Recent Advances in Radiocarbon Dating Lime lumps embedded ... · CIV Age control, 79 samples No Age...
Transcript of Recent Advances in Radiocarbon Dating Lime lumps embedded ... · CIV Age control, 79 samples No Age...
Roman Pozzolana and mortar datingC: Applications
and experiments29 samples
CI
2 inconclusivesamples
CI-CII
19 conclusivesamples
CIV
7 samplesfulfill less secureCriteria III and IV
CIII
1 inconclusivesample
Secondfractionsagree in 12 samples from Trajan’sMarket and Ostia
B: No age controlA: Age control
0
100
200
300
400
500
600
1 2 3 4 5 6 7 8
1
2
3
4
5
6
7
8
All mor-tars
Limemor-tars
Pozzo-lana
Lime lumps
H3PO4 HCl Clas-sical
Diagram of all mortar samples analyzed
Type Hydrolysis Chronology
Medi-eval
This poster focuses on recent methodological development in dating mortar, exspecially on classical archaeology and the dating
of lime lumps embedded in the mortar
Mortar is not an organic material. Yet the chemical process in the hardening in principle makes it into an ideal matrix for 14C dating. To make mortar, limestone has to be heated up to at least 900 ºC. After the carbon dioxide has been released in the process, calcium oxide (un-slaked lime) is mixed with water and aggregate, usually sand. In the hardening process the slaked lime reacts with atmospheric carbon dioxide, and calcium carbonate is produced. Thus the mortar absorbs the carbon dioxide from the atmosphere and thereafter behaves as if it were organic. Unburned limestone in the mixture can contaminate the result, yielding dates too old.
Diagram displaying mortar samples analyzed. By now the databank covers results from more than 550 analyses of some 470 individual samples. Some of the samples were analyzed repeatedly, in different laboratories. The samples include different sorts of mortar, and they cover both Classical and Medieval archaeology.
Recent Advances in Radiocarbon Dating of Ancient Roman Mortar and Concrete
Lime lumps embedded in mortar
In the process mortar is more easily soluble than limestone, thussthe first fractions should be free from contamination. Therefore, to illustrate the entire dissolution process, the gas-flows interrupted at several stages create a sequence of CO2 age profiles. The contamination is shown towards the end of the profile.
21 3 4 5
5 CO2-fractions
0 100CO2 in the sample (%)
14C-
age
(BP)
To avoid the effects of contamination different types of separation are needed. At first a mechanical separation with gentle crushing of the sample. The grains are then sieved into 39/45-75 microns for further analysis. In the following chemical separation 85% of phosphoric acid is poured over the sample, creating a gas of carbon dioxide.
LIQUIDNITROGEN
CO2 FRACTIONS
COLD TRAP
SAMPLE
PRESSUREGAUGE
VACUUM PUMP
Åsa Ringbom, Åbo Akademi University, FinlandJohn R. Hale, University of Louisville, Kentucky
Torre delle Milizie, Rome, The result of Rome 007Li, (Li=lime lump) as compared to analysis of Rome 007 from different AMS laboratories (Aarhus, Denmark, Oxford UK, Tucson Arizona). The lime lump analysis supports our earlier interpretations - that the top of Torre delle Milizie was erected towards the end of the 13th century.
Santa Costanza, at Via Nomentana, Rome. The age of construction is debated. It was built as a mausoleum either by Constantina, daughter of Constantine the Great, before 350, or by her brother–in–law Julian the Apostate some 10-12 years later. Mortar samples were analyzed in Oxford, Tucson and Aarhus all forming confusing age profiles. The lime lump Rome 042 was analyzed twice, resulting in an almost horizontal age-profile, which is easy to interpret. But because the calibration curve wiggles at this point the result is not helpful enough in pinpointing the chronology. We can never defeat the irregularities of the calibration curve.
Conclusions: a) Medieval lime mortars in Scaandinavia and Classical mortars based on marble (Torre de Palma) have yielded promising results. b) Hydraulic Pozzolana mortars have been less successful.c) Pozzolana mortars from Pompeii and Herculaneum cannot be dated, regardless of whether bulk mortars or lime lumps embedded in the mortars are used. d) Lime lumps embedded in the mortar have shown a great deal of success, both in lime - and pozzolana mortars. Lime lumps generally contain very little contamination from unburnt limestone, thus fewer CO2 fractions are needed, thus cheaper. e) Above all, for pozzolana mortars analyzing lime lumps may be the obvious solution.
Why mortar? The aim of archaeological excavations is often to establish the chronology of a site. Mortar, lime mortar or pozzolana mortar, is often the only datable material available, in abundance, from all the different building stages. Differently from other datable materials like dendrochronology and 14C of organic materials, and differently from archaeological artifacts such as coins and ceramics, mortar analysis dates the actual time of the construction, or when the mortar hardened. It would therefore be helpful to use mortar dating on a routine basis in archaeological excavations or in a process of conservation.
The Roman Villa of Torre de Palma, Portugal, mortar analyzed in 1997-2000, was our first encounter with Classical archaeology. Out of a total of 64 samples analyzed 18 yielded Criterion I results. Independently of other materials and methods these 18 samples could indicate the date of 12 out of 21 structures, thus marking the outlines of the chronology of the site. The earliest structure was the temple in the East Court (70-170AD), and the latest are the apse 3 of the Basilica (580-630AD) and the large font of the Baptistery (570-690AD).
Reliability criteria for the interpretation of the age profiles
Criterion I: when analyzed in two to five CO2 fractions and the results from the two first CO2 fractions agree Criterion II: when there is mutual agreement between the dates of the first CO2 fractions in a seriesof three or more samples from one single building.Criterion I and II yield a conclusive date independently of age control.Dating medieval lime mortars in Scandinavia has
yielded promising results.More than 96% if all the results agree with age control from other dating methods, as shown from the Åland Islands between Finland and Sweden
Dating pozzolana mortars, however, was problematic. Only some 50% of all samples could be considered successful, and the interpretation of the CO2 age profiles was seen as complicated.
A Mortar Dating Workshop in Åland, 2006: Fiona Brock, John R. Hale, Jan Heinemeier, Åsa Ringbom, Alf Lindroos and Pia Sonck-Koota.
The International Mortar Dating Project 1994 - Map of mortar dating sites, those in red mark lime mortars, those in green pozzolana mortars.
200 4000 km
N
CII
Conclusive results 45
Inconclusive results 26
CI
Not agreeing 4
Mutually agreeing results 75
CII
CIII CIV
Age control, 79 samples No Age control, 71 samples
Dendro Och 14CW
14C W
Dendro and 14C W
Dendro CI
CI-CII
CII
CI-CII
CI
CIII, Too few samples per building- unit. Age- Profiles cannot be interpreted
The mortar dating group, Lynne Lancaster, Jan Heinemeier, Åsa Ringbom and Alf Lindroos outside the Colosseum, where successful results meet the demands of Criterion I and Criterion and II, and the calibrated result agrees with written sources.
1800
1900
2000
2100
2200
2300
2400
2500
2600
2700
2800
2900
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1F
C-14 age BP Colosseum
003, 76-150 m
001, 46-75 m
002, 46-75 m
Heavilycontaminated
No re-crystallizationFirst fractions convergeand are correct
Atmospheric data from Reimer et al (2004);OxCal v3.10 Bronk Ramsey (2005); cub r:5 sd:12 prob usp[chron]
200CalBC 100CalBC CalBC/CalAD 100CalAD 200CalAD 300CalAD
Calibrated date
1800BP
1900BP
2000BP
2100BP
noitanimreted nobracoida
R
The Colosseum : 1940±17BP 68.2% probability 25AD (13.4%) 40AD 45AD (54.8%) 80AD 95.4% probability 10AD (86.5%) 90AD 100AD ( 8.9%) 130AD
Why lime lumps?
Lime lumps embedded in the mortar are highly interesting in this context. There may still be clods of quicklime in the putty, which become slaked and carbonated possibly already before the aggregate is added. These form aggregate free white lumps in the mortar. In principle therefore well-burnt lime lumps should be free from contamination.
CO2 CaCO3limestone
CaOunslaked lime
Ca(OH)2slaked lime
+ H2Owatercarbon-
dioxide
Statistics of results from 32 liumps embedded in the mortar. 25 lime lumps were identified in lime mortars, whereas 7 were embedded in pozzolana mortars. Of these 32 samples, 7 had been exposed to fire. The majority comes from medieval Scandinavia.
0
5
10
15
20
25
30
35
40
1 2 3 4 5 6 7
1
2
3
4
5
6
7
All limelumps
successrate
Nordicmedieval
Classical Pozzo-lanaRome
Pozzolana Pompeii
Torre dePalma
Current statistics of lime lumps
Terracina, Temple of Anxur. Repeated analysis of a bulk sample of pozzolana mortar (Terracina 001)resulted in two different looking age profiles, which seemed to converge at the first CO2 fractions. A lime lump embedded in the pozzolana confirmed the earlier interpretation.
500
700
900
1100
1300
1500
1700
1900
2100
2300
2500
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1
C-1
4 ag
e B
P
F
Rome, Torre delle Milizie
Oxford 76-150 m H3PO4
Sample Rome 007
Tucson 46-75 m H3PO4
Tucson 46-75 m HCl
ÅrhusLime lump 21-150μmH3PO4
Århus 46-75μm H3PO4
CO2CaCO3
CaO Ca(OH)2 +sand
+ H2O+ H2O
14CO2from atmosphere
Samples from Pompeii or
Herculaneum
Delayed hardening
Experiments
Crushed brickssec. opus floors
Too few fractions analyzed
Re-crystallization
with old layersof stuccho
200
45-80
10-22
6-3
Atmospheric data from Reimer et al (2004);OxCal v3.10 Bronk Ramsey (2005); cub r:5 sd:12 prob usp[chron]
Torre de Palma - Dates based on agreement between 1st and 2nd fractions in CO2
600BC 400BC 200BC BC/AD 200AD 400AD 600AD 800AD
Calibrated date
The Temple in East CourtAAR-3933 TP 108 Cat1 1885±35BP South Field WestAAR-5441 TP 186 1683±45BPAAR-5442 TP 188 1750±45BP south west houseAAR-3929 TP 069 1711±35BP The Baptistery, earlier structureAAR-10361 TP 013 1684±35BPAAR-3411 TP 201 1738±55BP Precinct wall AAR-5440 TP 182 1601±35BP The Olive PressAAR-4231-2 TP 083-2 1628±55BP The Basilica, phase 2AAR-3926 TP 023 1535±30BPAAR-4825 TP 143 1554±20BP Basilica, Apse 4AAR-5653 TP 209 1483±30BP North East House AAR-5428 TP 045 1543±35BPAAR-5643-1 TP 178-2 1515±45BP MaosoleumAAR-4228 TP 036-2 1576±45BP Basilica, Apse 3AAR-3927 TP 025 1410±35BPAAR-3928 TP 026 1448±30BPAAR-3414 TP 206 1417±30BP Babtistery, large font, second stageAAR-4822-3 TP 138-3 1393±40BP
North Barn
SOUTH F IELD WEST
Southwest Cemetery
(CW R)
Northwest CemeteryBASILICA
NORTHEAST BUILDING
Garden Quarter
Peristyle House
East Bath
Forge
Atrium House
East Court
South Hall
West Court
GateGate
Gate
Olive Press
Portico House
West Bath
Southwest House A
Southwest House B
(COMPLEX B)
(COMPLEX C)
(COMPLEX R)
South Field
TORRE DE PALMA
Location of Studies Samples
2325
26
1013
138
1434
182
10 m
209
144,219
145
211
147
175
32199139
TORRE DE PALMABasilica (Complex B)Criterion I (black)Criterion II (red)
17
144,1
1800
2000
2200
2400
2600
2800
3000
0 0,2 0,4 0,6 0,8 1
Terracina, temple of Jupiter Anxur
001; 46-75µm001Li; 21-150μm
F
Sample 001
Lime lumpH3PO4, Århus
Bulk mortars
14C
age
BP H3PO4 (Århus)
HCl (Tucson, Arizona)
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1
St Costanza, RomeC-14 age BP
F
Samples
Rome 042Rome 017
Rome 04646-75µm fractionsRome 042Li21-75 and 76-150μm (1 fraction; 3 fractions)
046
017
042
Lumps: 1716 15320-390 (42,6% 1σ)
+/-
Terracina 001Li R_Date(1909,35)95.4% probability
19 (95.4%) 214calAD
200 100 1calBC/1calAD 101 201 301 401
Calibrated date (calBC/calAD)
1600
1800
2000
2200
Rad
ioca
rbon
det
erm
inat
ion
(BP
)
OxCal v4.1.7 Bronk Ramsey (2010); r:5; Atmospheric data from Reimer et al (2009);