..

The chronology of the Neolithic of The chronology of the Neolithic of Southern region of Russia: Southern region of Russia:

reliability of reliability of the dates from the pottery carbonthe dates from the pottery carbon

ZaytsevaZaytsevaGannaGannaInstitute for History of Material Culture, Russian Academy of Sciences, St.

Petersburg, Russia

About the History of the Eastern Europe Neolithic

� Until the mid 1990s the chronology of Eastern European Neolithic was developing rather independently from the those of Western and Central Europe.

� This was at least partly due to the special character of the Eastern European Neolithic, quite distinct from other parts of Europe and the Near East

Chronology of the Neolithic of Russia� It should be remarked that the concept of Neolithic in Russia is quite

different from that adopted in Western Europe. � If in the West the beginning of Neolithic is viewed as the spread of

farming, Russian archaeology traditionally correlates it with the beginning of pottery making.

� During the last 20 years the situation with the age of Forest Neolithic changed considerably. The beginning of the Forest Neolithic in 1950-70-s was placed to the period about beginning of 3rd millennium BC, and now it is considered as about 6300 – 6000 millennium BC, follow the numerous radiocarbon dates first of all for the sites of the Upper Volga Early Neolithic culture.

� Recently available radiocarbon dates show, that the early pottery-making communities in the steppe and boreal areas of Eastern Europe started spreading at an early date, comparable to and even preceding in age early farming communities in the South-Eastern Europe.

DATABASE of Neolithic sites

• Now a lot amount of the 14C dates were produced for European Neolithic sites.

• Summarizing the 14C dates plays the important role for the comparison of different Neolithic cultures to determine the place of the cultures on the chronological time scale.

• Now the database of the Neolithic sites was created both for the Western and Eastern Europe.

• This database is numerated 5940 14C determinations for the Western Europe and 1260 ones for the Eastern Europe.

• The 14C determinations were done by AMS and conventional techniques from different samples.

Database of the 14C determinations of the Neolithic sites

� In the 14C Lab of the Institute for the History of material cultures the computer database of the 14C determinations was started to create using both dates produced by our Lab and published in the literature.

� Now this database is numerated more than 9000 determinations� Among them about 950 14C dates are related to the Neolithic of

European Russia.

� Among them 208 14C dates for the Southern regions of European Russia including 123 14C dates from the pottery.

Content of the Database for the Eastern and Western Europe

0

100

200

300

400

500

600

700

800

900

Belarus Estonia Latvia Lithuania Moldova Russia Ukraine

Belarus

Estonia

Latvia

Lithuania

Moldova

Russia

Ukraine

0

100

200

300

400

500

600

700

800

900

1

Albania

Austria

Belgium

Bosnia

Bulgaria

Croatia

Cyprus

Chech Republic

Denmark

France

Germany

Greece

Hungary

Ireland

Italy

Luxemburg

Macedonia

Nethelands

Norway

Poland

Portugal

Romania

Serbia

Slovakia

Spain

Sweden

Swetzerland

United KingdomEastern Europe

Western Europe

UKFrance

Russia

EurasiaEurasia: : earlier pottery productionearlier pottery production(by Prof. P.Dolukhanov)(by Prof. P.Dolukhanov)

The samples for dating

• For dating is using different carbon content material:

• 1. Organic materials: wood, charcoal, peat, bone, humus acids from soil.

• 2. Inorganic material: shells, apatite, carbonate.

• Now we will consider the particularities of each groups of samples.

The dating material

0

200

400

600

800

1000

1200

1400

1600

1 2 3 4

Charcoal

Animal bones

Human bones

Wood

Food residual

Shell

Peat

Seeds

Soil

Pottery

Western Europe Eastern Europe

Histogram of the distribution of the 14C ages of the Mesolithic-Neolithic sites

Distribution of the 14C dates for the Mesolithic-Neolithic sites of Russia

0

10

20

30

40

50

60

70

80

90

0 2000 4000 6000 8000 10000 12000 14000 16000

Radiocarbon age, BP

Fre

quen

ce o

f dat

es

Yelshanian Culture

The Yelshanian-type pottery as the earliest technology of this kind onthe East European Plain was first recognized in the Samara-Volga areain 1970s. The majority of the pottery vessels were not ornamented. By now the typical “Yelshanian” assemblages has been identified at several sites.

Yelshanka IV site

Yelshanian: 14C dates

The main dated materials are charcoal from the pottery, destroyed bones and shells. Shells are not available material due to the reservoir effect and theycan show the oldest age.

Northern Caspian Area

Early pottery sites have been identified invarious part of the North Caspian Lowland andAnalog the lower stretches of the River Volga.Two cultural groups have been distinguished:Kairshak-Tektensor and Jangar-Varfolomeyevian

Northern Caspian:Varfolomeyevka

The pottery was usually manufactured from the claywith crushed shells

North Caspian: 14C dates

800072006400560048004000

25

20

15

10

5

0

Data

Frequency

N_Cas

N_Cas_Coeval

Variable

Recently a large series of 14C dates have been obtained mostly from the organicmatter in the ceramics. The coeval sample test reveal T=5859±2376 cal BC.Significantly, there is a considerable number of dates falling beyond the subsamples and showing the age in the range of 8000-6500 BC the age.

Rakushechnyi Yar

Rakushechnyi Yar (RY) is a clear stratifiedSettlement located on a small island in thelower stretches of the River Don studied in 1970s Prof T. Belanovskay and later by A,.and V.Zybri.

The panoram of the Rakushechnyi Yar

Rakushechnyi Yar

The excavations exposed an area of c. 1,200 square meters, with 23 archaeological layers, ranging from the Bronze Age to the Neolithic. The deepest levels (23–6) belong to the Early Neolithic. The pottery which constitutes the main element of the material culture is encountered in large quantities starting with the lowermost level of the site.There are two sections with the shells Unio and Viviparus.

The cross section of the Rakushechny Yar site (2008 г.)

The samples for 14C dating the pollen analyses have been selected in 2008.

№№ Depth Litho logy

1 4.30 Charcoal layer

2 4.45 Charcoal layer

3 4.8-4.9 Charcoal layer

4 5.10-6.70 Charcoal layer

5 5.10 Charcoal layer

6 5.10-5.20 Charcoal layer

7 5.00 Charcoal (a little)

8 4.30 Charcoal layer

9 5.00 Charcoal layer

10 Bone

11 5.10-5.20 shell Unio

12 5.10-5.20 Shell Viviparus

7685±±±±70 BP

8050±±±±70 BP

0

50

100

150

200

250

300

350

400

450

500

550

600

Dep

th,

cm

20 40 60 80 100

Trees

Herbs

Spore

s

Picea

20

Pinus

Betula

Alnu s

Juni

perus

Querc

usUlm

usTilia Carp

inus

Salix

Corylu

sEph

edra

20

Poace

ae20

Cyper

aceae

Brass

icac

eae

Apiace

aeFab

acea

ePoly

gona

ceae

Rumex

Urtica

20 40

Chenop

odiac

eaeCar

yoph

yllace

ae

Ranunc

ulace

ae

Lam

iace

ae

Rubia

ceae

Valeria

naM

alvac

eae

Euphor

biace

ae

Rosac

eae

20 40

Astera

ceae

20 40

Cichor

iace

aeCen

taur

ea

20

Artem

isia

Typha

20

Varia

Polypo

diac

eae

Equise

tum

Zone6

5

4

3

2

1

Trees Herbs Spores

Rakuchechnyi Yar

Anal.: T.Sapelko1 2 3 4 5

Lithology

POLLEN SPECTRA

1- modern soil; 2 – sand loamy soil; 3 – loamy soil with the humic ; 4 – sand; 5 – sand with the loamy soil.

Pollen zone 1(525- 600 cm)The amount of the wood species here is rather relative high (about 11-20%). The pollen

of pine is predominated.Pollen zone 2(345 - 525 см)The percentage of the wood species was increased up to 25%. The anthropogenic factor

is visible. Pollen zone 3(265-245 см)This zone is corresponded to the humic loamy soil. The pollen of grass is predominated

up to 80 or 100%. Most probably the were the erosions. Pollen zone 4(183-265 cm)This zone is related to the humic loamy soil. The pollen concentration is increased. But

the pollen pine is predominated (up to 12%) the pollen of deciduous species is reached of the maxima. Climate was warm and damp.

Pollen 5 (40-183cm)Loamy sand soil. The pollen percentage is the same, but the pollen of deciduous is

practically disappeared. Grass is varied. The climate is became of more arid. Pollen 6 (0-40 cm)The modern soil.

In common for all zones, the pollen of the crops plants was not presented.

Rakushechnyi Yar pottery

Rakushechnyi Yar 14C Dates

One can determine at last 3 stages of settling this site: about 7000 BC, 6600 BCand 5800 BC

The Razdorskaya site

The RazdorskaySite is located on the along shore the Don Riveropposite the RakushechnyYar site.No ceramic was found here.

The 14C dates for the Razdorskaya site

Lab. index 14C age, BP Calibrated age, cal BC (1δ)

Calibrated age, cal BC (2δ)

Material dated

Ki-15177 7490±60 6412-6257 6439-6230 charcoal

Ki-15178 8210±80 7446-7081 7475-7059 charcoal

Ki-15179 7840±80 6970-6511 7032-6497 charcoal

Le-6873 7640±120 6639-6386 6754-6222 charcoal

Le-6950 7450±100 6412-6225 6459-6082 charcoal

Le-6952 7930±50 7028-6694 7028-6655 charcoal

Le-8795 7470±150 6456-6112 6592-6020 charcoal

Le-8430 7840±140 7029-6504 7075-6436 charcoal

Le-8425 6570±220 5713-5315 5894-5021 charcoal

Le-8426 8130±140 7448-6830 7478-6692 charcoal

Le-8427 8070±70 7285-6829 7308-7221 charcoal

Ki-15943 7810±70 6746-6503 6982-6464 charcoal

Le-8428 a 7920±110 7032-6655 7078-6503 Humic acid (hot)

Le-8428 b 8130±100 7322-6865 7451-6800 Humic acid (cold)

The finds of the Razdorskaya

Razdorskaya 14C dates

The 14C dates show the old age. Most probably this site is belong to theMesolithic-Neolithic transition.

South East European Plain Neolithic: 14C dates

Carbon-containing materials of pottery

• Since the 1950s the attempts are being made of direct measurement of organic carbon derived from the pottery matrix. Kohl and Quitta (1964) were among the first who obtained the dates for early Neolithic LBK by direct dating the pottery carbon. In 2002 the article was published (Bonsall, Cook et al.) where the review of the methods dating of the pottery for a long time was presented and discussed.

• The food residue of the pottery is dating the time of using the pottery, but this residual is not always remained. Besides, there are the archaeological sites which did not content the dated materials as wood, charcoal, and others. These sites are usually located in the southern regions where environmental conditions were not promoted the good preservation of the organic materials. The bone materials practically did not content the collagen which was destroyed. Here we will consider only the Neolithic sites because of they have a key position for the questions of spreading and developing of the Neolithic in Europe. These sites contain a lot of the pottery which are the main materials for the archaeological attributions.

• The age of pottery assemblages is usually estimated based on radiocarbon dates of samples of organic matter from the objects (hearths, seeds, wooden structure), which are deemed as synchronous with the pottery.

• Yet this synchronicity can never be absolute. Hence the main questions for the pottery dating are the origin of the organic matters.

• We will try to determine the components of the organic containing materials in the pottery using the method of Nuclear magnetic resonance.

CARBON-CONTANING MATERIAL IN POTTERY

• But there are a lot of problems connected with the origin of the carbon-containing materials in the pottery. Here we will not consider the food residue because this material can be dated by the time of use of the pottery. But there are carbon-containing materials within the clay mass of the pottery itself.

• For some sites the 14C dates have been produced as from the pottery, food residue from the pottery, pottery itself and charcoal, bone remains and wood. It is very interested to compare the results.

THE POSSIBLE SOURSES OF THE CARBON IN POTTERY

• The question is remained: which carbon-containing components are contained both in the food residue and in the clay mass of pottery.

• The origin of the carbon-containing component in the clay mass of pottery can be following:

• 1. Carbon can penetrate into pottery from the organic matter in the clay, which arose in a distant geological period. Hence, its age may be much older than that of the pottery;

• 2. Carbon derived from temper (grass, straw, chaff, dung, and ground shells), the age of which is contemporaneous with the manufacture of pottery. Yet in the case of shells the reservoir effect should be taken into account;

• 3. Carbon absorbed from fuel during firing in the kiln;• 4. Carbon resulting from contamination from the surrounding soil.

METHOD TO BE USED

• For the study the NMR spectrometer AVANCE-500 of the Bruker firm was used. .The working frequency is 500 MHz. We used the pottery on the surface which the food residue was preserved. Breaking fragment of pottery itself .shows the black lay looks like on the charcoal. Food residue and pottery fragments with the trace of charcoal were analysed by separately. At first the fragment of the pottery and the food residue were powdered and the components were extracted by hexane which then was removed and remainder were dissolved in CDCl3. Solution was analysed on the nucleus 1H and 13C. To relate the lines of spectra the model follow compounds were used: olive oil for the lines of the ethers of glycerines, cetylpalmitate (СН3(СН2)14С(О)О(СН2)15СН3), octyl ether CH3(CH2)7]2O; octadecyl alcohol (СН3(СН2)17ОН); decyloleat СН3(СН2)9ОС(О)(СН2)7СН=СН(СН2)7СН3; octadecan (paraffin) СН3(СН2)16СН3; stearic acid (СН3(СН2)16СООН) and beeswax. To records the spectra these compounds were dissolved in CDCl3 too. The spectra of samples were distinguished by the quantitative composition of the different organic compounds containing double bounds (chemical shift δ -5.35), the triglycerides of the unsaturated fatty acids (δСНО = 5.30, δСН2О = 4.32 and 4.15,), different ethers (δСН2ОС(О) = 4.06), alcohols ( δСН2О = 3.64), fatty acids ( δСН2С(О)ОН = 2.25÷2.40) and traces of the ethers (δСН2О = 3.38), besides the aromatic compounds (δСН =7.0÷7.8) were observed. The spectra of the food residue and the clay mass of the pottery were compared.

THE ZAMOST’E SITE 14C DATES

Lab. index Material dated 14C age, BP Calibrated age, cal BC (1δ)

Calibrated age, cal BC(2δ)

GIN-6198 Peat 6680±100 5663-5485 5746-5469

GIN-6557 Peat 6850±60 5786-5641 5840-5634

GIN-6564 Peat 7050±40 5986-5843 5994-5809

GIN-7985 Peat 6290±40 5317-5132 5361-5080

GIN-7988 Peat 7200±90 6202-5928 6231-5885

GIN-7986 wood 7000±70 5980-5801 5991-5730

Ki-15031 charcoal 6730±120 5727-5530 5842-5470

Ki-15030 Food residue 6440±120 5526-5298 5621-5079

Ki-15032 Food residue 6300±130 5465-5069 5482-4936

The samples of food residue and carbon in the clay mass of pottery had been presented in the Zamost’e Neolithic site located in the Central Part of European Russian Plain, Moscow district and were presented as wood, charcoal, peat and food residue

ANALYSES OF NMR SPECTRA

• Analyses of the 1Н NMR spectra of the extracts studied is shown that in both cases are presented rather complicated chemical compounds. The comparison of the spectra of the food residue and carbon-containing materials of the pottery is testified that as in the food residue and in the pottery are presented the compounds with the double bonds, ethers, alcohols and fatty, besides in the solution the aromatics were discovered too.

• The relative content of these compound are more in the food residue than in the pottery itself: the total content the organic compound in the food residue in 40 times exceeded in the pottery clay mass one. According to the 1Н NMR spectra of the extracts in the food residue there are additionally the components which is rather difficult now to interpret. The extracts of the pottery is demonstrated the more relative high content of the ethers (δ=4.05 and 4.3) which can be related to the components of the vegetable waxes.

• The 13C spectra of the food residue and pottery differ visibly too. • If the spectra of the pottery extract during the accumulation for 10 hours was shown

only weak signals of the residual hexane and paraffin then the spectra of the food residue extract is very diversity and in which there are the signals related to the unsaturated compounds as in the 1H spectra..

• According to the results obtained one can assume that the organic-containing materials in the food residue and pottery itself have the same origin. Most probably, these materials penetrated in the pottery during the firing therefore the 14C dates from the pottery itself can be considered as reliable reflected the time of the pottery used. . But it is only preliminary results which will be continued.

1H NMR spectra of food residue and pottery

13C NMR spectra of food residue and pottery

SUMMARY of THE POTTERY STUDY

• The first attempts to study the origin of the organic-containing materials in the pottery were done used the Nuclear magnetic resonance.

• The results obtained were shown that the organic components both in the food residue and the pottery are practically the same but were differed by quantitatively.

• According to the first results one can assume that the 14C dates produced from carbon-containing materials from the pottery itself can be reflect the time of the pottery using as the food residue. This study will be continued late.

CONCLUSIONS� The classical theory views the European Neolithic as essentially resulting from the

spread of farming from Western Asia either by means of direct migrations or by absorption and acculturation of indigenous Mesolithic populations. In south-eastern Europe the earliest manifestations of agriculture are acknowledgeable at c. 8.6-7.5 kyr cal BC (Franchthi Cave).

� The above-cited new evidence indicates that early pottery making developed in the forest-steppe areas of East European Plain much earlier than first farming communities appeared in south-eastern Europe.

� The earliest signals of pottery-making are apparent in the North Caspian area, the Middle-Lower Volga (Yelshanian, c. 8-7 kyr cal BC) and the Lower Don (Rakushechnyi Yar; c. 7 kyr cal BC). The stable settlement as indicated by the coeval subsamples is acknowledgeable in the Middle-Lower Volga (Yelshanian) at 6.8 kyr cal BC, and in the Caspian Lowland and on the Lower Don at c. 6 kyr cal BC. Remarkably, in all studied areas, the early Neolithic coincided with the optimal environments of the Atlantic period, which included a notable increase of the rainfall, acknowledgeable in the radiocarbon-controlled pollen data.

� The reported evidence confirm the previously formulated model (Davison et al 2007), which suggests that the spread of the Neolithic involved at least two waves propagating from distinct centres, the western one stemming from the Near East, and the eastern one, spreading through the east via the ‘steppe corridor’, resulting in the establishment of the ‘eastern version’ of the Neolithic in Europe.

Thank you for your attention!