www.luomus.fi
Research applications of stable and radioactive
isotopes
Dr (PhD) Markku Oinonen
Unit Director, adjunct professor
Natural Sciences Unit / Laboratory of Chronology
Finnish Museum of Natural History
University of Helsinki
www.luomus.fi
Finnish Museum of Natural HistoryFirst step towards nature
Exhibitions at Pohjoinen
Rautatienkatu 17, Helsinki
4 units: Zoology, Botany, Natural
Sciences, General Services
Natural Sciences Unit:
Laboratory of Chronology
Geological Museum
Personnel: ~15
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
LHC
ALICE
2002-2006
14C,
TL/OSL
2007-
JYFL, CERN
1992-2001
Time travellingwith various methods…
JYFL, CERN
LHC/ALICE
Presently: Quantifying the last
100 000 years by radiocarbon
measurements, Luminescence
dating, Stable isotope ratios
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Contents
1. Hour:
• Cosmogenic nuclei and stable isotopes
• Methodologies: IRMS, AMS
• Basics of decay and accumulation clocks
• Radiocarbon dating, basics
2. Hour:
• Radiocarbon dating continues
• Past: Archaeological and multidisciplinary studies in chronological order
• Present (and future): Environmental applications (Greenhouse gas studies,Biofraction measurements)
www.luomus.fi
Both radioactive and stableisotopes matter
Background radioactivities of
Earth have been (and are)
produced throughout the history
of the Universe
Cosmogenic nuclei are
produced by cosmic ray
bombardment (e.g. 14C)
All radioactive nuclei eventually
decay to stable ones from which
the Earth and its spheres mostly
consist of
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Cosmic raysBehind cosmogenic nuclei
http://photojournal.jpl.nasa.gov/jpeg/PIA16938.jpg,
https://commons.wikimedia.org/wiki/File%3AStructure_of_the_magnetosphere-en.svg, Masarik and Beer 2009
Magnetic field lines (strength) at polar regions allow easier entry of CR’s
into atmosphere (vertical cut-off rigidity)
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Production of cosmogenic nucleiTrace elements to study past
https://commons.wikimedia.org/wiki/File:Atmospheric_Collision.svg
https://commons.wikimedia.org/wiki/File%3AProtonshower.jpg
Secondary particles cause nuclear
reactions → cosmogenic nuclei,
such as 14C, 10Be, are produced
These enter into elemental cycles
of the Earth, 14C as 14CO2
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Stable isotopesMass-dependent effects
Quantum mechanics: Isotopic mass affects the energy levels, strength of
chemical bonds, and vibrational, rotational and translational motion of
atoms/molecules
Mass-dependent effects on isotopic concentrations: larger for light
elements
isotope1 isotope2 m1 m2 mass difference m2-m1(%)
H D 1 2 100,0
12C 13C 12 13 8,3
14N 15N 14 15 7,1
16O 18O 16 18 12,5
see http://www.geo.cornell.edu/geology/classes/Geo656/656notes03/
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi 23.2.2017 9
Stable isotope ratiosMass-dependent effects
http://pubs.usgs.gov/of/2001/ofr01-257/images/figure1.gif
Hoefs J 1987. Stable Isotope Geochemistry. Springer-
Verlag Berlin – Heidelberg – New York, ISBN 3-540-
173141-2
→ lighter molecules break-up easier
→ lighter isotopes favoured in reactions
Lighter isotopes/molecules more mobile
Mass-dependent (process &
temperature!) effects on isotopic
concentrations
Carbonates: d13C ~0 ‰
Atm CO2: d13C ~ -8 ‰
Wood cellulose: d13C ~ -25 ‰
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Mass Spectrometry (MS) ja Accelerator Mass Spectrometry (AMS)
Negative ions
with Cs sputtering
Analysis by
momentum
ME/q2
Acceleration to
strip the ions
to positive
Analysis by
momentum
ME/q2
Analysis by
energy
E/q
Ion
identification
Stable isotope ratios
(IRMS for e.g. 13C/12C) or abundant
radioactive isotopes
Cosmogenic
(trace) isotope
ratios
(e.g. 14C/13C)
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi 11
”The cause must be prior to the effect” Essence of Chronological Analyses
Chronological methods
provide fundamental means
to assess order of events
Spectra of natural events,
cultural phases, most
probable event sequences
Foundation for discussing
causes and effects
Hume D 1740; Bronk-Ramsey C 2009. Bayesian analysis of radiocarbon dates. Radiocarbon 51(1): 337-60.
Oinonen M, Pesonen P, Onkamo P et al 2014. Event reconstruction through Bayesian chronology: Massive mid-Holocene
lake-burst triggered large-scale ecological and cultural change. Holocene 24(11): 1419-1427.
-4000 -3900 -3800 -3700
0,00
0,01
0,02
0,03
0,04
cale
ndar
year
pro
babili
ty
year (cal BC)
Vuoksi breakthrough
Early Asbestos Ware ends
Typical Comb Ware starts
Lake Saimaa region
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Datings without radioisotopes
1) Dendrochronology
1 year accuracy, >50 tree rings, even 12460 years (Friedrich et al 2004. Radiocarbon 46, 1111–1122.),
2) Varve counting
Sediment- and ice layers, may reach 1 year accuracy
3) Paleomagnetic datings
Sediment layers with magnetic particles: alignmentaccording to contemporaneus magnetic field lines
4) Lichenometry
Growth of lichen on rock surfaces
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Datings with radioisotopes
Exploiting the background radiation in total:
Luminescence dating
Exploiting the fallout due to nature, nuclear tests and Chernobyl:137Cs, 210Pb dating
Exploiting in-situ production:
Surface-exposure dating
Exploiting the decay characteristics:
Radiometric datings
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Radiometric datingsgeneral
Decay clock
Time can be determined by counting
what is left ↔ parent atoms left after
radioactive decay
OR
Accumulation clock
By combining it to what is
accumulated ↔ ratio of parent
atoms left and daughter atoms
accumulated after radioactive decay
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
decay clocks:
accumulation clocks:
Radiometric datingsfundamental equations
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Decay clocks: no exchange of parent
isotope within environment after sample
formation
e.g. death of an animal causes a system
closure: the exchange of 14C with the
environment is ceased
Accumulation clocks: no exchange of
parent or daughter isotope within
environment after sample formation
e.g. cooling of volcanic rock causes a
system closure: no 40Ar diffused out after40K decay
Dating of system closurespreconditions
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Radiocarbon methodologyHistory
1949: Arnold, J. R.; Libby, W. F. 1949. Age Determinations by
Radiocarbon Content: Checks with Samples of Known Age. Science
110 (2869): 678–680 - Nobel Prize of chemistry for Libby in 1960
1st 14C revolution 1950-1970: scientific chronologies to parallel
historical
2nd 14C revolution 1967→: calibration due to changes in atm 14C
content
1977 →: Accelerator Mass Spectrometry (AMS), formerly b counting(Purser et al 1977, Bennett et al 1977)
1990s →: Utilization of Bayesian chronological models
Markku Oinonen / Physics Days 2014
www.luomus.fi
Photosynthesis samples carbon14C (and 13, 12C) from atmosphere to plants and animals
Cosmic rays produce 14C in
atmosphere via nuclear
reaction:
1nspall + 14N → 14C + 1H
14C (and 13, 12C) ends up to
plants and animals via
photosynthesis and food
chain
14C concentration equals to
contemporary atmospheric
one
Graphic: H.Bonner, Design: M. Oinonen for
Elämän Historia-exhibition / LUOMUS
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Radiocarbon methodOnce upon a time during Stone Age...
Half of the radiocarbon is
left after 5730 years
Carbon exchange may
stop at some moment...
Graphic: H.Bonner, Design: M. Oinonen for
Elämän Historia-exhibition / LUOMUS
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Radiocarbon methodOnce upon a time at present…
An archaeologist finds the
human remains
Hopefully he/she is
scientifically oriented…
Graphic: H.Bonner, Design: M. Oinonen for
Elämän Historia-exhibition / LUOMUS
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
The sample goes through multiple
phases in the laboratory:
1) Cleaning
2) Chemical pretreatment
3) Combustion/acid release → CO2
4) 13C/12C measurement (d13C)
5) Reduction → C
6) Packing
7) 14C measurement by AMS
8) Result analysis
Eventually, the sample quantified as
a number
Radiocarbon methodA little later in the laboratory
Graphic:
H.Bonner
Design:
M. Oinonen
for Elämän
Historia-exhibition
at LUOMUS
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Basic principlesStuiver M & Polach H 1977. Radiocarbon 19(3):pp. 355-363.
1) a half-life of 5568 years i.e. λ = 8033 yr-1 (not true!);
2) the assumption that all 14C reservoirs have remained constant
through time (not true!);
3) the use of Oxalic acid I or II or appropriate secondary radiocarbon
standards as the modern radiocarbon standard;
4) correction for sample isotopic fractionation (d13C) to a value of -25.0
per mille relative to the ratio of 12C/13C in the carbonate standard
VPDB;
5) the use of 1950 AD as year 0
→ Measure 14C content (Pt , AMS: 14C/13C ratio) with respect to the year
1950 standard (P0) → radiocarbon age t in units of BP i.e. before
present
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Curve deduced by
measuring 14C contents of
tree rings with 5-10 year
time difference
The radiocarbon age and its
statistical distribution
reflected to calendar year
axis via the curve
Calendar year probability
distribution
23
Reimer P J et al. 2009. IntCal09 and Marine09 Radiocarbon Age Calibration Curves, 0–50,000 Years cal BP.
Radiocarbon 51: pp. 1111-1150.
Bronk Ramsey C 2009. Bayesian analysis of radiocarbon dates. Radiocarbon 51(1): pp. 337-360.
Calibration to calendar yearsCalibration curve
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi 24
Beauty of Bayesian methodsBayes T and Price R 1763. An Essay towards solving a Problem in the Doctrine of Chance. By the late
Rev. Mr. Bayes, communicated by Mr. Price, in a letter to John Canton, A. M. F. R. S.. Philosophical Transactions of the Royal Society of London 53 (0): 370-418.
Priof beliefs are updated in light of new information…
Is that what all the scientists do every day?
When a scientist is performing research, she/he is frequently ”updating
her/his prior beliefs”
Bayesian principle converts the qualitative thinking to be
quantitative
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
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Calibration to calendar yearsBayesian analysis
Buck C E, Cavanagh W G, Litton C 1996. Bayesian Approach to Interpreting Archaeological Data. Wiley & Sons Ltd.
ISBN 978-0-471-96197-0.
Bronk Ramsey C 2009. Bayesian analysis of radiocarbon dates. Radiocarbon 51(1): pp. 337-360.
Radiocarbon age (x) converts a priori (uniform) calendar year probability
distribution p(θ) to a posteriori calendar year probability distribution p(θ|x)
posterior:
”result”prior:
”archaeology”
likelihood:
”dates and calibration”
25Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Bayesian chronological modelsBronk Ramsey C 2009. Bayesian analysis of radiocarbon dates.
Radiocarbon 51(1): pp. 337-360.
26
Ordering and time difference of events can be integrated within
Bayesian framework (e.g Oxcal software)
Forms calendar year probability distributions based on ANY
chronological information (14C, luminescence dating, tree-ring data,
historical data etc)
Provides versatile means to quantitatively assess timing of events,
beginnings and ends of cultural phases
Another 14C revolution…
Yields to time spectra of events, layers and phases
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Climatic reconstructions: pollen14C provides the timeline (50 years)
Pollen-based climatic
reconstructions use 14C data to
define timeline
Warm phase of Holocene
Climatic Optimum around 8000
– 3500 cal BC
Observed throughout the
Northern Hemisphere
Heikkilä M, Seppä H (2003) A 11 000 yr palaeotemperature reconstruction from the southern boreal zone in Finland, Quat Sci Rev
22:541–554.
-10000 -8000 -6000 -4000 -2000 0 20000
2
4
6
8
ann
ua
l m
ean
T(C
)
year (cal BC/AD)
◦ ◦ ◦
Holocene climatic optimum
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Temporal distribution of 14C dates14C in Eastern Fennoscandian archaeology
2588 archaeological dates
summed as a function of time
Maximum at ~5000 BP coincides
with the warm phase of the
Holocene period
Mostly due to spread of innovative
and expansive Typical Comb Ware
culture
Triggered by Lake Saimaa
discharge through Vuoksi river? Tallavaara M, Pesonen P, Oinonen M 2010. Prehistoric population
history in eastern Fennoscandia, Journal of Archaeological
Science 37: pp. 251-260.
Oinonen M, Pesonen P, Tallavaara M 2010. Archaeological radiocarbon dates for studying the
population history in eastern Fennoscandia, Radiocarbon 52: pp. 393-407
10000 8000 6000 4000 2000
0
5
10
15
20
25
30
35
40
45
50
Holocene Climatic Optimum
nu
mb
er
of
14C
da
tes/5
0 y
ea
rs
radiocarbon age (BP)
Reproduced from Oinonen et
al 2010. Radiocarbon 52:393-407.
Lake Saimaa discharge i.e.
Vuoksi breakthrough
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi 23.2.2017 29
Vuoksi breakthroughInteraction between Nature and Man
Ancient Lake Saimaa bursted through
a ridge around 6000 years ago and its
waters started to flow towards Lake
Ladoga
Water level dropped 4 meters and
revealed thousands of km2 residual
wetlands
Nearly the same time, the most
important eastern Fennoscandian
culture arrives and old one ends
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi 23.2.2017 30
Vuoksi breakthroughInteraction between Nature and Man
Vuoksi burrowed into the soil and rock of Salpausselkä ridge
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi 31
Archaeological cultures at easternFinland c. 6000 years ago
EAW, Early Asbestos Ware ~4600 calBC
onwards
• Using asbestos(!) in clay matrix
• Thinner, Heat resistance?
TCW, Typical Comb Ware ~3800 calBC
onwards
• Clear changes in archaeological material
(pottery changes, red ochre graves, pit
houses, flint, amber, copper)
• Possibly the most influential culture in
eastern Fennoscandian Stone Age
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi 32
Radiocarbon dates (N = 61):
1. 14C dates of settlements above the highest shoreline of
transgressed ancient Lake Saimaa or below Vuoksi floodplain
→ pre-Vuoksi
2. 14C dates of settlements below the highest shoreline on the
residual wetlands or above the Vuoksi floodplain → post-
Vuoksi
Model: Vuoksi event dating (VB) as calendar year probability
distribution of a Boundary (in Oxcal language) between pre-Vuoksi and
post-Vuoksi dates
Chronological modelVuoksi breakthrough
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
-4000 -3900 -3800 -3700
0,00
0,01
0,02
0,03
0,04
ca
lend
ar
yea
r p
roba
bili
ty
year (cal BC)
Vuoksi breakthrough
Early Asbestos Ware ends
Typical Comb Ware starts
23.2.2017 33
Sequence P1 P2 P3 P4
VB > eEAW > sTCW 0.380 0.331 0.343 0.294
VB > sTCW > eEAW 0.237 0.337 0.279 0.441
eEAW > VB > sTCW 0.220 0.168 0.192 0.129
sTCW > eEAW > VB 0.077 0.084 0.084 0.078
sTCW > VB > eEAW 0.044 0.047 0.055 0.038
eEAW > sTCW > VB 0.042 0.033 0.046 0.020
Vuoksi breakthroughInteraction between Nature and Man
Vuoksi and cultural events
dated with 118 14C dates
Bayesian model allows for
estimating the most probable
order of events
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi 23.2.2017 34
Vuoksi breakthroughAmount of moose bone finds
Archaeology &
Osteology:
Amount of moose bone
finds increase by factor
of 2-5 during the post-
Vuoksi Typical Comb
Ware culture
Moose population
supported the human
population increase
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi 23.2.2017 35
Chronology → Causes and effects
Nearly inevitable on revealed lands:
1)Pioneer vegetation occupies the land →
2) Fauna (such as moose) takes advantage on increased
resources →
3) People occupy the land and take advantage of large prey
The environmental catastrophy was mediating the cultural change
Chronology (within multidisciplinary effort) allows for
reconstructing Causes and Effects
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Details of human timeline14C in Eastern Fennoscandian archaeology
Holocene Climatic
Optimum and Vuoksi both
contributed in shaping the
human timeline
DNA studies: genetic
bottleneck at around 3600
BP: we see a minimum
Rise of the signal coincides
with start of Bronze Age at
3200 BP
What about agriculture? Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
10000 8000 6000 4000 2000
0
5
10
15
20
25
30
35
40
45
50
Holocene Climatic Optimum
Bottleneck 3600 BP
Bronze Age 3200 BP
Agriculture starts?
Vuoksi breakthrough
num
ber
of
14C
date
s/5
0 y
ea
rs
radiocarbon age (BP)
Reproduced from Oinonen et
al 2010. Radiocarbon 52:393-407.
www.luomus.fi
Role of agriculture14C in Eastern Fennoscandian archaeology
Datings of cereal pollen have been
summed to form calendar year
probability distribution (c)
Archaeological (b) and agricultural
signal (c) correlate with R = 0.87-
0.98
Advance of agriculture
explains the increase of
human population
Lahtinen M, Oinonen M et al 2016. Published online before
print August 8, 2016 in The Holocene.
doi:10.1177/0959683616660164.
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
-2500 -2000 -1500 -1000 -500 0 500 1000 1500
0,0
0,1
0,2
-2500 -2000 -1500 -1000 -500 0 500 1000 1500
0,0
0,1
0,2
-2500 -2000 -1500 -1000 -500 0 500 1000 1500
0,00
0,04
0,08
0,12
-2500 -2000 -1500 -1000 -500 0 500 1000 1500
-1
0
1
2
3
4
c) Pollen
d) PC1
b) Archaeological
a) Artificial
ave.
sum
med
cal
enda
r ye
ar p
roba
bilit
y
ave.
PC
1 sc
ore
year (BC / AD)
www.luomus.fi 23.2.2017 38
Kivutkalns (Kivilinna) at Väinä riverFollowing the footsteps of Väinämöinen(’s mother)
Kivutkalns
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
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Kivutkalns (Kivilinna) at Dvina riverFollowing the footsteps of Väinämöinen’s mother?
Oinonen M, Vasks, A., Zarina, G. & Lavento, M 2013. STONES, BONES
AND HILLFORT – RADIOCARBON DATING OF ĶIVUTKALNS BRONZE-
WORKING CENTRE. Radiocarbon 55: 1252-1264 and M.Oinonen et al to
be published
Cemetery (200 humans) and
hillfort at the same 2500
year old Bronze Age site
C, N isotopes: Mostly
terrestrial diets (e.g.
agriculture)
Very narrow time and dietary
distribution makes
wondering whether deaths
were contemporaneous
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Combining 14C and ancient DNABronze-Age cemetery in river Dvina, Latvia, 2500 BP
14C makes timeline of
phylogenetic trees (DNA
analyses) factor of 10 more
accurate compared to
molecular clock
Genetic continuity to
modern Latvians and other
populations around the
Baltic Sea, including Finns
Dvina river and Baltic Sea
has been a genetic highwayYears (cal BP)
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Timeline nearly reconstructed14C in Eastern Fennoscandian archaeology
The human timeline in
Eastern Fennoscandia starts
to be grossly reconstructed
1500 years ago there is a
sudden drop in human
activity
Fimbulvinter of Nordic
Sagas?
→
Ask trees…Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
10000 8000 6000 4000 2000
0
5
10
15
20
25
30
35
40
45
50
Holocene Climatic Optimum
Bottleneck 3600 BP
Bronze Age 3200 BP
Agriculture starts
Vuoksi breakthrough
nu
mb
er
of
14C
da
tes/5
0 y
ea
rs
radiocarbon age (BP)
Reproduced from Oinonen et
al 2010. Radiocarbon 52:393-407. Fimbulvinter?
www.luomus.fi
Carbon isotopes in tree (C3-plants)Stable isotopes
1. Carbon dioxide of air
currently yields a δ13C value
of about -8 ‰
2. Fractionation due to
diffusion is -4.4‰
3. Fractionation when internal CO2 is
utilised by the photosynthetic enzyme
4. Further fractionations yielding
lower δ13C values when leaf
sugars are used to make
cellulose and lignin
→ δ13C ~ -25 ‰.
CO2
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi 23.2.2017 43
Sample material: subfossil pine (Pinus sylvestris) trees
from Finnish Lapland (close to auroral oval!)
Lakes Hattulompolo, Pitkäjärvi, Luolajärvi, Kompsiojärvi,
Namatesjärvi ja Juomusjärvi
-26
-25
-25
-24
-24
-23
1900 1920 1940 1960 1980 2000
δ13C‰
8
9
10
11
12
13
14
15
16
17
Te
mp
era
ture
°C
δ13C corrected
Jul-Aug T
Use 7500 –year long tree-ring series to study carbon stable isotopic ratios
(d13C) in tree rings for multiproxy climatic reconstruction record
environmental conditions:
Isotopes in climatic reconstructionsCARATE consortium, funded by Academy of Finland
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
CARATE consortiumHard work of pulling, sawing, cutting, cooking,
weighing, measuring x 21000, analysing, writing…
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
CARATE results
Our calibration data from the
last century:
Tree-ring carbon isotopic ratios
(d13C) in Lapland correlate
strongly (R ~ 0.6-0.7) with
measured Sunshine hours and
Global radiation i.e. Light
Towards understanding the
long chronology…
Helama S., Arppe L., Uusitalo J., Mäkelä H.M., Oinonen
M. & Mielikäinen K. 2016. Agricultural and Forest
Meteorology. DOI: 10.1016/j.agrformet.2016.06.005. Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
”Mystery cloud” of 536-537ADHistorical evidence
”the sun was dark and its darkness lasted for eighteen months…light was
only a feeble shadow”
John of Ephesos on Mesopotamia
”…the air is dense of rising moisture – as happened…for a nearly a
whole year as Belisarius held the consular office…”
John Lydos on Constantinople
Fimbulvinter of 3 years in Nordic sagas, ”one lived without Sun, without
Moon…” in Finnish folklore
after Rampino et al 1988. Ann. Rev. Earth Planet. Sci 16: 73-99; Keys, D P 2000. Catastrophe: an investigation into the
origins of the modern world. ISBN 0-345-40876-4.; Gräslund, B. & Price, N. 2012. Antiquity 86: 428-443.; Arjava A 2005.
Dumbarton Oak Papers 59: 73-94.; SKVR search 11/2013, http://dbgw.finlit.fi/skvr/.
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Climate anomaly of 536-542 ADCARATE case study on volcanic or extraterrestrial origin
Cold period of several years in
536 - 542AD based on tree-
ring widths: real Fimbulvinter?
Anomaly seen throughout the
northern Hemisphere
A multi-proxy analysis based on
tree-ring widths, d13C values
and 14C data400 500 600 700
10
15
20
542 AD536 AD
Ju
ly m
ean
te
mp
era
ture
(C
)
year (cal AD)
535 AD
Baillie M.G.L.(1994) Dendrochronology raises question about the nature of the AD 536 dust veil event. Holocene 4:212-217.
Larsen, L. B., et al. (2008) New ice core evidence for a volcanic cause of the A.D. 536 dust veil, Geophys. Res. Lett., 35, L04708,
Helama S., Macias Fauria M., Mielikäinen K., Timonen M. & Eronen M. 2010: Sub-Milankovitch solar forcing of past climates: mid
and late Holocene perspectives. Geological Society of America Bulletin 122 (11/12): 1981-1988.
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Tree-rings record the climate anomalyd13C, d14C and ring-widths from Lapland
520 525 530 535 540 545 550 555 560 565 570
-30
-28
-26
-24
-22
-20
d13C
(‰)
year(AD)
CA02
530 535 540 545 550
8
12
16
20
530 535 540 545 550
-28
-27
-26
-25
-24
-23
-22
530 535 540 545 550
-32
-28
-24
-20
-16
-12
T(°
C)
reconstructed TJuly
d13C
(‰)
average d13
CCA01-CA03
d14C
(‰)
year(AD)
radiocarbon concentration
Helama, Arppe, Mielikäinen, Uusitalo and Oinonen
2016. To be published
d13C (and d14C) sensitive to PAR (Loader et
al 2013. QSR 62: 97-113) → consistent with light
intensity loss due to the cloud → primary
productivity of the Past?Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Cyclic d13C records11-year solar cycle and North Atlantic Oscillation
Ogurtsov M, Sonninen E, Hilasvuori E, Koudriavtsev I, Dergachev V, Jungner H 2011. Variations in tree ring stable
isotope records from northern Finland and their possible connection to solar activity. Journal of Atmospheric and Solar -
Terrestrial Physics 73(2-3): 383-387. http://dx.doi.org/10.1016/j.jastp.2010.02.020; this work
0,0 0,1 0,2 0,3 0,4 0,5 0,6
0,00
0,02
0,04
0,06
0,08
0,10
3.6 yr, NAO
Frequency
Pow
er
density
10.5 yr
CARATE calibration data 1800-1950, CA14 Stable carbon isotopic spectra
reveal also cyclic behavior
3.6 year → NAO
10.5 year → 11-yr solar cycle
Isotopic signals contains
multitude of
environmental information
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
14C provides activity of the Sundendrochronology provides the timeline (5-10 years)
If Sun is active, the
interplanetary magnetic
field between the Sun and
Earth is strong
This bends the galactic
cosmic rays from the
atmosphere → 14C content
decreases
Little Ice Age is opposite:
low activity of Sun implied
high 14C production
1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000
-30
-20
-10
0
10
20
30
40
50
Wolf minimum
Spörer minimum
14C
(‰)
years (cal AD)
Reimer P J et al. 2004.
IntCal04 terrestrial radiocarbon age calibration, 0-26 cal kyr BP.
Radiocarbon 46: pp. 1029-1058.
Maunder minimum
Little Ice Age
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Drastic increase of 14C in AD775 Sun, supernova or comet?
Drastic increase of 14C in
tree rings at AD775 was
recently found in Japan
Proposed origin of the
event: Sun, supernova g
rays, cometary impact
If Sun is to blame, there
should be latitudinal
dependence since vertical
cutoff rigidity769 770 771 772 773 774 775 776 777 778 779 780
-30
-20
-10
0
10
14C
(‰)
year(AD)Miyake F et al. 2012. Nature, 486, pp. 240–242.
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
775 AD anomaly in Arctic treesPolar enhancement?
Miyake F et al. 2012. Nature, 486, pp. 240–242. Uusitalo J, MSc thesis 2016.
Our data: visible in Arctic
tree-rings with significantly
higher intensity: polar
enhancement of the signal
confirmed
Event strength clearly larger
than the largest Solar Proton
Event of historical era →
significant consequences on
present day societies, if
again
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Estimating the origin of carbon Human bone collagen d13C & d15N
23.2.2017 53
Öland: Eriksson G et al 2008. Journal of Anthropological Archaeology 27: 520–543; Östergötland: Lindberg T 2009. Master thesis
The Archaeological Research Laboratory 2009 Stockholm University; Sigtuna: Kjellström A et al 2009. Journal of Archaeological
Science 36: 2689–2699; Gotland: Kosiba S et al 2007. Journal of Anthropological Archaeology 26: 394–411.
Carbon and nitrogen stable
isotope ratios stored in
human bones provide means
to model diets of individuals
-30 -28 -26 -24 -22 -20 -18 -16 -14 -12 -10
2
4
6
8
10
12
14
16
18
20
22
TERRESTRIAL
FRESHWATER
d15N
(‰)
d13
C(‰)
Smörkullen, Östergötland
Sigtuna, Sweden
Zvejnieki, Latvia
Ridanas, Gotland
Köpingsvik, Öland
Västerbjers, Gotland
MARINE
Kivutkalns individual
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Reservoir effect correctionsFuture finetuning of 14C datings
23.2.2017 54
Fernandes R et al 2014. Plos One
If an individual has obtained
carbon from other reserve
than atmosphere (aquatic
sources), the conversion to
calendar years based on
atmospheric data does not
hold
Dietary modelling provide
means to correct the 14C
dates
Boosted during the recent
years only → gain more
importance in the future
Kivutkalns individual
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi 23.2.2017 55
Present (and future) environment and 14C
12C - 98.89%, 13C - 1.11% 14C -0.00000000010%
Circulation of carbon
within Earth defines
our future
Release of carbon
storages to
atmosphere increase
the amount of
greenhouse gases,
such as CO2 and CH4
14C (and 13C, 12C)
provides access to
characterize these
flows
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Carbon sinks at Amazonas Past 14C for the future
O.Lähteenoja, K.Ruokolainen, L.Schulman, M.Oinonen 2009. Amazonian peatlands: an ignored C sink and
potential source. Global Change Biology 15: 2311–2320.
Carbon sinks exists in Amazonas and the peatlands larger than previously
thought: deforestation would result in huge C load into atmosphere
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Soil carbon decompositionto CO2
Carbon sinks and sources
Molecular sieve methodology developed for
universal sampling of CO2 (Hämäläinen et al
2009, Palonen&Oinonen 2013): presently the best
approach worldwide
14C due to atmospheric nuclear tests used
as timemark for soil carbon fractions
Different soil fractions react differently
against global warming: should be taken
into account in climate models
Palonen, V, Oinonen, M 2013. Molecular Sieves in 14CO2 Sampling and Handling. Radiocarbon 55: 416-420 and Yle Prisma
9.2.2010 and Karhu K et al 2010. Temperature sensitivity of soil carbon fractions in boreal forest soil. Ecology 91(2): 370-376
and Hilasvuori, E et al 2013. Temperature sensitivity of decomposition in a peat profile. Soil Biology & Biochemistry 67: 47-
54.
1950 1960 1970 1980 1990 2000 2010
1,0
1,2
1,4
1,6
1,8
2,0
2,2
Fra
ctio
n m
od
ern
Calendar year
Levin I and Kromer B. 2004. Radiocarbon 46:pp.1261-1272
Radiocarbon content in the atmosphere as fraction modern FM
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Since half-life of 14C is 5730
years, fossil material does
not contain 14C anymore
Oldest measurable samples
are typically ~50 000 years
old
Modern biogenic material
has the present atmospheric
concentration of 14C
58
Fossils do not contain 14C…but biogenics do
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Bio/fossil –ratio measurements14C applications for our future
Oinonen M et al 2010, Hämäläinen K et al 2007, ASTM D6866-12, Supported by TEKES (Biocarbon
1,2; CO2-SERVICE, BioMonitor)
After periods of a) 200 000 years(!) of bioeconomy and b) 300 years of
fossil economy, society is turning back to bioeconomy in its attempt to
replace fossil materials by biogenic ones
“There exists an unequivocal method for distinguishing between carbonaceous
material arising from biological sources and that from fossil fuels such as coal,
oil, and natural gas. This method is based on the carbon-14 content of the living
materials.” Clayton G D, Arnold J R, Patty F A 1955. Science 122: pp. 751-753
14C content of fossil material is ~0 → if 14C content of biobased material
is known, the biobased fraction can be determined by measuring the 14C
concentration
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Liquid fuel biofractionmeasurements
Future of the Earth
Methods to measure bio/fossil
fuel ratios from liquid fuels and
flue gases(Oinonen M et al 2010, Hämäläinen K et al 2007)
Beyond the standardization:
faster, more reproducible and
more user-friendly compared
to standard methods(ASTM D6866-12)
0 5 10 15 20 25 30
0
5
10
15
20
25
30
0
5
10
15
20
25
30
Me
asu
red
bio
-%, C
TC
Weighed bio-%
R2 = 0.999
= 0.11
R2 = 0.999
= 0.15
CTC
Me
asu
red
bio
-%, E
A
EA
Fraction of biogenic carbon can be determined by measuring amount
of 14C
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Gaseous fuel biofractionmeasurements
Setup
Oinonen M, Palonen V, Uusitalo J. 2015. Biofraction measurements of methane for environmental and metrological
applications. Radiocarbon conference, Dakar, Senegal, November 2015
Catalytic combustion of CH4 combined with molecular sieve trapping of
resulting CO2
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Gaseous fuel biofractionmeasurements
Results
Oinonen M, Palonen V, Uusitalo J. 2015. Biofraction measurements of methane for environmental and metrological
applications. Radiocarbon conference, Dakar, Senegal, November 2015 and to be published 2016.
First 5 methane biofraction
measurements → immediate
success
Results within industrial
standard (ASTM D6866-12)
Allows for characterization of
biogas/natural gas mixtures
(100% CH4) and field
measurements (<1% CH4)
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Soil carbon decomposition to CH4Carbon sinks and sources
Portable (semi…) setup allows for field collections of CH4 → Arctic
methane emissions due to permafrost melting?Oinonen M, Palonen V, Uusitalo J. 2015. Biofraction measurements of methane for environmental and metrological
applications. Radiocarbon conference, Dakar, Senegal, November 2015
Palonen V. ECAART 2016 conference.
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Summary & future
I hope I have provided you a view that radiocarbon measurements
are not only for dating of archaeological finds
They, particularly supplemented by stable isotopic measurements, contribute
in understanding the carbon circulation throughout the carbon cycle
Future: 1) Bayesian time spectra and data mining based on archaeological,
scientific, genetic and even linguistic multiproxy data
2) Influence of carbon origin on 14C chronologies (reservoir effects)
3) Biofraction measurements proceed towards Ecolabel to give a consumer
the power to choose whether to use fossil or biogenic product
Thank you for your attention!
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Early urbanization of TurkuWiggle matching on Aboa Vetus museum
65
Wood can be dated
by coupling multiple14C dates & order &
time difference
Narrowing the
calendar year
probability
distributions by factor
of 5-10
Oinonen, M, Hilasvuori, E, Mehtonen, H, Uotila, K & Zetterberg, P 2013, 'On the eve of urbanization: Bayesian model dating
for medieval Turku' Radiocarbon, Vuosikerta / volyymi 55, Nro 2-3, Sivut 1265-1277., 10.2458/azu_js_rc.55.16244
Markku Oinonen / Quantifying the past / Natural
Sciences
www.luomus.fi
Early urbanization of Turku5 layers, 11 dates from Aboa Vetus museum
66
Early urbanization
of Turku studied
with Bayesian
dating model
Overcomes the 14th
century challenges
by narrowing the
calendar year
probability
distributions by
factor of 5-10
M. Oinonen, E. Hilasvuori,H. Mehtonen,K. Uotila,P. Zetterberg. 2013. ON THE EVE OF URBANIZATION
– BAYESIAN MODEL DATING FOR MEDIEVAL TURKU. Accepted for publication in Radiocarbon.
Markku Oinonen / Quantifying the past / Natural
Sciences
www.luomus.fi
Background radiation
ionizes mineral crystals
The ejected charges are
trapped in potential wells of
crystal defects
Graphic: H.Bonner, Design: M. Oinonen for
Elämän Historia-exhibition / LUOMUS
67
Luminescence datingLong time ago…
www.luomus.fi
Our ancestors have a dinner
at a fireplace
Heat brings in excess of
energy and empty the traps
→ luminescence light is
emitted
68
Graphic: H.Bonner, Design: M. Oinonen for
Elämän Historia-exhibition / LUOMUS
Luminescence datingHave a dinner…
www.luomus.fi
Fireplace is found after a
long period of time…
The traps have been
meanwhile filled and their
amount corresponds to the
absorbed radiation dose
during that long period of
time
69
Graphic: H.Bonner, Design: M.
Oinonen for
Elämän Historia-exhibition /
LUOMUS
Luminescence datingFireplace is found…
www.luomus.fi
Excess of energy (heat,
light) is again given for the
mineral grains
→ amount of emitted
luminescence light
(paleodose) is measured
Dose rate is measured on
samples and/or in the field
70
Graphic: H.Bonner, Design: M. Oinonen for
Elämän Historia-exhibition / LUOMUS
Luminescence datingIn the laboratory…
www.luomus.fi
Luminescence datingMore scientific explanation…
Aitken M J 1998, An introduction to optical dating,
Oxford Science Publications.
Ionization by
radiation
L
T
E
hole
electron conduction band
valence band
1) Irradiation 2) Storage 3) Eviction
light,
heat
light
71
Measured from sample
and/or from field
www.luomus.fi
Luminescence datingSummary
1) Paleodose measurement by luminescence technique
2) Radiation dose rate measurements (alfa, beta, gamma, cosmic)
Typically 5-10% accuracies obtained
Range 50-300 000 a
Datable events: manufacturing of pottery, heating of fireplaces,
sediment layers (aeolian(airborne) or alluvial(water) sand)
www.luomus.fi
210Pb datingdecay clock
210Pb due to decay chain of 238U
210Pb integrated in silicates and
precipitates in sediments
If feeding from decay chain of 238U is measured
→
Remaining 210Pb decays
according to its T1/2 (22,3 a)
Amount left provides info on
sedimentation rates of the last
100-200 years
http://www.nndc.bnl.gov/nudat2/
www.luomus.fi
Radiometric datingsBasics
Naturally occurring background radioactivities can be exploited in
dating studies provided that some prerequisities are fulfilled
The most common (40K, U-series) are also the ones most used in
radiometric datings
The longer the T1/2, the older ages could be determined
Production continues by cosmic rays
→ production of cosmogenic isotopes
→ plants, sediments, glaciers, lithosphere ...
www.luomus.fi
Ice age in Svalbard14C & Luminescence
Courtesy of Kaakinen A, Salonen V-P, Department of Geology, University of Helsinki
Expeditions following the
footsteps of Nordic pioneers
on Nordaustlandet, Svalbard
(2007-2010)
Aim to better understanding of
the region where the
topography and sedimentary
environment resemble those
of Finland during the
Weichselian glacial stage:
120 000 – 10 000 BC
www.luomus.fi
3/11 & 3/14 2/7 & 2/8 5/27 & 5/28
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
50000
ag
e(c
al B
P)
sample ID
OSL: grey14
C: black
Ice age in SvalbardLuminescence vs. 14C
A.Kaakinen, V.-P.Salonen, F.Kubischta, K.Eskola, M.Oinonen 2009. Weichselian glacial stage in
Murchisonfjorden, Nordaustlandet, Svalbard. Boreas 38: 718-729.
www.luomus.fi
0 200 400 600 800 1000 1200 1400 1600 1800 2000
0
10
20
30
40
50
60
am
ou
nt o
f 1
4C
da
tes
AD
Archaeological radiocarbon datesLast 2000 years
Based on Oinonen M, Pesonen P,
Tallavaara M 2010. Radiocarbon 52: pp. 393-407.
Interestingly, minimum
between the warm
periods at ~600AD
Coincidence?
Southern
Ostrobothnia known
to have shortage of
finds
Roman warm
period
Medieval warm
period i.e. MCA
Markku Oinonen / Quantifying the past / Natural
Sciences
www.luomus.fi
Temporal distribution of 14C dates14C in Eastern Fennoscandian archaeology
Tallavaara M, Pesonen P, Oinonen M 2010. Prehistoric population history in eastern
Fennoscandia, Journal of Archaeological Science 37: pp. 251-260.
Oinonen M, Pesonen P, Tallavaara M 2010. Archaeological radiocarbon dates for studying the
population history in eastern Fennoscandia, Radiocarbon 52: pp. 393-407
Markku Oinonen / Quantifying the past / Natural
Sciences
www.luomus.fi
Early ceramics in easternFennoscandia
Bayesian model dates of food crust samples attached to pots
Pesonen P, Carpelan C, Oinonen M, Onkamo P 2012. EARLY SUBNEOLITHIC CERAMIC SEQUENCES IN EASTERN
FENNOSCANDIA – A BAYESIAN APPROACH. Radiocarbon 54: pp. 661-676.
d13C values carry information of
marine/terrestrial nature of samples
Correction of marine effects makes Arctic
Sea dates more reasonable
Markku Oinonen / Quantifying the past / Natural
Sciences
www.luomus.fi
Bayesian analysis in Oxcal 4.1Bronk Ramsey C 2009. Bayesian analysis of radiocarbon dates.
Radiocarbon 51(1): pp. 337-360.
80
Ordering and time difference of events can be exploited within Bayesian
frameworkPlot()
{
D_Sequence( "All")
{
First( );
R_Date("Hela-2179", 621, 29);
Gap( 20);
R_Date("Hela-2177", 640, 31);
Gap( 10);
R_Date("Hela-2176", 632, 30);
Gap( 10);
R_Date("Hela-2175", 691, 30);
Gap( 10);
R_Date("Hela-2174", 678, 28);
Gap( 10);
R_Date("Hela-2173", 653, 30);
Gap( 10);
Date("Felling date");
};
}; Probability of impossible is zero…Markku Oinonen / Quantifying the past / Natural
Sciences
www.luomus.fi
TL, sto
nes
OSL,
san
dC-1
4
land
uplift
cera
mics
-10000
-9000
-8000
-7000
-6000
-5000
-4000
-3000
-2000
-1000
0
1000
2000
Ag
e (
ca
l yr)
Dating method
Eskola K O, Okkonen J, Jungner H 2003,
Luminescence dating of a coastal Stone Age
dwelling place in Northern Finland, Quaternary
Science Reviews 22, pp 1287-1290.
Kastelli, Jätinkirkko
Giant’s Church in KastelliLuminescence and 14C in archaeology
Giant’s church
(Jätinkirkko) in Kastelli,
Pattijoki has been
considered to be a
calendar (Ridderstad et al)
OSL and 14C datings
reveal its use to a period
3000-2000 cal BC i.e.
5000-4000 years ago
Te same time mammoths
wandered in Wrangel…
www.luomus.fi 23.2.2017 82
Water burial of 100 humansLevänluhta, Southern Ostrobothnia, Finland
• 1km from Kyrö river, presently in middle of a field
•1674 AD Isokyrö vicar Alftanus: human bones seen coming from the
spring ”throughout the times”
• 1886, 1912, 1982-1984 AD: bonesof almost 100 humans excavated
• presently a spring with iron-containing reddish water
• present archaeological dating to 4th-8th centuries AD (Wessman
2009)
Wessman A 2009. LEVÄNLUHTA – A PLACE OF PUNISHMENT, SACRIFICE OR JUST A COMMON CEMETERY?
Fennoscandia archaeologica XXVI: pp. 81-105 and references therein.
Isokyrö,
Southern
Ostrobothnia,
FinlandLevänluhta
Kyrö river
1 km
Markku Oinonen , Radiocarbon and Diet 2014
www.luomus.fi
Witnessing the post-glacial land uplift
23.2.2017 83
• Post-glacial land uplift has been
(still is) extensive in
Ostrobothnia
• Land rises still ~1cm/year
(eventually there will be a
isthmus connecting Finland and
Sweden)
• This has had significant
consequences on peoples lives
• Levänluhta people have
witnessed ~4 meters of land
uplift during the 4th-8th centurieshttp://walkfinland.blogspot.fi/2012/07/korsholm-bjorkoby-
bodvattnet-nature.html
Markku Oinonen , Radiocarbon and Diet 2014
www.luomus.fi
• 536 AD & 540’s: Cold years of Fimbulvinter?
• Anomaly observed in tree rings throughout
the northern Hemisphere
• Levänluhta people have witnessed the largest
climatic anomaly of the last 2000 years
• SA CARATE 2011-2015: tree-ring d13C
evidences a loss of light intensity
23.2.2017 84
Witnessing the climatic anomaly of 536AD
Baillie M G L 1994. Holocene 4:212-217 and refs therein.
Oinonen M & Mielikäinen K 2011. Funding decisions #251287 and 251441 for CARATE project by the Academy of
Finland.
Markku Oinonen , Radiocarbon and Diet 2014
520 525 530 535 540 545 550 555 560 565 570
-30
-28
-26
-24
-22
-20
d13C(
‰)
year(AD)
CA02
www.luomus.fi
Time dependence of isotopic values through 536AD
23.2.2017 85
350 400 450 500 550 600 650 700 750
-24
-22
-20
-18
-16
350 400 450 500 550 600 650 700 750
10
11
12
13
14
15
d13C
d15N
year
• Tvauri: crop failures and
demographic catastrophes in
Estonia
• Gräslund: widespread
disruption of settlement and
population displacement in Sweden
• Higher isotope ratios after
536AD indicate pronounced use
of marine resources → towards
more mobile lifestyle?
Tvauri A 2014. The impact of the climate catastrophe of 536-537AD in Estonia and neighboring areas. Estonian Journal of
Archaeology 18(1): 30-56.
Gräslund B and Price N 2012. Twilight of the gods? The “dust veil event” of AD 536 in critical perspective. Antiquity 86: 428-443.
Markku Oinonen , Radiocarbon and Diet 2014
536AD
www.luomus.fi
Labview controlled → process parameters stored
Elemental Analyzer option → fast combustion
Molecular sieve option for CO2 samples
Increases the throughput of 14C-AMS measurements
Quality control by Sixth International Radiocarbon
Intercomparison 2014
HASE – Helsinki Adaptive SampleprEparation line2nd generation 14C process
Palonen, V, Pesonen, A, Herranen, T, Tikkanen, P, Oinonen, M 2013, HASE – The Helsinki adaptive sample preparation
line, Nuclear Instruments & Methods in Physics Research. Section B: 294. http://dx.doi.org/10.1016/j.nimb.2012.08.056
AMS
Markku Oinonen / ICOS 2014
Aerosols
Soil CO2
Biofractions
www.luomus.fi
neutrons
protons
Mass known
Half-life knownnothing known
s process
stellar burning
Big Bang
p process
Supernovae
Cosmic Rays
H(1)
Fe (26)
Sn (50)
Pb (82)
Origin of Elements
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Cosmogenic isotopes
IsotopeTerrestrial targets
atmosp. / lithosp.
T1/2 (a)
10Be N, O / O, Mg, Si, Fe 1,5 × 106
14C N, O / O, Mg, Si, Fe 5730
22Na Ar / Mg, Al, Si, Fe 2,61
26Al Ar / Cl, K, Ca, Fe 7,16 × 105
32Si Ar / Cl, K, Ca, Fe 276
36Cl Ar / Cl, K, Ca, Fe 3,08 × 105
39Ar Ar / K, Ca, Fe 269
41Ca Kr / Ca, Ti, Fe 1,03 × 106
81Kr Kr / Rb, Sr, Zr 2,13 × 105
129I Xe / Te, Ba, Ce, La 1,57 × 107
Wide variety of half-lives → long time span of usage
Typically trace elements → Measurable by accelerator mass
spectrometry (AMS)Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Isotope Ratio Mass Spectrometry (IRMS)stable isotopes / methods
http://pubs.usgs.gov/of/2001/ofr01-257/images/figure1.gif
Since stable isotopes are plenty,
IRMS measures ion current
For instance 13C/12C
with delta-notation (in ‰)
Carbonates → d13C ~ 0 ‰
Plants → d13C ~ -25 ‰
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
d13C = (13C/12Csample – 13C/12Cstandard) / 13C/12Cstandard × 1000
www.luomus.fi
Uranium-series dating (of closed systems)accumulation clock
Multiple possibilities within the chain
U is soluble in water, but Th not → All Th is
radiogenic in material precipitated from water (down
to 500000 years back)
U in ZrSiO4, but Pb rejected → All Pb is radiogenic
(down to 4,5 billion yrs)
Thermal ionization mass spectrometry TIMS vrt AMS
for 14C (NOT TRACE ELEMENT!)
U/Th: corals, mollusk shells, egg shells (carbonates),
speleothems; U/Pb: age of earth, rocks
238U
234Th
234Pa
234U
230Th
a
b-
b-
a
a
235U
231Th
231Pa
a
b-
a
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
40K-40Ar datingaccumulation clock
40K (T1/2 = 1,26 × 109 years) one of the most common radioactive
elements in nature (clay, minerals)
Ar escapes from molten rock
Solid rock: the ratio between 40K and 40Ar is related to the time
elapsed since when system was closed
Vulcanic activities, archaeological deposits in Olduvai etc
McDougall, I.; Harrison, T. M. 1999. Geochronology and thermochronology by the 40Ar/39Ar
method. Oxford University Press. ISBN 0-19-510920-1.
Tattersall, I. 1995. The Fossil Trail: How We Know What We Think We Know About Human
Evolution. Oxford University Press. ISBN 0-19-506101-2.
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Age of the EarthUranium-series dating
Assumption: the Earth and the
rest Solar System formed at the
same time
The first: U/Pb ratio measured
from the The Canyon Diablo
meteorite fallen to Earth
All Pb due to decay of U series
4,54 × 109 years, confirmed by
hundreds of later datings
Patterson C 1956. Age of meteorites and the earth. Geochimica et Cosmochimica Acta 10:
230-237.
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi 23.2.2017 93
Operating within life-supportingcycles (C, N, H2O)
12C - 98.89%, 13C - 1.11% 14C -0.00000000010%
Operating within
major life-supporting
cycles (carbon,
nitrogen, water)
Stable isotopes
provide access to
origin of carbon and
processes within the
cycle
Radiocarbon provides
timeline
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Mammoths in Finland14C in paleontology
http://www.fmnh.helsinki.fi/mammutit/tietoa/suomi.htm
10 findings of
mammoth remains
from Finland
Dated ca. 32000 – 23500 BP
→
Before the Last Glacial Maximum
around 18000 BP Finland was
icefree with mammoths
wandering
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
Mammoths in Wrangel island 2000 BC14C in paleontology
S. L. VARTANYAN, Kh. A. ARSLANOV, T. V. TERTYCHNAYA and S. B. CHERNOV, Radiocarbon Dating
Evidence for Mammoths on Wrangel Island, Arctic Ocean, until 2000 BC, Radiocarbon Volume 37,
Number 1, 1995, pp. 1-6
Remains of miniature
mammoths discovered from
Wrangel island
Radiocarbon measurements
reveal the ages of around
4000 years only
Humans known to inhabit
Wrangel ca. 1700 BC
→ last mammoth hunters ?
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz
www.luomus.fi
1. Carbon dioxide in air:
isotopic ratio δ13C ~ -8
‰
2. CO2 to cells: diffusion is
an example causing
kinetic fractionation,
since lighter isotope (12C)
moves faster than a heavy
one (13C)
3. Sugars produced in complicated
reactions through photosynthesis
4. Sugars used to form
lignin, cellulose and
eventually the plant
structure
CO2
Through mass-dependent
effects, the terrestrial plants
contain less 13C than
atmosphere: δ13C ~ -25 ‰
96
First step of the food chain12,13,14C from air to plants
Figure: Wikipedia Commons
Markku Oinonen / Baltic Bioarchaeology, Riga 16th
May, 2014
www.luomus.fi
Climatic reconstructions: tree ringsdendrochronology provides the timeline (1 year)
Tree-ring width -based climatic
reconstructions use
dendrochronology to define
timeline
Pointer years of volcanic
activity, comets, unusual local
climate400 500 600 700
10
15
20
542 AD536 AD
Ju
ly m
ean
te
mp
era
ture
(C
)
year (cal AD)
535 AD
Helama S., Macias Fauria M., Mielikäinen K., Timonen M. & Eronen M. 2010: Sub-Milankovitch solar forcing of
past climates: mid and late Holocene perspectives. Geological Society of America Bulletin 122 (11/12): 1981-
1988.
Markku Oinonen / Natural Sciences for Euroschool
2016, Mainz