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Arne Jouttijärvi

Heimdal-archaeometry

A variety of laboratory- bound X-ray fluorescence (XRF) spectrometers have been used successfully for the investigation of archaeological, historical and art materials for more than fifty years. It is only recently through the advent of powerful portable systems that this non-destructive technology can be fully exploited. Working in situ, portable spectrometers have extended the range of XRF technology to virtually any type of object.

Håndholdt XRF (pXRF)

+ Hurtig

+ Genstanden behøver ikke flyttes

+ Lave detektionsgrænser for de fleste elementer

+ Relativt billig

- Kan ikke se lette grundstoffer (Na, S. Cl m. fl.)

- Analyserer en meget stor flade (3-5 mm)

- Kan IKKE anvendes ikke-destruktivt

Hodgkinson, Anna K. 2016. “Amarna glass: from Egypt through the ancient world.” Egyptian Archaeology 48: 23-27.

Na2O MgO Al2O3 SiO2 K2O CaO TiO2 MnO Fe2O3 Co CuO PbO SUM

Rosd3 0 2,415 76,12 0,998 6,189 0,064 0,188 0 0,033 4,965 90,972

P13 1,693 4,788 76,84 0,837 5,511 0,14 0,058 0,22 0,004 2,744 92,835

P13 1,977 4,633 76,87 0,824 5,467 0,14 0,055 0,211 0,004 2,753 92,934

P20 1,911 5,953 71,61 0,508 6,072 0,224 0,021 2,013 0,58 0,009 88,901

P20 1,988 5,759 71,98 0,53 6,1 0,228 0,02 1,942 0,577 0,01 89,134

P21 2,052 5,964 72,12 0,511 5,725 0,245 0,021 1,943 0,784 0,009 89,374

P21 2,183 6,045 72,35 0,518 5,692 0,226 0,015 1,896 0,76 0,009 89,694

P20 2,586 5,89 71,76 0,519 5,718 0,224 1,941 0 0,794 0,009 89,441

P21 1,73 5,565 71,39 0,52 6,189 0,222 2,111 0 0,636 0,009 88,372

P31:1 0 1,593 28,75 0,159 11,25 0,168 1,848 0 0,706 0,006 44,48

P31:2 1,538 5,026 72,34 0,516 5,746 0,225 1,101 0 0,341 0,004 86,837

P31:3 2,55 6,874 72,01 0,579 5,806 0,23 2,316 0 0,627 0,007 90,999

M47908:1 0 0 47,07 0,42 5,12 0,149 1,556 0,093 0 9,708 64,116

M47908:2 0 0 64,98 0,601 4,319 0,101 1,369 0,091 0 10,31 81,771

P24 0 4,107 77,58 0,924 5,907 0,165 0,319 0 0,008 3,212 92,222

P28 4,872 0 77,46 0,306 3,732 0,032 0,145 0 0,15 0,063 86,76

P58:1 0,523 0 23,01 0,007 1,541 0 0,559 0 0 0,056 25,696

P58:2 1,372 0 46,47 0,038 3,448 0,187 1,191 0,007 0,002 0,11 52,825

Et par eksempler

morter Cu Sn Zn Pb Sb Ag As Ni

pXRF 76,04 3,79 11,94 5,48 0,16 0,10 0,16 0,00

SEM-EDS 74,4 3,5 10,8 5,1 0,2 0,0 0,0 0,1

Genstand A Cu Sn Zn Pb Sb Ag As Ni

pXRF 78,49 8,53 0,24 0,00 1,00 0,06 1,28 0,51

pXRF snit 85,58 4,12 0,29 0,22 1,32 0,72 0,33 0,39

SEM-EDS 91,0 4,2 0,0 0,5 0,4 0,0 0,4 0,5

Genstand B Cu Sn Zn Pb Sb Ag As Ni

pXRF 83,41 8,50 0,14 0,46 0,81 0,11 1,60 0,27

pXRF snit 89,57 3,47 0,23 1,13 0,85 0,53 0,51 0,37

SEM-EDS 91,0 3,7 0,0 0,4 0,3 0,1 0,1 0,4

Genstand C Cu Sn Zn Pb Sb Ag As Ni

pXRF 40,90 67,09 0,00 11,06 0,81 0,00 0,00 0,01

SEM-EDS 79,7 13,8 0,0 2,6 0,6 0,0 0,1 0,0

Genstand C Cu2O SnO2 ZnO PbO Sb2O3 Ag2O As2O3 NiO

SEM-EDS 16,3 58,8 0,0 15,2 1,6 0,2 0,3 0,0

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pXRF

SEM-EDS

-og hvad det kan føre tiltinbarrerne fra Løgstrup Sø

VSM 09398 Cu Sn Zn Pb Sb Ag As

pXRF 24,90 30,15 0,06 3,32 0,28 0,13 0,70

SEM-EDS x59 80,5 14,1 0,0 0,3 0,5 0,2 0,1

SEM-EDS x63 81,6 13,6 0,0 0,4 0,0 0,0 0,0

SEM-EDS x167 77,6 15,5 0,0 0,8 0,2 0,2 0,3

Paul Eklöv Pettersson: Fynd av råmaterial för bronsgjutning vid Løgstrup SØ: KFLRAPPORT 14/0326 Keramiska Forskningslaboratoriet Kvartärgeologiska avdelningen Lunds Universitet

Sammenligning mellem tinindhold målt med pXRF på afrenset overflade og målt med EMPA på udtaget prøve

V. Orfanou, Th. Rehren 2015 "A (not so) dangerous method: pXRF vs. EPMA-WDS analyses of copper-based artefacts"Archaeological and Anthropological Sciences vol.7, #3

samme prøver, forskellig metode

Afrenset og ikke afrenset

…it is possible to obtain reasonable quality data regarding the nature and approximate concentrations of the main components present in copper-based alloys such as tin and lead, provided that a metallic surface large enough for the spot of the instrument can be exposed (approx. 1–3 mm).

… it is safe to argue that all objects are copper-based (as already indicated by their green corrosionsurfaces) and that tin and occasionally lead are the main alloying agents, even if it is not possible to give an accurateestimation of the original alloy composition.

…for corrosion layers of up to ca. 25 μma portable XRF can yield very accurate quantification results.

However, when investigating highly corroded bronzes i.e. archaeological artifacts, some damage to the patina of the artifact during sample preparation (polishing) is imminent for a very precise quantification

D. Šatović, V. Desnica, S. Fazinić: Use of portable X-ray fluorescence instrument for bulk alloy analysis on low corroded indoor bronzes; Spectrochimica Acta Part B 89 (2013) 7–13

Overfladeanalyser = Usandsynlige analyser

K. Verlaeckt, Between river and barrow. A reappraisal of Bronze Age metalwork found in the province of East-Flanders (Belgium), Oxford, (= British Archaeological Reports. I nternational Series, 632)

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• Nogle metaller bliver udvasket ved korrosion, andre koncentreres

Cu Zn Pb Fe Sn Ni As Bi Sum Kilde

økse 55,44 0,19 4,13 0,27 39,57 0,14 0,22 0,03 Koen Verlaeckt 1996

pålstav 73,57 0,34 1,03 0,64 23,84 0,23 0,17 0,04 Koen Verlaeckt 1996

sværd 43,25 0,14 39,44 0,80 15,52 0,07 0,13 0,14 Koen Verlaeckt 1996

økse 36,31 0,47 19,79 0,18 41,34 0,07 1,18 0,10 Koen Verlaeckt 1996

Ikke engang pæne overflader er ikke repræsentative

• Overfladebelægninger

• Bevidste overfladeændringer

Afstand og overfladebelægninger

(lak og maling)

Dylan Smith, “Handheld portable X-rayfluorescence analysis of Renaissance bronzes: Practical approaches to quantification and acquisition” in Aaron Shugar and Jennifer Mass, eds., Practical Handheld X-Ray Fluorescence for Art Conservation and Archaeology (Studies in Archaeological Sciences, no. 3), Leuven, 2012, pp. 37–74

Robert H. Tykot:Using NondestructivePortable X-ray FluorescenceSpectrometers on Stone,Ceramics, Metals, and Other Materials in Museums: Advantages and Limitations; Applied Spectroscopy2016, Vol. 70(1) 42–56

Vinkel og ujævne overflader

Kalibrering• Mange af instrumenterne kan

ikke umiddelbart kalibreres over for standardmaterialer, men har en software-”kalibrering”

• Forskellige instrumenter kan give forskellige resultater på samme materiale

Goodale, N., Bailey, D. G., Jones, G. T. Prescott, C., Scholz, E., Stagliano, N., and Lewis. C. 2012. pXRF: a study of inter-instrument performance. Journal of Archaeological Science, 39, 875-883.

Two pXRF instruments, Delta and Omega models both manufactured by Olympus Innov-X Systems, were utilized to obtain the trace element signatures of obsidiansources

Metoden kan bruges til enkeltstående undersøgelser, men analyser lavet med forskellige apparater kan ikke nødvendigvis samemnlignes. Kræver brug af fælles standarder.

Robert J. Speakman, M. Steven Shackley: Silo science and portable XRF in Archaeology; Journal of Archaeological Science 40 (2013) 1435e1443

Homsher, R.S., Tepper, Y., Drake, B.L., Adams, M.J., and David, J. : From the bronze age to the “lead age”: Observations on sediment analyses at two archaeological sites in the Jezreel Valley, Israel; Mediterranean Archaeology and Archaeometry. (Mediterranean Archaeology and Archaeometry, 2016, 16(1):203-220)

Sammenlignelighed

Statue of Mercury, Martigny, Switzerland

Skal man kunne udnytte større mængder data fra forskellige kilder, er det vigtigt, at de kan sammenlignes

Arne Jouttijarvi: Roman AlloyingPractice; Materialsand ManufacturingProcesses, under udgivelse

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Ricardo Fernandes, Bertil JH van Os, Hans DJ: The use of Hand-Held XRF for investigating the composition and corrosion of Roman copper-alloyed artefactsHuisman Heritage Science 2013, 1:30 (16 September 2013)

Sample code Location Description Copper alloy Observations 128 Vechten Lump Lead-tin-brass (Low zinc content)

Photos (10-50x amplification)

Pitting Colour Surface P. Shape P. Soil A. Corrosion S. Remarks

1 23 ? ? 3 0 -

Composition of treated artefact (%) Cu Pb Zn Sn Bi Sb Mo Se Ni Cr

88,043 2,381 1,432 3,014 0,014 0,17 0,003 0,011 0,017 0,013 Co Fe Mn P Al Si Ti Zr Pd -

0,018 4,313 0,019 N.M. N.M. N.M. 0,145 0,032 0,011 -

Composition of untreated artefact (%) Cu Pb Zn Sn Bi Sb Mo Se Ni Cr


0,142 31,848 0,975 N.M. N.M. N.M. 3,24 0,86 0,083 -

Sample code Location Description Copper alloy Observations 12 Vechten Unknown Lead-tin-brass (Low zinc content)



1 3 ? 1 3 0 -



0,034 7,987 0,073 N.M. N.M. N.M. 0,341 0,06 0,013 -



0,069 18,136 0,786 N.M. N.M. N.M. 1,575 0,35 0,077 -

Sample code Location Description Copper alloy Observations 52 Vechten Lump Gunmetal



1 23 ? ? 3 0 -



0,032 6,74 0,087 N.M. N.M. N.M. 0,294 0,005 0,009 -



0,019 3,847 0,105 N.M. N.M. N.M. 0,322 0,03 0,01 -

Sample code Location Description Copper alloy Observations 445 Vechten Plaque

fragment Gunmetal


Pitting Colour Surface P. Shape P. Soil A. Corrosion S. Remarks 2 3 3 ? 1 1 -



0,048 13,549 0,03 N.M. N.M N.M. 0,405 0,002 0,007 -

Composition of untreated artefact (%)

Cu Pb Zn Sn Bi Sb Mo Se Ni Cr 40,566 2,527 0,192 40,971 0,014 0,042 0,002 0,005 0,027 0,025

Co Fe Mn P Al Si Ti Zr Pd - 0,049 14,711 0,031 N.M. N.M N.M. 0,543 0,002 0,007 -

ConclusionsA Hand-Held XRF (HH XRF) device is an analytical toolwell suited for investigating major elemental compositionof metallic archaeological artefacts. It can be deployed formeasurements in situ ensuring limited or no damage tomeasured artefacts.

-og deraf kan man lære….

• pXRF analyse kan kun foretages når genstanden står med blank metaloverflade, er plan, og ikke lakeret o.s.v.

• Tro ikke på alt hvad sælgeren siger

Presentations & Public Speaking

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