Tatiana R. Usacheva (ISUCT, Ivanovo)

Study and diagnosis of environmental deterioration of
historical parchments through correlation between
chemical-physical and innovative multispectral
imaging techniques
Giuseppe Della Gatta
Formerly at Dept of Chemistry, University of Turin, Italy
Elena Badea
Faculty of Sciences, University of Craiova, Romania (on leave at University of Turin, Italy)
Tatiana R. Usacheva
Ivanovo State University of Chemistry and Technology, Ivanovo, Russia
Alessandro Vitale Brovarone
Department of Humanistic Studies, University of Turin, Italy
Giuseppe Rossi, Paola Iacomussi
Optics Division, National Institute of Metrological Research, Turin, Italy

Our Partners
Prof. Giuseppe Della Gatta
Coordinator of the research on
environmental deterioration
of historical parchments
Prof. Giuseppe
Della Gatta
giuseppe.dellagatta@unito.it
Visit to Ivanovo State University of Chemistry and Technology (2004)

Study and diagnosis of environmental
deterioration of historical parchments…
In collaboration with UNITO, Dept of Chemistry
Prof. Giuseppe Della Gatta
Prof. Salvatore Coluccia
Dr. Elena Badea
EC project IDAP (Improved Damage Assessment of Parchment)
2002-2005
http://www.idap-parchment.dk
Piedmont Region project OPERA (Old Parchment: Evaluating
Restoration and Analysis) 2006-2009
www.opera-parchment.it
In collaboration with UNITO, Dept of Humanistic Sciences, and INRiM, Optics Division
Prof. Alessandro Vitale Brovarone, Prof. Giuseppe Della Gatta, Dr. Elena Badea
Dr. Eng. Giuseppe Rossi, Dr. Paola Iacomussi
MuSA-System
Compagnia di San Paolo Foundation project MuSA-System
(Study and Diagnosis of Historical Parchments Using Improved
Systems for Multispectral Analysis) 2011-2012

PARCHMENTS - WHAT THEY ARE
Some famous examples of historic
Parchments belong to the most valuable objects of the cultural
heritage since they are bearers of historical facts and ideas,
which have shaped the development parchments: of our society over a period
of many centuries.
The Dead Sea Scrolls (200 B.C. to 68 A.D.)
Plinius described the preparation of new support for writing
invented Codex in Vaticanus, Pergamon at Codex the beginning Sinaiticus of 2(4 th th century) B.C. It
represented an excellent substitute for papyrus.
The Treaty of Perpetual Peace (1502)
Parchment (pergaminus in Latin) is named after the city where it
was The perfected. Constitution of the United States of America
(1787)
Although parchment never interrupted being used (primarily for
governmental and official documents) it had ceased to be a
primary choice for writing supports by the end of 15 th century.

DAMAGE ASSESSMENT - a preliminary step for
preservation and restoration of parchment
Parchments (documents, bookbindings, various artefacts) are exposed
to deterioration by a number of external factors (UV-Vis light, humidity
and temperature variation, atmospheric pollution, micro-organisms, etc).
We have simulated old parchment
environmental ageing by exposing new
parchment to temperature, humidity,
light, NO x and SO 2 action aiming to
correlate degradation effects induced in
weeks to the damage sustained over a
number of centuries.
We investigated changes in thermal & structural stability of collagen occurring on
environmental deteriorating action. This allowed us to drawn a rather large damage picture
of artificial ageing and better describe/assess deterioration aspects in old parchments.

Our part of tasks
Study of deterioration pathways of collagen in parchment by differential
scanning calorimetry (DSC) in excess water and in dry condition
Elaboration of damage assessment protocols and models for long-term
prediction of structural stability of parchment subjected to
environmental impact
Differential scanning calorimetry
Thermal denaturation of collagen within parchment
Thermal stability of parchment
Characterisation and ranking of deterioration

Differential scanning calorimetry
On heating, collagen undergoes a transition to a disordered structure,
a mixture of single or multi-stranded polypeptides with random coil structure,
called thermal denaturation. It gives rise to a DSC endotherm peak.
Denaturation enthalpy, denaturation
temperature and shape of the DSC
peak are thermodynamic parameters
correlated to parchment stability.
(1) molecular collagen in solution
(2) parchment in excess water
(3) parchment in dry condition
T d , D d H, DT 1/2
Changes in these quantities depend
on specific changes in parchment,
i.e. helix-coil transition,
gelatinisation, crosslinking,
hydrolysis.

Environmental ageing effect on DSC
peak parameters
DSC curves for a series of parchments exposed to accelerated ageing at 80 C
and daily relative humidity (RH) alternations (40% and 80%) showing progressive
shifting to lower temperatures, strong broadening and a small transition at T < 30 C.

Environmental ageing effect on DSC
peak parameters
DSC denaturation curves of the samples aged for 32 days at
(a) 40 °C; (b) 60 °C; (c) 80 °C

Environmental ageing effect on DSC
peak parameters
Historic bookbinding (TO-108) dated 1352
Historical Archives of the City of Turin
6
5
Cover (external)
new parchment
6
5
Cover flap (internal)
new parchment
4
4
C p
/ J K -1 g -1
C p
/ J K -1 g -1
3
2
CR55
CR43
TO108_2
(historic parchment)
3
2
SC 106
SC 185
TO108_1(historic parchment)
1
1
0
0
20 30 40 50 60 70 80 90 100
temperature / °C
CR 43 – new parchment exposed to 50
ppm SO 2 + heat + light for 4 weeks
CR 55 – new parchment exposed to (SO 2
+ NO x + heat) for 4 weeks
20 30 40 50 60 70 80 90 100
temperature /°C
SC 185 – new parchment exposed to humid
heating (80 C + 80% and 40% RH) for 32 days
SC 106 – new parchment exposed to humid
heating (80 C + 80% RH) for 32-day

Environmental ageing effect on DSC
peak parameters
Historic bookbinding (TO-104) dated 1380
Historical Archives of the City of Turin
6
5
Cover (external)
new parchment
6
5
Cover flap (internal)
new parchment
4
4
C p
/J K -1 g -1
3
2
1
CR20 (aged parchment)
TO104_1(historic parchment)
C p
/ J K -1 g -1
3
2
1
SC105 (aged parchment)
TO104_2 (historical parchment)
0
0
20 30 40 50 60 70 80 90 100
temperature / °C
20 30 40 50 60 70 80 90 100
temperature / °C
CR 20 – new parchment exposed to 50
ppm NO x and daylight irradiation for 16
weeks
SC 105 – new parchment exposed to
16-day humid heating (80 C + 80% RH)

Protocols for Damage Ranking in Old Parchments
Damage ranking of a group of archival bookbindings.
Historical Archives of the City of Turin, XIV century
Sample 4 comprehensively displays increasing damage of its inner
part (F4), outer part (C4) and more exposed part (S4).

Damage ranking for a group
of archival bookbindings
Historical Archives of the City of Turin, XIV century
sample
Document
year
damage level
DSC SEM pathways
cross-
TO 102_1 medium slight denaturation, cross-linking
TO 102_2 1363 major medium molecular denaturation,
/heavy linking, hydrolysis
TO 102_3 major medium molecular denaturation, crosslinking,
hydrolysis
TO 102_4
TO 104_1 1380 medium slight /
medium
TO 104_2
TO 106_1
TO 106_2
TO 106_3
1404
major medium denaturation, cross-linking
slight /
medium
medium
/ major
medium
/ major
slight /
medium
heavy
heavy
cross-linking, hydrolysis
cross-linking, hydrolysis
gelatinisation, cross-linking
gelatinisation, cross-linking
medium slight gelatinisation, high cross-linking
TO 107_1 1375 medium medium hydrolysis, cross-linking
TO 107_2
major medium gelatinisation, cross-linking
TO 108_1 1415 medium medium high cross-linking, hydrolysis
TO 108_2
medium
/ major
medium
gelatinisation, cross-linking

MuSA System: Study and Diagnosis of Historical Parchments
Using Improved Systems for Multispectral Analysis
Funded by the Compagnia di San Paolo Foundation, Turin
Partners
National Institute of Metrological Research (INRiM), Turin, Italy
University of Turin (UNITO), Italy
Collaborators
School of Conservation, Royal Danish Academy of Fine Arts, Denmark
National Research-Development Inst.Textile & Leather, Bucharest, Romania
Institute of Natural Sciences and Technology in Art, Vienna, Austria
Ivanovo State University of Chemistry and Technology
End-users
State Archives of Turin
Historical Archives of the City, Turin
Historical Archives of the University of Turin
National University Library of Turin
Royal Library, Turin
State Archives of Genoa

MuSA System
Stage 1
Software Development
Reference samples collection
Chemical-physical analises
(micro DSC, MHT, SEM)
Digitalisation and MSA analysis
(non-destructive)
DATA BASE
chemical-physical data
DATA BASE
multispectral data
Correlation analysis
Diagnosis software
Digital scanning
(Visible spectra achievement)
Historical Documents
Damage assessment
Stage 2
Digitalisation and Damage Ranking

Thank you for your attention

Joint Papers in ISI Journals
Parchments
Della Gatta G, Badea E, Ceccarelli R, Usacheva T, Mašić A. Assessment of Damage in
Old Parchment by DSC and SEM, J. Therm. Anal. Cal. 82, 637-649 (2005).
Badea E, Della Gatta G, Usacheva T, Effects of Temperature and Relative Humidity on
Fibrillar Collagen within Parchment: A Micro Differential Scanning Calorimetry Study (micro
DSC), Polym Degrad Stab 97, 346-353 (2012).
Badea E, Miu L, Kurysheva A, Carsote C, Della Gatta G. The Relation between the
Thermal Stability at Micro and Mesoscopic Levels in Parchment and Leather: a Differential
Scanning Calorimetry and Thermal Microscopy Study, J. Cult. Heritage 2011 (submitted).
Badea E, Poulsen Sommer DV, Mühlen Axelsson K, Kurysheva A, Della Gatta G, Larsen
R, Standardised Methods for Damage Ranking in Parchment: from Microscopic Evaluation
to Collagen Denaturation Assessment, e-Preservation Science 2012 (submitted).
Solution Chemical Thermodynamics
Della Gatta G, Usacheva T, Badea E, Palecz B, Partial Molar Heat Capacities of Small
Peptides in Water at 298.15 K by Isothermal Calorimetry, J. Chem. Thermodyn. 38, 1054-
1061 (2006).

Joint Papers in Proceedings (2011 – 2008)
Badea E, Della Gatta G, Usacheva T, Kurysheva A, Effect of Temperature and Relative Humidity on Molecular and
Mesoscopic Structure of Parchment, in Proceedings of ART’11 - 10 th International Conference on non-destructive
investigations and microanalysis for the diagnosticsand conservation of cultural and environmental heritage,
Florence, 13-15 April 2011.
Badea E, Della Gatta G, Odlyha M, Larsen R, Usacheva T, Physical-Chemical Tools for the Assessment of Indoor
Environmental Effects on Archival Parchment Heritage in a Changing Climate. XIII International Scientific and
Technical Conference “High-Tech in Chemical Engineering 2010”, Ivanovo-Suzdal, 29 June-2 July 2010.
Badea E, Usacheva T, Della Gatta G, Thermodynamic Study of Hydration at Infinite Dilution of Uncharged Small
Peptides by Isothermal Microcalorimetry. Annual Symposium of the Commission of Thermal Analysis and Calorimetry
- Romanian Academy of Sciences, Bucharest, 12 th February 2010.
Badea E, Della Gatta G, Budrugeac P, Usacheva T, Assessment and Ranking of Archival Parchment Deterioration by
an Integrated Thermal Analysis Approach. 9 th Mediterranean Conference on Calorimetry and Thermal Analysis
(MEDICTA 2009), Marseille, 15-18 June 2009.
Della Gatta G, Badea E, Budrugeac P, Poulsen DV, Giurginca M, Usacheva T, Miu L, Degradation of collagen in
parchments by NO x and SO 2 : an integrated physical-chemical approach. XXXVII Congresso Nazionale di Chimica
Fisica, Camogli - Genova, 24-29 Febbraio 2008.
Badea E, Usacheva T, Saczuk M, Della Gatta G, Ageing Features in Various Parchments Materials: a DSC
Comparison Study of Bookbindings, Rolls and Individual Sheets. International Seminar and Workshop “Conservation
and Restoration of Parchments” (CRP 2008), Turin, 5-7 September 2008.

Joint Papers in Proceedings (2007– 2005)
Badea E, Della Gatta G, Usacheva T, Ceccarelli R, Mašić A, DSC Study of Parchments Deterioration: from Micro to
Molecular Structure. 41 st IUPAC World Chemistry Congress, Turin, 5 – 10 August, 2007.
Miu L, Budrugeac P, Gaidau C, Kurysheva A, Badea E, Della Gatta G, Age-Related Stability of Old Leather. 41 st
IUPAC World Chemistry Congress, Turin, 5 – 10 August, 2007.
Della Gatta G, Badea E, Abate L, Usacheva T, Odd-Even Effect In Fusion Properties Of Some Homologous Series of
Terminally Bifunctional Alkyl Compounds. XVI Russian International Conference on Chemical Thermodynamics,
Suzdal, 1 - 6 July, 2007.
Badea E, Mašić A, Ceccarelli R, Usacheva T, Della Gatta G, Structural and Thermal Stability of Collagen within
Parchment: a Mesoscopic and Molecular Approach. 9 th European Symposium on Thermal Analysis and Calorimetry,
Kraków, 27 – 31 August 2006 and XXXV Congresso Nazionale della Società Chimica Italiana, Florence 10 – 15
September 2006.
Della Gatta G, Badea E, Mašić A, Kurysheva A, A Protocol for the Deterioration Assessment and Ranking of Historical
Parchments Based on DSC, SEM, ATR-IR and NMR Study. COST international meeting “Cultural Heritage and
Science: An Interdisciplinary Approach for the Conservation of Museum Objects”, Ghent University, 5 - 7 December
2006.
Badea E, Della Gatta G, Mašić A, Usacheva T, Coluccia S, Benedetto B, Braghieri A, Environmental Ageing of
Parchment Bookbindings: a DSC, SEM and Unilateral NMR Study. XXXIV Congresso Nazionale della Divisione di
Chimica Fisica – Società Chimica Italiana, Siena, 20 - 24 Giugno 2005.
Della Gatta G, Badea E, Usacheva T, Mašić A, Benedetto S, Braghieri A, Comparative study of environmental ageingrelated
changes in parchments by calorimetry and electron microscopy. ICOM-CC
14 th Triennial Meeting, The Hague, 12 - 16 September 2005.
Badea E, Della Gatta G, Usacheva T, Ceccarelli R, Mašić A, Ichim D, Damage Assessment in Old Parchments:
Collagen Structure and Thermodynamic Properties. 7 th Mediterranean Conference on Calorimetry and Thermal
Analysis (MEDICTA 2005), Thessaloniki, 2 – 6 July, 2005.
Della Gatta G, Badea E, Mašić A, Ceccarelli R, Usacheva T, Kurysheva A, Collagen Structure And Its
Thermodynamic Properties In Parchments. Russian International Conference on Chemical Thermodynamics,
Moscow, 27 June - 2 July, 2005.

Joint Papers in Proceedings (2004 – 2003)
Della Gatta G, Badea E, Ceccarelli R, Mašić A, Usacheva T, Stability of Collagen In Artificially Aged and Old
Parchments. 13th Conference of the International Confederation for Thermal Analysis and Calorimetry (ICTAC 13),
Chia Laguna – Cagliari, 12-15 September 2004.
Badea E, Mašić A, Ceccarelli R, Usacheva T, Della Gatta G, Bodo B, Artificial ageing of collagen in parchment in
presence of NO 2 . VIII Congresso Nazionale do Chimica dell’Ambiente e dei Beni Culturali, Colle Val d’Elsa - Siena,
8 – 11 June 2004.
Della Gatta G, Usacheva T, Badea E, Pałecz B, Calorimetric Study of Solvation of Some Small Peptides in Water.
XXXIII Congresso Nazionale della Divisione di Chimica Fisica – Società Chimica Italiana, Naples, 21 - 25 June
2004.
Della Gatta G, Usacheva T, Badea E, Pałecz B, Calorimetric Study of the Solvation of Some Small Peptides In
Water At 298.15 K. Plyos, 28 June-2 July 2004
Della Gatta G, Usacheva T, Badea E. Pałecz B, Partial Molar Heat Capacities of Small Peptides in Water at 298.15
K by Isothermal Calorimetry. 6 th Mediterranean Conference on Calorimetry and Thermal Analysis (MEDICTA 2003),
Porto, 27 – 30 July 2003.
Della Gatta G, Pałecz B, Usacheva T, Badea E, Thermodynamics of Solvation of some Small Peptides in Water
Solution at 298.15 K. 9 th Conference on Calorimetry and Thermal Analysis (CCTA9), Zakopane, 31 August – 5
September 2003.