Study of organic residues in vessels of archaeological ...
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Study of organic residues in vessels of archaeological origin with physicochemical analytical techniques Koupadi Kyriaki (address: Olympias 6, Rhodes 85132, Greece, phone number: 0030 6970988028, [email protected]) Department of Antiquities and Works of Art Conservation, TEI of Athens Bibliography 1. Kotzamani D., Phoca A., Karydi G., Zacharia M., Kantarelou V., Karatasios G., Boyatzis S. C. and Perdikatsis V., “The Metallurgical Investigation of Copper-Alloys Metalwork of the Benaki Museum Dated in the 4th-7th Centuries A.D.”, History, Technology and Conservation of Ancient Metal, Glasses and Enamels International Symposium, Athens 2011, oral presentation 2. Drandaki Α., 2008, Bronze vessels of the Late Antiquity: technique, typology, use, terminology according to the collection of the Benaki Museum, Phd dissertation 3. Colombini M. P., Modugno Fr., Ribechini E, 2005, “Organic mass spectrometry in archaeology: evidence for Brassicaceae seed oil in Egyptian ceramic lamps”, Journal of Mass Spectrometry, vol.40, pp. 890-896 4. Evershed, (2008), Organic residue analysis in archaeology: the archaeological biomarker revolution, Archaeometry, 50: 7, 895–924 5. Evershed R. P., Dudd St N., Copley M. S., Berstan R., Stott A. W, Mottram H., Buckley St. A., Crossman Z., (2001), Chemistry of Archaeological Animal Fats, Accounts of Chemical Research , 35: 661 6. Mills J., White R., (1999), Organic Chemistry of Museum Objects (Conservation and Museology), Routledge, 31-55, 95-128 7. Serpico M., White R, (2000), Ancient Egyptian Materials and Technology, Nicholson P, Shaw I (eds). Cambridge University Press, 390-405 FTIR results # C 6 H 14 CH 2 Cl 2 (CH₃)₂CO CH₃OH 11544 plasticisers plasticisers & inorganic compound fatty acids & esters fatty esters 11550 fatty acids, esters & salts of carboxilic acids 11551 - plasticisers 11573 plasticisers & inorganic compound fatty esters - 11596 - 11598 plasticisers plasticisers & inorganic compound 11622Α 11633Α fatty acids & esters fatty esters Acetone : FTIR spectra 4000,0 3000 2000 1500 1000 500 370,0 cm-1 %T 2921 2852 1709 1175 1736 1461 1412 1379 1228 1095 935 724 2925 2854 1711 1261 724 800 1026 1095 1181 1410 1461 1376 1744 1716 1458 1376 1259 1383 1461 1259 1742 886 2926 2855 1458 1259 1376 798 1092 1019 11544 11551 11550 11598 11633Α 11573 11596 11622Α Fatty acids Fatty esters 0 5 10 15 20 25 oil lamp 11544 oil lamp 11550 oil lamp 11551 small bottle 11573 tripod vessel 11596 spouted vessel 11598 stemmed bowl 11622A stemmed bowl 11633A Results GC-MS Results The identified main components using GC-MS analysis on derivatised samples are: • glycerol along with C16 and C18 monoacyloglycerols • a wide variety of even numbered saturated fatty acids ranging from C8 to C26, as well as two odd numbered saturated fatty acids (C9 and C15). • hydroxy- and dihydroxy- fatty acids: 2- hydroxy-heptanoic (C7(2-OH):0), 9,10-dihydroxy-octadecanoic acid (C18 (9,10-diOH):0), 13,14-dihydroxy- docosanoic acid (C22 (13,14-diOH):0 • a series of linear dicarboxilic acids, both even and odd numbered: C4 to C14. • β-sitosterol is also present in a number of samples • a wide variety of two different hydrocarbon types, Cv 1 H2v 1 and Cv 2 H2v 2-1 , with v 1 ranging from 28 to 31 and v 2 ranging from 43 to 49 in some of the samples • markers for oxidative degradation of pine resin: dehydroabietic, 7-hydroxy-/ 7-oxo -/ dehydroabietic, in sample 11622A 7 Acknowledgments Thesis was conducted and presented at the Dept. of Conservation of Antiquities and Works of Art, Technological Educational Institute of Athens; supervised by Prof. S. C. Boyatzis. Information on the samples and the objects were provided by Ms D. Kotzamani, conservator at the «Laboratory for Metal - Glass and Bone Artifacts Conservation» of Benaki Museum. Part of the experimental work was conducted at the Dept. of Nutrition & Dietetics of Harokopio University of Athens; supervisory assistance on GC-MS sample workup and GC-MS runs was offered by Dr. M. Roumpou and Prof. N. Kalogeropoulos. Conclusions The compounds found in the samples were identified as • Oils collected from plants of the Brassicaceae family in all samples 3,4,5 • Degradation products of castor oil 3 in samples 11550, 11596,11544 • Fats 6 of unknown origin in sample 11544 • Pine resin biomarkers 7 in sample 11622A • The results provide considerable help for the conservator, in order to choose a suitable conservation treatment for the artifacts 11544, 11550, 11551, 11573, 11596,11598, 11622 Α ,11633Α C6H14 (CH₃)₂CO CH 2 Cl 2 CH₃OH Soluble FTIR Remnant CH 2 Cl 2 :CH 3 OH 2:1 Soluble Soluble Soluble Soluble Evapo- ration Refrigerator (~0°C) I.S.:C 16 H 34 +BSTFA TMS ESTERS GC-MS Methodology The scheme below illustrates the experimental procedures for sample workup and analysis. # 11544 11550 11551 11596 11598 11573 11622A 11633A Vessel Type Oil lamp Tripod vessel Spouted vessel Small bottle Stemmed bowl Relative Chronology 5 th – 7 th c. A.D. 5 th – 8 th c. A.D. 5 th c. A.D. 5 th – 7 th c. A.D. 5 th – 6 th c. A.D. 5 th c. A.D. Origin Egypt Unknown Egypt Sample description Vessels’ inner surface Surface edges Sample picture Vessels & Samples A number of copper alloy vessels were selected from the Byzantine Collection of the Benaki Museum in Athens(128 artefacts, purchased from Egyptian markets by the museum founder, A. Benakis, during the early 20th century) 1 . As there was no archaeological record of these objects, all information listed in the table bellow originates from the Doctoral Thesis of Dr Drandaki 2 , curator of the Byzantine Collection at the Benaki museum. CH 3 CH 3 COOH C H 3 CH 3 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 0 500000 1000000 1500000 2000000 2500000 3000000 3500000 4000000 4500000 5000000 Time--> Abundance Χ C4di C6di C10di C11di C16:0 C13di C18:0 C14di C20:0 C22:0 C24:0 C5di C12di Glc C16 C9:0 & Χ C8di Χ C8:0 Glc Glc C18 C10:0 C16H34 (I.S.) C7di C12:0 C9di C14:0 7DH-DHAA DHAA Χ 7O-DHAA C22 (13,14-diOH): 0 Χ C20 (11, 12-diOH): 0 Chromatogram: #BEN11622A diluted C18 (9,10-diOH): 0
Transcript of Study of organic residues in vessels of archaeological ...
Study of organic residues in vessels of archaeological origin with
physicochemical analytical techniques Koupadi Kyriaki
(address: Olympias 6, Rhodes 85132, Greece, phone number: 0030 6970988028, [email protected])
Department of Antiquities and Works of Art Conservation, TEI of Athens
Bibliography 1. Kotzamani D., Phoca A., Karydi G., Zacharia M., Kantarelou V., Karatasios G., Boyatzis S. C. and Perdikatsis V., “The Metallurgical Investigation of Copper-Alloys Metalwork of the Benaki
Museum Dated in the 4th-7th Centuries A.D.”, History, Technology and Conservation of Ancient Metal, Glasses and Enamels International Symposium, Athens 2011, oral presentation
2. Drandaki Α., 2008, Bronze vessels of the Late Antiquity: technique, typology, use, terminology according to the collection of the Benaki Museum, Phd dissertation
3. Colombini M. P., Modugno Fr., Ribechini E, 2005, “Organic mass spectrometry in archaeology: evidence for Brassicaceae seed oil in Egyptian ceramic lamps”, Journal of Mass Spectrometry,
vol.40, pp. 890-896
4. Evershed, (2008), Organic residue analysis in archaeology: the archaeological biomarker revolution, Archaeometry, 50: 7, 895–924
5. Evershed R. P., Dudd St N., Copley M. S., Berstan R., Stott A. W, Mottram H., Buckley St. A., Crossman Z., (2001), Chemistry of Archaeological Animal Fats, Accounts of Chemical Research, 35: 661
6. Mills J., White R., (1999), Organic Chemistry of Museum Objects (Conservation and Museology), Routledge, 31-55, 95-128
7. Serpico M., White R, (2000), Ancient Egyptian Materials and Technology, Nicholson P, Shaw I (eds). Cambridge University Press, 390-405
FTIR results
# C6H14 CH2Cl2 (CH₃)₂CO CH₃OH
11544 plasticisers
plasticisers
& inorganic
compound fatty acids
& esters
fatty esters
11550 fatty acids,
esters
& salts of
carboxilic
acids
11551
-
plasticisers
11573
plasticisers
& inorganic
compound fatty esters -
11596 -
11598
plasticisers
plasticisers
& inorganic
compound
11622Α
11633Α fatty acids
& esters fatty esters
Acetone : FTIR spectra
4000,0 3000 2000 1500 1000 500 370,0
cm-1
%T
2921
2852
1709
1175
1736
1461
1412
1379
1228
1095
935724
2925
2854
1711
1261
724800
10261095
1181
1410
14611376
1744
1716
14581376 1259
13831461
1259
1742
886
2926
2855
1458
12591376 7981092 1019
11544
11551
11550
11598
11633Α
11573
11596
11622Α
Fatty acids Fatty esters
0
5
10
15
20
25
oil lamp 11544
oil lamp 11550
oil lamp 11551
small bottle 11573
tripod vessel 11596
spouted vessel 11598
stemmed bowl 11622A
stemmed bowl 11633A
Results GC-MS Results The identified main components using
GC-MS analysis on derivatised
samples are:
• glycerol along with C16 and C18
monoacyloglycerols
• a wide variety of even numbered
saturated fatty acids ranging from C8
to C26, as well as two odd numbered
saturated fatty acids (C9 and C15).
• hydroxy- and dihydroxy- fatty acids: 2-
hydroxy-heptanoic (C7(2-OH):0),
9,10-dihydroxy-octadecanoic acid
(C18 (9,10-diOH):0), 13,14-dihydroxy-
docosanoic acid (C22 (13,14-diOH):0
• a series of linear dicarboxilic acids, both even and odd numbered: C4 to C14.
• β-sitosterol is also present in a number of samples
• a wide variety of two different hydrocarbon types, Cv1H2v1 and Cv2H2v2-1, with v1 ranging from 28
to 31 and v2 ranging from 43 to 49 in some of the samples
• markers for oxidative degradation of pine resin: dehydroabietic, 7-hydroxy-/ 7-oxo -/ dehydroabietic,
in sample 11622A 7
Acknowledgments
Thesis was conducted and presented at the Dept. of Conservation of
Antiquities and Works of Art, Technological Educational Institute of Athens;
supervised by Prof. S. C. Boyatzis. Information on the samples and the objects
were provided by Ms D. Kotzamani, conservator at the «Laboratory for Metal -
Glass and Bone Artifacts Conservation» of Benaki Museum. Part of the
experimental work was conducted at the Dept. of Nutrition & Dietetics of
Harokopio University of Athens; supervisory assistance on GC-MS sample
workup and GC-MS runs was offered by Dr. M. Roumpou and Prof. N.
Kalogeropoulos.
Conclusions The compounds found in the samples were identified as • Oils collected from plants of the Brassicaceae family in all
samples 3,4,5 • Degradation products of castor oil3 in samples 11550,
11596,11544 • Fats6 of unknown origin in sample 11544 • Pine resin biomarkers7 in sample 11622A • The results provide considerable help for the conservator, in order
to choose a suitable conservation treatment for the artifacts
11544, 11550, 11551, 11573, 11596,11598, 11622Α,11633Α
C6H
14
(CH₃)₂C
O
CH
2C
l 2
CH₃O
H
Soluble
FTIR
Remnant
CH
2C
l 2:C
H3O
H
2:1
Soluble
Soluble
Soluble
Soluble
Eva
po
-
rati
on
Refrigerator
(~0°C)
I.S
.:C
16H
34
+B
ST
FA
TMS ESTERS
GC-MS
Methodology
The scheme below illustrates the experimental
procedures for sample workup and analysis.
# 11544 11550 11551 11596 11598 11573 11622A 11633A
Vessel Type
Oil lamp
Tripod
vessel
Spouted
vessel
Small
bottle Stemmed bowl
Relative
Chronology
5th – 7th
c. A.D.
5th – 8th
c. A.D. 5th c. A.D.
5th – 7th
c. A.D.
5th – 6th c. A.D.
5th c. A.D.
Origin Egypt Unknown Egypt
Sample
description Vessels’ inner surface Surface edges
Sample
picture
Vessels & Samples A number of copper alloy vessels were selected from the Byzantine Collection of
the Benaki Museum in Athens(128 artefacts, purchased from Egyptian markets
by the museum founder, A. Benakis, during the early 20th century)1. As there was
no archaeological record of these objects, all information listed in the table bellow
originates from the Doctoral Thesis of Dr Drandaki 2, curator of the Byzantine
Collection at the Benaki museum.
CH3
CH3
COOHCH3
CH3
6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.000
500000
1000000
1500000
2000000
2500000
3000000
3500000
4000000
4500000
5000000
Time-->
Abundance
TIC: BEN116~2.D
Χ
C4di
C6di C
10di C
11di
C16:0
C13di
C18:0
C
14di
C20:0
C22:0
C24:0
C5di
C12di
Glc
C16
C9:0
& Χ
C8di
Χ
C8:0
Glc
Glc
C18
C10:0
C16H
34 (
I.S
.)
C7di
C12:0
C9di
C14:0
7D
H-D
HA
A D
HA
A
Χ
7O
-DH
AA
C22 (
13,1
4-d
iOH
): 0
Χ
C20 (
11,
12-d
iOH
): 0
Chromatogram: #BEN11622A diluted
C18 (
9,1
0-d
iOH
): 0
