1
2
3
A Study of the Deterioration of Aged Parchment Marked with
Laboratory Iron Gall Inks Using ATR-FTIR Spectroscopy and
Micro Hot Table
4
Stamatis C. Boyatzis§, Georgia Velivasaki and Ekaterini Malea
5
6
SUPPLEMENTARY MATERIAL
7
8
9
10
1. ATR--FTIR Spectra of all areas of selected specimens
All areas refer to designation shown in Figure 2 of paper.
11
12
13
LIG Specimen: 2 days artificial ageing
Ink-free areas
1. 87
1137
1. 6
1. 4
1. 2
1625
601
1. 0
1535
1030
551
A
0. 8
1445
1200
2921
667
0. 6
1233
3400
3520
1334
0. 4
1164
2852
0. 2
0. 0
-0.14
14
3996.3
3000
2000
1500
1000
500
349. 1
cm-1
15
16
Figure S1: ATR-FTIR spectra of ink-free areas in parchment specimen with LIG after 2
days artificial ageing
17
18
19
20
21
22
LIG SPECIMENS, 2 DAYS AGEING;
LIG SPECIMENS, 2 DAYS AGEING;
LIG SPECIMENS, 2 DAYS AGEING;
LIG SPECIMENS, 2 DAYS AGEING;
LIG SPECIMENS, 2 DAYS AGEING;
areaP1
areaP2
areaP3
areaP4
areaP6
1
1
Inked areas
1. 59
1134
1. 4
1. 2
1630
1. 0
601
1534
555
0. 8
1030
A
1444
1162
0. 6
1200
667
1106
1227
3399
0. 4
3518
1334
2923
0. 2
0. 0
-0.09
2
3996.3
3000
2000
1500
1000
500
349. 1
cm-1
3
4
Figure S2: ATR-FTIR spectra of inked areas in parchment specimen with LIG after 2 days
artificial ageing
5
6
7
8
9
LIG SPECIMENS, 2 DAYS AGEING;
LIG SPECIMENS, 2 DAYS AGEING;
LIG SPECIMENS, 2 DAYS AGEING;
LIG SPECIMENS, 2 DAYS AGEING;
areaI1
areaI1 back face
areaI2
areaI3
10
2
1
2
LIG Specimen: 4 days artificial ageing
Ink-free areas
1. 87
1. 6
1136
1. 4
1. 2
600
1629
552
1. 0
1537
1031
A
0. 8
1449
669
1234
0. 6
3304
1335
3398
0. 4
1205
2924
3544
1163
1082
0. 2
825
0. 0
-0.12
3
4
5
6
7
8
9
10
11
3996.3
3000
2000
1500
1000
399. 2
cm-1
Figure S3: ATR-FTIR spectra of ink-free areas in parchment specimen with LIG after 4
days artificial ageing
LIG SPECIMENS, 4 DAYS AGEING;
LIG SPECIMENS, 4 DAYS AGEING;
LIG SPECIMENS, 4 DAYS AGEING;
LIG SPECIMENS, 4 DAYS AGEING;
LIG SPECIMENS, 4 DAYS AGEING;
areaP1
areaP2
areaP3
areaP4
areaP6
12
3
1
Inked areas
1. 55
1. 4
1133
1. 2
1631
1. 0
1155
599
1532
1030
0. 8
A
1446
1200
667
0. 6
1230
1161
3289
2923
0. 4
1333
2853
3395
3523
0. 2
0. 0
-0.07
2
3996.3
3000
2000
1500
1000
500
349. 1
cm-1
3
4
5
6
7
8
9
10
Figure S4: ATR-FTIR spectra of inked areas in parchment specimen with LIG after 4 days
artificial ageing
LIG SPECIMENS, 4 DAYS AGEING;
LIG SPECIMENS, 4 DAYS AGEING;
LIG SPECIMENS, 4 DAYS AGEING;
LIG SPECIMENS, 4 DAYS AGEING;
areaI1
areaI1 back face
areaI2
areaI3
11
12
4
1
2
LIG Specimen: 8 days artificial ageing
Ink-free areas
1. 68
1. 6
1135
1. 4
1. 2
1635
1441
1149
598
1114
1. 0
1535
548
2922
1030
531
0. 8
A
1446
1205
2852
0. 6
667
1335
3304
0. 4
3522
1741
873
824
0. 2
0. 0
-0.08
3996.3
3
4
5
6
7
8
9
10
11
3000
2000
1500
cm-1
LIG SPECIMENS, 8 DAYS AGEING; areaP1
LIG SPECIMENS, 8 DAYS AGEING; areaP2
LIG SPECIMENS, 8 DAYS AGEING; areaP3 (scraped)
LIG SPECIMENS, 8 DAYS AGEING; areaP3_ back face
LIG SPECIMENS, 8 DAYS AGEING; areaP4
LIG SPECIMENS, 8 DAYS AGEING; areaP5 (scraped)
LIG SPECIMENS, 8 DAYS AGEING; areaP6 (scraped)
12
5
1000
399. 2
1
Inked areas
2
1. 14
1632
1. 0
0. 9
1534
0. 8
552
0. 7
1030
0. 6
597
1447
1161
A
1201
0. 5
3292
1101
2923
0. 4
2854
0. 3
831
0. 2
1334
0. 1
-0.04
3996.3
3
3000
2000
1500
cm-1
4
5
6
7
8
9
LIG SPECIMENS, 8 DAYS AGEING; areaI1_
LIG SPECIMENS, 8 DAYS AGEING; areaI1 back face_
LIG SPECIMENS, 8 DAYS AGEING; areaI2_
LIG SPECIMENS, 8 DAYS AGEING; areaI3_
10
11
6
1000
399. 2
1
2
LIG Specimen: 16 days artificial ageing
Ink-free areas
3
1. 47
1. 4
1141
1. 2
1627
599
1. 0
1536
553
1030
0. 8
528
1447
A
668
0. 6
1336
3395
0. 4
2924
3292
2853
3525
833
0. 2
0. 0
-0.06
3996.3
4
5
6
7
8
9
10
11
12
13
3000
2000
1500
cm-1
LIG SPECIMENS, 16 DAYS AGEING; areaP1
LIG SPECIMENS, 16 DAYS AGEING; areaP2
LIG SPECIMENS, 16 DAYS AGEING; areaP3 (scraped)
LIG SPECIMENS, 16 DAYS AGEING; areaP3_ back face
LIG SPECIMENS, 16 DAYS AGEING; areaP4
LIG SPECIMENS, 16 DAYS AGEING; areaP5 (scraped)
LIG SPECIMENS, 16 DAYS AGEING; areaP6 (scraped)
14
7
1000
399. 2
1
Inked areas
1. 17
1. 1
1633
1. 0
0. 9
1143
0. 8
1533
1112
0. 7
597
1030
1446
0. 6
A
549
0. 5
1160
1100
3295
0. 4
2923
1335
1231
0. 3
0. 2
0. 1
-0.04
3996.3
2
3000
2000
1500
cm-1
3
4
5
6
7
8
LIG SPECIMENS, 16 DAYS AGEING; areaI1
LIG SPECIMENS, 16 DAYS AGEING; areaI1 back face
LIG SPECIMENS, 16 DAYS AGEING; areaI2
LIG SPECIMENS, 16 DAYS AGEING; areaI3
9
10
8
1000
399. 2
1
2
LIG Specimen: 32 days artificial ageing
Ink-free areas
1. 87
1. 6
1136
1. 4
1. 2
600
1629
552
1. 0
1537
1031
A
0. 8
1449
669
1234
0. 6
3304
1335
3398
0. 4
1205
2924
3544
1163
1082
0. 2
825
0. 0
-0.12
3
4
5
6
7
8
9
10
11
12
3996.3
3000
2000
1500
1000
399. 2
cm-1
Figure S5: ATR-FTIR spectra of ink-free areas in parchment specimen with LIG after 32
days artificial ageing
LIG SPECIMENS, 32 DAYS AGEING;
LIG SPECIMENS, 32 DAYS AGEING;
LIG SPECIMENS, 32 DAYS AGEING;
LIG SPECIMENS, 32 DAYS AGEING;
LIG SPECIMENS, 32 DAYS AGEING;
LIG SPECIMENS, 32 DAYS AGEING;
areaP1
areaP2
areaP3
areaP4
areaP5
areaP6
13
14
9
1
Inked areas
1. 55
1. 4
1133
1. 2
1631
1. 0
1155
599
1532
1030
0. 8
A
1446
1200
667
0. 6
1230
1161
3289
2923
0. 4
1333
2853
3395
3523
0. 2
0. 0
-0.07
2
3996.3
3000
2000
1500
1000
500
349. 1
cm-1
3
4
5
6
7
8
9
10
11
12
13
Figure S6: ATR-FTIR spectra of inked areas in parchment specimen with LIG after 32
days artificial ageing
LIG SPECIMENS, 32 DAYS AGEING;
LIG SPECIMENS, 32 DAYS AGEING;
LIG SPECIMENS, 32 DAYS AGEING;
LIG SPECIMENS, 32 DAYS AGEING;
areaI1
areaI1 back face
areaI2
areaI3
xxxxxxxxxxxxxxxxxxxxxxxxx
14
10
1
2
LIGG Specimen: 2 days artificial ageing
Ink-free areas
1.75
1.6
1129
1.5
1114
1.4
1.3
1.2
1.1
1638
1135
1.0
601
1538
0.9
A
555
1449
0.8
1030
527
0.7
667
1204
2923
0.6
1234
1624
0.5
3399
2853
1337
0.4
3523
1163
1083
0.3
1741
0.2
0.1
-0.03
3996.3
3
4
5
6
7
8
9
10
11
12
13
3000
2000
1500
1000
399.2
cm-1
Figure S7: ATR-FTIR spectra of ink-free areas in parchment specimen with LIGG after 2
days artificial ageing
LIGG SPECIMENS, 2 DAYS AGEING; areaP1
LIGG SPECIMENS, 2 DAYS AGEING; areaP2
LIGG SPECIMENS, 2 DAYS AGEING; areaP3
LIGG SPECIMENS, 2 DAYS AGEING; areaP3 back face
LIGG SPECIMENS, 2 DAYS AGEING; areaP4
LIGG SPECIMENS, 2 DAYS AGEING; areaP5
LIGG SPECIMENS, 2 DAYS AGEING; areaP6
11
1
Inked areas
1.30
1030
1.2
1.1
1630
1081
1139
1.0
1116
0.9
1539
1149
0.8
550
1447
1204
597
0.7
1229
A
0.6
0.5
2923
1281
1337
3301
0.4
2853
1161
1081
0.3
0.2
1742
831
0.1
-0.04
3996.3
2
3000
2000
1500
1000
399.2
cm-1
3
4
Figure S8: ATR-FTIR spectra of inked areas in parchment specimen with LIGG after 2
days artificial ageing
5
6
7
8
9
LIGG SPECIMENS, 2 DAYS AGEING; areaI1
LIGG SPECIMENS, 2 DAYS AGEING; areaI1 back face
LIGG SPECIMENS, 2 DAYS AGEING; areaI2
LIGG SPECIMENS, 2 DAYS AGEING; areaI3
10
12
1
2
LIGG Specimen: 4 days artificial ageing
Ink-free areas
2. 12
2. 0
1135
1. 8
1. 6
1. 4
1624
1. 2
601
A
1. 0
1539
1031
554
1449
528
0. 8
1204
667
0. 6
1231
3399
2923
0. 4
3524
1336
1165
1085
2852
831
0. 2
-0.06
3
4
5
6
7
8
9
10
11
12
3996.3
3000
2000
1500
1000
399. 2
cm-1
Figure S9: ATR-FTIR spectra of ink-free areas in parchment specimen with LIGG after 4
days artificial ageing
LIGG SPECIMENS, 4 DAYS AGEING; areaP1
LIGG SPECIMENS, 4 DAYS AGEING; areaP2
LIGG SPECIMENS, 4 DAYS AGEING; areaP3
LIGG SPECIMENS, 4 DAYS AGEING; areaP4
LIGG SPECIMENS, 4 DAYS AGEING; areaP4
LIGG SPECIMENS, 4 DAYS AGEING; areaP6
13
13
1
Inked areas
1. 33
1. 2
1630
1. 1
1084
1. 0
1534
1030
1137
0. 9
1154
0. 8
553
526
1446
597
0. 7
A
0. 6
1234
0. 5
3292
0. 4
1335
1201
1028
2923
1165
3397
0. 3
1082
2853
0. 2
3525
823
0. 1
-0.04
2
3996.3
3000
2000
1500
1000
399. 2
cm-1
3
4
Figure S10: ATR-FTIR spectra of inked areas in parchment specimen with LIGG after 4
days artificial ageing
5
6
7
8
9
LIGG SPECIMENS, 4 DAYS AGEING; areaI1
LIGG SPECIMENS, 4 DAYS AGEING; areaI1 back face
LIGG SPECIMENS, 4 DAYS AGEING; areaI2
LIGG SPECIMENS, 4 DAYS AGEING; areaI3
10
14
1
2
LIGG Specimen: 8 days artificial ageing
Ink-free areas
1. 74
1114
1. 6
1135
1. 4
1623
600
1. 2
1539
1. 0
552
1029
0. 8
A
1449
2921
0. 6
667
1233
1203
3294
0. 4
3527
2852
1083
1340
1166
0. 2
0. 0
-0.13
3996.3
3
4
5
6
7
8
9
10
11
3000
2000
1500
cm-1
LIGG SPECIMENS, 8 DAYS AGEING; areaP1
LIGG SPECIMENS, 8 DAYS AGEING; areaP2
LIGG SPECIMENS, 8 DAYS AGEING; areaP2_ back face
LIGG SPECIMENS, 8 DAYS AGEING; areaP3 (scraped)
LIGG SPECIMENS, 8 DAYS AGEING; areaP4
LIGG SPECIMENS, 8 DAYS AGEING; areaP5 (scraped)
LIGG SPECIMENS, 8 DAYS AGEING; areaP6_ back face
12
15
1000
399. 2
1
Inked areas
1. 19
1. 1
1627
1. 0
1101
599
1029
0. 9
1533
549
0. 8
0. 7
0. 6
2924
A
1446
0. 5
3292
2852
0. 4
0. 3
3737
1340
0. 2
1743
2165
0. 1
0. 0
-0.06
3996.3
2
3
4
5
6
7
8
3000
2000
1500
cm-1
LIGG SPECIMENS, 8 DAYS AGEING; areaI1
LIGG SPECIMENS, 8 DAYS AGEING; areaI1 back face
LIGG SPECIMENS, 8 DAYS AGEING; areaI2
LIGG SPECIMENS, 8 DAYS AGEING; areaI3
LIGG SPECIMENS, 8 DAYS AGEING; areaI3 back face
9
10
16
1000
399. 2
1
2
LIGG Specimen: 16 days artificial ageing
Ink-free areas
1. 59
1. 4
1. 2
1627
599
1. 0
1542
1033
1102
0. 8
1448
549
1156
A
0. 6
3278
2921
0. 4
1203
1232
2852
1340
1085
1167
0. 2
0. 0
-0.12
3996.3
3
4
5
6
7
8
9
10
11
12
3000
2000
1500
cm-1
LIGG SPECIMENS, 16 DAYS AGEING; areaP1
LIGG SPECIMENS, 16 DAYS AGEING; areaP2
LIGG SPECIMENS, 16 DAYS AGEING; areaP2 back face
LIGG SPECIMENS, 16 DAYS AGEING; areaP3 (scraped)
LIGG SPECIMENS, 16 DAYS AGEING; areaP3 back face
LIGG SPECIMENS, 16 DAYS AGEING; areaP4
LIGG SPECIMENS, 16 DAYS AGEING; areaP5 (scraped)
LIGG SPECIMENS, 16 DAYS AGEING; areaP6
13
17
1000
399. 2
1
Inked areas
1. 22
1635
1. 1
1108
1. 0
0. 9
1542
551
0. 8
1029
599
1100
0. 7
1156
0. 6
A
1436
628
0. 5
1204
0. 4
3290
2925
667
1231
1082
0. 3
1161
1338
0. 2
0. 1
0. 0
-0.12
3996.3
2
3
4
5
6
7
3000
2000
1500
cm-1
LIGG SPECIMENS, 16 DAYS AGEING; areaI1
LIGG SPECIMENS, 16 DAYS AGEING; areaI1 back face
LIGG SPECIMENS, 16 DAYS AGEING; areaI3
LIGG SPECIMENS, 16 DAYS AGEING; areaI3 back face
8
9
10
18
1000
399. 2
1
2
LIGG Specimen: 32 days artificial ageing
Ink-free areas
1,52
1,4
1,3
1,2
1,1
1638
1151 1103
1,0
598
0,9
1542
0,8
1031
A 0,7
0,6
1448
559
0,5
1033
3298
0,4
0,2
1203
1232
2923
2957
0,3
3507
3067
667
1340
2854
1164
1085
0,1
0,0
-0,06
3996,3
3000
2000
3
4
5
6
7
8
9
10
11
12
1500
1000
399,2
cm-1
Figure S11: ATR-FTIR spectra of ink-free areas in parchment specimen with LIGG after
32 days artificial ageing
LIGG SPECIMENS, 32 DAYS AGEING; areaP2
LIGG SPECIMENS, 32 DAYS AGEING; areaP3
LIGG SPECIMENS, 32 DAYS AGEING; areaP4
LIGG SPECIMENS, 32 DAYS AGEING; areaP5
LIGG SPECIMENS, 32 DAYS AGEING; areaP6
19
1
Inked areas
1,24
1,2
1,1
1635
1099
1,0
0,9
1029
0,8
549
603
1523
0,7
628
0,6
1436
3274
A
474
0,5
0,4
0,3
1203
1233
3069
1162
1081
2929
0,2
2879
837
875
1338
0,1
0,0
-0,08
3996,3
2
3
4
5
6
7
8
9
10
3000
1500
2000
1000
399,2
cm-1
Figure S12: ATR-FTIR spectra of inked areas in parchment specimen with LIGG after 32
days artificial ageing
LIGG SPECIMENS, 32 DAYS AGEING; areaI1
LIGG SPECIMENS, 32 DAYS AGEING; areaI1 back face
LIGG SPECIMENS, 32 DAYS AGEING; areaI2
LIGG SPECIMENS, 32 DAYS AGEING; areaI3
LIGG SPECIMENS, 32 DAYS AGEING; areaI3 back face
11
12
13
20
2
Ferrous Sulfate Monohydrate
2.6
3333
2.5
1085
2. Additional Reference Spectra
2954
1
2.4
2319
1378
2.2
1459
1625
654
2.3
2.1
2
3500
3000
2500
2000
Absorbance / Wavenumber (cm-1)
1000
500
Paged Z-Zoom CURS OR
File # 1 : FERROUS S ULFAT E_NIS T-IR2
3
1500
30/3/2016 11:02 ðì Res=None
FERROUS S ULFAT E
4
5
6
Figure S13. Infrared spectrum of ferrous sulphate (FeSO4.H2O). Source: NIST Chemistry Webbook
Database; http://webbook.nist.gov/cgi/cbook.cgi?ID=B6000547&Units=SI&Mask=80#IR-Spec
Source reference: Coblentz No. 547. Coblentz Society
Collection ©2009 copyright by the U.S. Secretary of Commerce
on behalf of the United States of America. All rights reserved.
Notes
Spectral contamination due to oil around 2900, 1450, 1380 cm-1
7
8
9
10
21
Calcium Sulfate Semihydrate
1151
1118
1
1095
2
601
661
1.5
464
1008
3560
1622
3614
1
2362
.5
0
4000
3500
3000
2500
2000
%T / cm-1
1500
1000
500
Paged Z-Zoom CURS OR
File # 1 : ST D_038
5/9/2005 12:24 ìì Res=None
Gypsum / KBr
2
3
Figure S14. Infrared spectrum of calcium sulfate semihydrate (CaSO4.½H2O).
4
5
Source: Spectrum recorded at the Department of Conservation of Antiquities of Works of Art, TEI
of Athens.
6
7
22
Calcium Sulfate, Anhydrous
1160
1122
1
2.8
2.6
279
3465
2.2
615
680
2.4
2
3500
3000
2500
2000
Absorbance / Wavenumber (cm-1)
1000
500
Paged Z-Zoom CURS OR
File # 2 : CA LCIUM S ULFAT E ANHYDROUS_NIST - 7778-18-9
2
1500
14/8/2012 11:20 ðì Res=None
CA LCIUM S ULFAT E, ANHYDROUS
3
4
5
6
Figure S15. Infrared spectrum of anhydrous calcium sulphate (CaSO4). Source: NIST Chemistry
Webbook Database; http://webbook.nist.gov/cgi/inchi?ID=C7778189&Mask=80#IR-Spec
Source reference
Coblentz NO. 4672. Coblentz Society
Collection ©2009 copyright by the U.S. Secretary of Commerce
on behalf of the United States of America. All rights reserved.
7
8
9
10
23