Palacky University in Olomouc
Faculty of Science
Department of Anlalytical Chemistry
Identification of Historical Colourants
by Mass Spectrometry
Volodymyr Pauk
under the supervision of prof. Lemr
Ref. [1]
Olomouc 2012
18.05.2012 by V.Pauk
Outline
1. Introduction
2. Experimental
3. Results
4. Conclusion
18.05.2012 by V.Pauk
18.05.2012 by V.Pauk
Introduction
1. Identification of colourants:
• restoration
• evaluation
• approximate dating
2. ‘The Legend’
a
b
c
Partial views of ‘Crucifixion’, St. Šebestian church on St. Hill in Mikulov
Ref. [2]
18.05.2012 by V.Pauk
Introduction
3. Prussian Blue vs Indigo
Prussian blue
Indigo
•dark-blue shade
•small shaped particles
• high tinting strength
•highly insoluble in water and organic solvents
Synthetic,18th century, Berlin
18th – 19th century
Natural, plant origin
Antique times – 19th century
(replaced by synthetic dye)
Fe4[Fe(CN)6]3
Iron (III) hexacyanoferrate (II)
Indigotine
Ref. [3, 4, 5]
Experimental
18.05.2012 by V.Pauk
Equipment:
Micromass Q-TOF Premier, Z-spray ESI source, negative mode;
Acquity UPLC system; Elma S40H ultrasound bath, 0.45 µm filters.
Sample preparation:
Eq. 1
Fe4[Fe(CN)6]3 + NaOH → Fe(OH)3↓ + Na4[Fe(CN)6]
Eq. 2
Data acquisition and processing:
m/z 133.95 (Prussian blue), m/z 263.08 (indigotin),
Mass lynx v. 4.0 (Waters Laboratory Informatics)
QC Expert v. 3.2 (TriloByte LTD.)
Results
18.05.2012 by V.Pauk
a) and b) FIA masschronograms of
Prussian blue and
indigo;
curves I, II, and III
respond to 100, 1000
and 5000 ng/mL ,
respectively;
integrated peak areas
for 5000 ng/mL are
shown;
c) MS spectrum
d) MS spectrum
of Prussian blue
of indigo
LOD: 10 ng/mL,
LOD: 12 ng/mL,
47 pg absolute
59 pg absolute
Linear calibration up to 5000 ng/mL
Traces of Prussian
blue in samples !!!
Conclusion
18.05.2012 by V.Pauk
Developed method:
•successful in analysis of real samples
•fast
•sensitive
•no chromatographic separation
Application:
Fast screening of Prussian blue and indigo in historical
and art objects
References
18.05.2012 by V.Pauk
[1] Reproduction of Peter Paul Rubens - La découverte de la pourpre available on
http://no.wikipedia.org/wiki/Fil:Peter_Paul_Rubens__La_d%C3%A9couverte_d
e_la_pourpre.JPG.
[2] Partial photos of the painting of ‘Crucifixion’, St. Šebestian church on St. Hill in
Mikulov, Czech Republic, available on
http://breclavsky.denik.cz/multimedia/galerie/2328622.html?section=1,1.
[3] Kirby, J.; Saunders, D. Fading and colour change of Prussian blue: methods of
manufacture and the influence of extenders. National Gallery Technical Bulletin
(London), 2004, 25: 73 – 99.
[4] Bartoll, J. The early use of prussian blue in paintings. 9th International
Conference on NDT of Art, Jerusalem Israel, 25–30 May 2008.
[5] Bechtold, T.; Mussac, R. Handbook of natural colorants. Wiley, 2009, 412 p.
18.05.2012 by V.Pauk
Thank You for attention