain event, the letter is a terminus ante quem
for the event, because the event happened before it was described in the letter.

101

Terminus post quem

Literally Limit after which. A terminus post quem describes a point in time after which a certain
event happened. Example: When a coin is found in a grave, it is a terminus post quem for the burial,
because the person was buried after the coin was produced.
Transgression
The spread of the sea over land areas and the consequent unconformable deposit of sediments on older
rocks (www.merriam-webster.com on 07.03.2008)
Xylem
The word xylem derives from the Greek word for wood. It is a transport tissue in plants and wood is
the most commonly known tissue of this type. It mainly transports water.

102

List of Tables
Average 15 N values in bone collagen of different terrestrial and marine animals (Schoeninger
and DeNiro 1984) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

25

2.1
2.2
2.3
2.4
2.5
2.6
2.7

Combustion and graphitisation of graphite . . . . . . . . . .

Combustion and graphitisation of Gel A . . . . . . . . . . .
Single and double combustion and graphitisation of GelA .
Graphitised samples for C/N measurements and SEM . . .
Graphitisation yield of small samples . . . . . . . . . . . . .
Quartz tube combustion and graphitisation of GelA samples
CO2 trapping tests . . . . . . . . . . . . . . . . . . . . . . .

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4.1

Sherd samples from Kayhude and Schlamersdorf: sample type, NaOH concentration for pretreatment and pretreatment yield. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Quality of extracted collagen. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Trave - modern samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Trave - reservoir ages of modern samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Trave - archaeological samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Alster - modern samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Alster - reservoir ages for modern samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Alster - archaeological samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
C/N data of archaeological food crusts from Kayhude and modern food crusts . . . . . . . . .

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1.1
1.2
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1.6
1.7
2.1
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2.6
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2.14
2.15
2.16

3.1
3.2
3.3
3.4
3.5

The radioactive decay of 14 C . . . . . . . . . . . . .

Bomb pulse in atmosphere and oceans . . . . . . . .
A tandem accelerator . . . . . . . . . . . . . . . . .
Particle detector . . . . . . . . . . . . . . . . . . . .
AMS measurement procedure . . . . . . . . . . . . .
Fractionation of 13 C and 14 C during photosynthesis,
groundwaters . . . . . . . . . . . . . . . . . . . . . .
13
C ranges in natural compounds . . . . . . . . . . .

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Normal-sized graphitisation reaction tubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

The part of the graphitisation system with small reactors. . . . . . . . . . . . . . . . . . . . .
Graphitisation of two identically sized samples with cobalt and iron as catalyst. . . . . . . . .
Start of graphitisation with Co and Fe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Graphitisation of samples of different size with iron . . . . . . . . . . . . . . . . . . . . . . . .
Graphitisation of Water Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
SEM pictures of graphitised samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Graphitisation of small samples in normal-sized (R11-R17) and small (R19 and R110) reactors
Small sample graphitisation on cobalt. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Graphitisation of two small samples in small reactors on cobalt . . . . . . . . . . . . . . . . .
Graphitisation yield as a function of sample size for graphitisation on iron and cobalt . . . .
The continuous flow elemental analyzer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Sample transfer for 13 C dual inlet (DI) measurements . . . . . . . . . . . . . . . . . . . . . .
Trapping CO2 from EA combustion for graphitisation . . . . . . . . . . . . . . . . . . . . . .
The valves that control the trapping process . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Combustion and graphitisation of GelA - comparison between different graphitisation parameters after traditionel combustion in quartz tubes . . . . . . . . . . . . . . . . . . . . . . . .

3.6
3.7

Map of EBK sites with dated food crusts . . . .

Map of Schlamersdorf and its surroundings . . .
Map of Kayhude and its surroundings . . . . . .
Funnel beaker . . . . . . . . . . . . . . . . . . . .
The reconstructed Erteblle settlement
Photograph by Peter Marling/Scanpix Nordfoto .
Rebuilding a pointed-base vessel . . . . . . . . .
Copies of EBK pottery . . . . . . . . . . . . . . .

4.1
4.2
4.3
4.4
4.5

Water sample preparation . . . . . . . . . . . . . .

Photographs of the modern fish and shell samples.
Finishing a pointed-base vessel . . . . . . . . . . .
Firing of the pointed-base vessels . . . . . . . . . .
Food crust production of fish and meat . . . . . . .
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Bomb pulse extended with exponential decrease fit . . . . . . . . . .

Calibration of the archaeological samples from Schlamersdorf . . . .
Calibration of the archaeological samples from Kayhude . . . . . . .
The bomb pulse in the atmosphere and different parts of the oceans.
13 C and 15 N values of food crusts . . . . . . . . . . . . . . . . . .

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Index
14

C dating, 1
N, 24
15
N, 24

Glutamic acid, 29
Glycine, 29

14

Absolute international standard activity (AISA), 12

Accelerator Mass Spectrometry, 6
Alanine, 29
Alster, 57, 60
Ancylus Lake, 62
Archaeological science, I
Archaeometry, I
Atlantic period, 60
Baltic Sea
formation, 62
Blubber, 64
Bomb pulse, 4
High precision radiocarbon dating, 4
Calibration (Radiocarbon), 5
Calibration curve, 4
Catalyst, 38
Catastrophe theory, 69
Cysteine, 29
Dating of pottery, 26
Decay law, 2
Dendrochronology, 6
Ellerbek culture, 62
Erteblle
culture, 61
sedentariness, 63
pottery
lamp, 64
pointed base vessel, 64
site, 61, 62
economy, 63
Fractionation, 5
Freshwater reservoir effect, 13
Funnel Beaker culture, 61, 68
Garden of Eden argument, 66

Hardwater effect, 14
High Atlantic climatic optimum, 62
Kkkenmddinger, 61
Kayhude, 56
Kitchenmidden, 61
Kitchenmiddens, 61
Late Mesolithic, 61
Libbys half-life, 4
Litorina Sea, 62
Litorina transgressions, 62
Marine reservoir effect, 13
Marl, 60
Mesolithic, 65
Methionine, 29
Michelsberg culture, 67, 68
Neolithic, 61, 65
Neolithic revolution, 65
Neolithisation, 65, 66
Nordic Terminal Mesolithic, 61
North Sea
formation, 62
Oxalic acid, 12
Pee Dee belemnite, 22
Percent modern carbon, 12
Photosynthesis
Calcin cycle (C3 ), 22
Crassulacean acid metabolism (CAM), 23
Hatch-Slack cycle (C4 ), 23
pmC, 12
Pointed base vessel, 64
Pot boiler, 57
Proto-neolithic, 61
Radiocarbon
Decay counting, 2

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half-life, 1
Radiocarbon dating, 1
Radiocarbon dating of pottery, 27
Radiocarbon Revolution
Second Radiocarbon Revolution, 6
Radiocarbon revolution, 1
Reservoir effect, 13
Run-off effect, 24
Schlamersdorf, 56
Spitzboden (pointed base vessel), 64
Suess effect, 4
Tandem Accelerator, 11
Temper, 26
Third radiocarbon revolution, 10
Trave, 56, 60, 62
Typological sequence, 26
U-technique (pottery), 65
USGS Radiocarbon Dating Laboratory, 4
Water hardness, 14, 60
Water Samples
Graphitisation, 41
Wiggles, 4

114

Declaration:
I hereby declare that I wrote this thesis independently and that I did not use any sources and auxiliary
means other than the ones indicated.

Erklarung:
Ich versichere, da ich diese Arbeit selbstandig verfasst und keine anderen als die angegebenen Quellen
und Hilfsmittel benutzt habe.

Heidelberg, March 31, 2008.

............................................
Bente Philippsen

115