Abstract

The huge experience of the Institute in non destructive analysis and characteriza- key-words
tion of pigments, inks, colours and dyes allows to recognize the palettes used by
miniaturists, sometimes distinguishing the scriptoria themselves, identify posterior pigments
treatments and additions and assess the proper methods and products to be used xrf
in conservation. raman
α-pixe
We present the results obtained by means of non destructive spectroscopic molecular
mosaic gold
(Micro Raman) and elemental (XRF and α-PIXE) techniques in three case study, the
Pontificale 492 (13th century, Museo Diocesano, Salerno, Italy), the Bibbia Amiatina
(7th-8th century, Biblioteca Medicea Laurenziana, Firenze, Italy) and the ms. Piana
3.207 (13th century, Biblioteca Malatestiana Cesena, Italy). •

Agradecimentos por ajuda na configuração do texto e sugestões de Ana Catarina Sousa, Pedro Fialho
de Sousa, Justino Maciel, Felix Teichner e Heidi.
illuminations:
secrets, alchemy
and conservation in
three case studies
m a r i n a b i cc h i e r i
Istituto centrale restauro e conservazione patrimonio archivistico e librario, Roma (Italy), Head of Laboratory of Chemistry, marina.
[email protected]

mich el a mo n t i
Istituto centrale restauro e conservazione patrimonio archivistico e librario, Roma (Italy), Researcher of Laboratory of Chemistry, michela.
[email protected]

g i ova n n a p i a n ta n i da
Istituto centrale restauro e conservazione patrimonio archivistico e librario, Roma (Italy), Researcher of Laboratory of Chemistry, giovanna.
[email protected]

a r m i da s o d o
Istituto centrale restauro e conservazione patrimonio archivistico e librario, Roma (Italy), Researcher of Laboratory of Chemistry, and
Università di Roma Tre. Department of Physics, [email protected]

Achieving highly accurate information on miniatures composition allows to customize

conservation and restoration strategies aiming at the best preservation with the least
impact. Cultural heritage objects represent complex and multifaceted problems and
conclusions drawn from observations with the naked eye are likely as faulty as those
drawn from limited diagnostics. Moreover, the use of destructive techniques as many
traditional methods actually are is to be avoided, since samples are often unique,
priceless specimens. In order to work out reliable, unambiguous information from non
destructive methods a truly scientific approach, based on multidisciplinary analyses,
laboratory simulations and proper statistics, must be combined to the knowledge of
history, art and of course alchemy that guide the illuminator’s hand.
From the experimental point of view, a rich literature upon the use of elemental
(XRF, LIBS, EXAFS, α-PIXE ...) and molecular (ATR-FTIR, DRIFT, FT-Raman, Micro-
Raman...) spectroscopies can be found. In the light of previous experiences (Bicchieri

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et al. 2001, 169), the combination of XRF, α-PIXE and Micro Raman was considered
the proper setup choice.
XRF spectrometry is often (Malzer et al. 2004, 229; Cesareo et al. 2004, 703) ap-
plied to pigments and dyes analysis: information can be achieved in reasonable times
(minutes). Unfortunately, such information is only qualitative on paper and parch-
ment substrates, since elements lighter than Al (Si, in some cases) give a fluorescence
response below the detection limit, so it is impossible to detect organic substrates
even though the organic matrix contributes to the global spectrum. At the same time,
the X-rays penetration depth increases inversely to the atomic weight of the target
element and a sheet of paper or parchment is completely crossed. Quantitative XRF
analysis requires, in fact, that the thickness of the sample could be considered as
infinite, i.e. greater than the average thickness crossed by the used XRF radiation.
Calibration of the measuring arrangement and the use of reliable calibration model
that must be representative of the matrix and target element morphology (particle
size distribution, heterogeneity and surface condition) and concentration ranges of
the sample to be analysed are also necessary.
Contrariwise, α-PIXE allows controlling the penetration into the sample and quanti-
tative elemental information even on trace and lighter elements (above Na) can be
obtained. The simultaneous use of XRF and α-PIXE gives an almost complete charac-
terization of the elemental composition of the sample (Pappalardo et al. 2005, 114).
Raman spectroscopy is a technique sensitive to vibrational states of matter, that
actually constitute a «fingerprint» of the material. Raman spectroscopy can be used
(Colthup et al. 1990, 60) to identify the molecular composition or even the different
state of aggregation of the species in the sample under investigation. The advantages
of Raman spectroscopy consist in the short measurement time (seconds-minutes)
and in the high sensitivity to inorganic compounds. The main problem with Raman
applications is that fluorescence is excited together with the molecular states and
sometimes «screens» the measurement, making it impossible to extract data.
As far as measurements on the Pontificale 492 and Bibbia Amiatina are concerned,
the portable α-PIXE and XRF spectrometers were entirely designed and developed
at LNS/INFN laboratory and the portable micro-Raman spectrometer was a custom-
made instrument developed at Physics Dpt, Roma Tre University.
Measurements on the ms. Piana 3.207 were performed with the Assing Lithos 3000
portable XRF spectrometer and the Renishaw In-Via Reflex Raman microscope cur-
rently owned by the Institute (Bicchieri et al. 2008, 1074).
The full sets of analyses on Bibbia Amiatina and Pontificale 492, including the
instruments and their specifications, are fully described in dedicated articles. (Bic-
chieri et al. 2001, 169; Pappalardo et al. 2008, 466). They will be only synthetically
reviewed in present work, whereas a major focus will be given to the investigation
campaign on the ms. Piana 3.207 and the related experimental work on pigments
analysis and simulation of mosaic gold.
The Bibbia Amiatina, Codex Amiatinus, ms. Laur. Amiat. 1, is the last surviving out
of three copies of the Bible produced in Ceolfrith’s scriptorium in the area of the

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twin monasteries of Wearmouth Jarrow in Northumbria between the end of the 7th
century and the beginning of the 8th. It is composed of 1029 parchment sheets,
measures 345 mm x 540 mm and weighs around 50 kg. The manuscript is the most
ancient and complete witness to the Vulgate Latin Bible and it is also a great example
of English uncial writing and of illuminations in anglo-saxon style, influenced by the
Mediterranean-Bizantine one. Therefore its historical interest is inestimable.
The first goal of the analyses laid in the establishment of the original arrange-
ment of the sheets present in the first booklet. Some pigments, in fact, left offsets
on the adjacent sheet that were analyzed under ultraviolet light of two different
wavelengths (253 nm and 365 nm). It should be underlined that the ordering of
the sheets coming out from such a method did not necessarily correspond to the
original one, but rather represented the sequence that the pages had likely followed
for the bulk of the document’s lifetime. However, scholars agreed to adopt it when
re assembling the book.
For a complete characterization of the precious manuscript all illuminations were
analyzed coupling Raman, XRF and α-PIXE and have been recognized and classi-
fied (Table 1).

table 1 the bibbia amiatina palette

The ms. 492 Pontificale of Museo Diocesano di Salerno is dated back to a period
from the end of 13th century and the incoming of the 14th.
The manuscript consists of 349 parchment sheets each having dimensions 400 x 285
x 80 mm. The miniatures of excellent quality, ascribed to anonymous illuminators
working in the Bologna area, were not always completed: in some cases only the
preliminary design was present, in other cases the preparation was not covered by
the gold-leaf. These circumstances gave the unique opportunity to investigate the
different techniques used by the miniaturists and in particular the composition of the
gold preparations and their comparison with the medieval recipes. Using the differ-

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ent penetration depth of the three applied techniques it was possible to carry out a
completely non-destructive stratigraphy. Resulting palette is summarized in Table 2 .

table 2 the pontificale palette.

The experimental results also allowed to prepare laboratory reproductions of the

original illuminations, that were artificially aged and deteriorated in order to test
different adhesives on them and to choose the best and less invasive preservation
treatment.
The Decretum Gratiani, ms. Piana 3.207 (13th-14th c.), also known as Concordantia
discordantium canonum is a collection of Canon law. The code consists of 329 parch-
ment sheets (455 mm x 280 mm) and is preserved at the Biblioteca Malatestiana
in Cesena, Italy.
The restoration of ms. Piana 3.207 was the topic of project Salviamo un codice 2nd
edition, an initiative of Alumina – Nova Charta press – with the High Patronage of
the President of the Italian Republic (Savoia 2008). Ms. Piana 3.207 had been pre-
served in a very good condition up to the ‘80s, when it was dramatically maimed:
thirteen pages were torn off, damaging the sewing of the binding, and stolen. In the
following years, the law enforcement retrieved all the missing pages but one (c.107)
which is now considered lost. ICPL (now Icpal), the institutional authority appointed
for library materials preservation, was responsible for the thorough scientific analysis
of the manuscript and for the subsequent restoration.
XRF and Raman measurements allowed us to characterize the palette (Table 3).
Very interesting was the discovery that gilded miniatures had been realised either
with pure gold or with mosaic gold (tin IV sulphide; Fig.1 and 2). The latter pigment,
a yellow crystalline powder that closely resemble gold, was widely used in Europe in
the Middle Age and in the Renaissance and in ms. Piana was applied not as gold-
imitation but in order to obtain particular hues.
To confirm the presence of mosaic gold, a standard Raman spectrum was necessary.
Due to the fact that modern preparation of stannic sulphide differs from the an-
cient methods and that Raman spectra from literature (Edwards et al. 2003, 2291)

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table 3 the ms. piana palette.

1. Handbook of technical recipes, written in Latin had been obtained from the modern compound, we decided to prepare mosaic gold
by anonymous authors in the 14th century and following ancient recipes. Many texts were consulted, but the most detailed recipe
currently kept at the Biblioteca Nazionale di Na- was found in De Arte Illuminandi 1. Concerning amounts of reagents, not cited in
poli (Napoli, Italy).
the recipe, we decided to use the proportions suggested by Villavecchia: Dizionario
di Merceologia e di Chimica Applicata (Villavecchia 1932).
The procedure foresees many steps: preparation of Hg-Sn amalgam, addition of sul-
phur and ammonium chloride and heating for a long time, choosing the temperature

fig.1 x spectrum of mosaic gold from the original (christ robes). x ray source 96mo;
collimator 0.5 mm diameter, acquisition time 600s, x tube tension 25 kv, current
0.300 ma, esd silicon detector, resolution 160ev at 5.9kev

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in order to obtain the desired hue. In this process we can recognize the two first steps 2. Sulphur and Mercury are the alchemic pair.
of the alchemic Opus Magnum, the nigredo (mixing amalgam and the two others They are transported into the «labyrinth of the
compounds the mixture becomes black) and the albedo (during heating, dense white transformation of matter» by the external fire. In
the Temple (crucible, Ed.) their marriage is cele-
fumes rise) 2. When no more fumes appear, heating is stopped and a gold-coloured
brated and is only possible with the help of the
powder is found in the crucible: this is mosaic gold. arcane fire of salt – the alchemic Priest – able to
transform the metals. In chemical terms, amal-
gam increases the reactivity of tin; mercury re-
duces sulphur to sulphide. In meantime elemen-
tal tin is oxidized to tin IV. Ammonium chloride
decreases the reaction temperature, allowing the
formation of stannic sulphide.

fig.2 comparison between the raman spectra of mosaic gold laboratory sample (black
line, microscope image «a») and of the original pigment (red line, microscope image
«b»). excitation λ = 785 nm

Even when observed at the microscope, the similarity between the mosaic gold pre-
pared in the lab and the pigment used on the ms. Piana 3.207 is total and Raman
spectroscopy demonstrates that the two compounds had the same structure.
The effectiveness of the presented techniques in analysis of such invaluable manu-
scripts, the related scientific advance and the more than positive feedback from
restorers who take advantage from the obtained information, confirmed once more
the Institute choice of pioneering and always pursuing multidisciplinarity based on
strictly non-destructive methods. •

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