Post on 27-Dec-2015
Identification of Historical Colourantsby Mass Spectrometry
Volodymyr Pauk
under the supervision of prof. Lemr
18.05.2012 by V.Pauk Palacky University in Olomouc
Faculty of ScienceDepartment of Anlalytical Chemistry
Olomouc 2012Ref. [1]
Outline
1. Introduction
2. Experimental
3. Results
4. Conclusion
18.05.2012 by V.Pauk
Introduction
1. Identification of colourants:• restoration• evaluation• approximate dating
2. ‘The Legend’
18.05.2012 by V.Pauk
Partial views of ‘Crucifixion’, St. Šebestian church on St. Hill in Mikulov
a b c
Ref. [2]
Introduction
3. Prussian Blue vs Indigo
18.05.2012 by V.Pauk
Ref. [3, 4, 5]
Prussian blue Indigo
• dark-blue shade• small shaped particles• high tinting strength
•highly insoluble in water and organic solvents
Synthetic,18th century, Berlin18th – 19th century
Natural, plant originAntique times – 19th century(replaced by synthetic dye)
Fe4[Fe(CN)6]3
Iron (III) hexacyanoferrate (II)
Indigotine
Experimental
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.)
18.05.2012 by V.Pauk
a) and b) FIA mass-chronograms 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;
18.05.2012 by V.Pauk
Results
c) MS spectrum of Prussian blue
d) MS spectrum of indigo
Linear calibration up to 5000 ng/mL
Traces of Prussian blue in samples !!!LOD: 10 ng/mL,
47 pg absoluteLOD: 12 ng/mL, 59 pg absolute
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
18.05.2012 by V.Pauk
Conclusion
References[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_de_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
18.05.2012 by V.Pauk