Micro-Raman on lead based pigments on a wall

painting
Ilaria Costantinia, Danilo Bersania, Antonella Casolib, Daniele Pontirolia,c,
Pier Paolo Lotticia
a

Physics and Earth Sciences Department, University, Parco Area delle Scienze 7/a, 43124 Parma, Italy
Chemistry Department, University, Parco Area delle Scienze 17/a, 43124 Parma, Italy
c
Laboratorio di Micro e Submicro Tecnologie abilitanti dell'Emilia Romagna (MIST.E-R), via P.
Gobetti 101, 40129 Bologna, Italy
b

Micro-Raman spectroscopy analyses have been carried out on some pictorial

fragments taken from a portion of a fresco in the Chapel of St. Stephen, situated in
Montani, Val Venosta (BZ), Italy, and painted around 1430. Especially on the apse
and on the vault, a dark alteration of lead based pigments is clearly visible. The
pigment was presumably mainly white lead, used to create light and dark effects.
Samples were taken from altered blackened areas and from areas cleaned according to
the traditional method of conversion of white lead, using a solution of acetic acid and
hydrogen peroxide in cellulose pulp. The cleaned samples appear in their original
colors, yellow and green.
The Raman spectra (LabRAM Horiba Jobin-Yvon instrument with 632.8 nm
excitation) have been taken at very low (< 0.1 mW) laser power due to the complex
behavior of lead oxides for photo-thermal effects induced by the laser excitation [1].
For the "cleaned" samples, characteristic spectra of lead-tin yellow pigments, both
type I and type II, were identified predominantly in green colored zones. Goethite,
haematite, celadonite, and lapis lazuli have also been found.
The micro-Raman spectra from blackened degraded samples, however, gave no
evidence of white lead: they show always a structured wide band centered at about
515-520 cm-1 which may be attributed to plattnerite (PbO2), a well known alteration
product of lead based pigments, especially in presence of moisture and in strongly
alkaline environment. In addition to the large width of the main Raman band, the
spectra show a feature at about 230 cm-1 that cannot be attributed to lead oxides
(Figure 1). The peak at 82 cm-1 has been found also in the Raman spectrum of mineral
plattnerite. XRD analysis confirmed the presence of plattnerite in the form of
nanosized crystals. Raman spectra collected in brownish red areas show often the
bands of red lead (Pb3O4) probably used as a pigment. The formation of plattnerite
could also be due to the degradation of red lead.
The Raman spectra taken at very low excitation light power on the samples often show
PbO (litharge/massicot) features of varying intensities. Traces of biological activity
were not detected. Sulfur compounds as lead sulfide (galena PbS) or lead sulfate
(anglesite PbSO4) were not identified on degraded samples.
A careful analysis of the behavior of synthetic powdered plattnerite under laser
irradiation was then performed. With increasing laser power, a band grows at about

390 cm-1 and subsequently a phase transformation is observed, corresponding to the

formation of massicot (-PbO) and litharge (-PbO) (Figure 2), orthorhombic and
tetragonal forms of lead monoxide, respectively.
The Raman spectra of massicot and litharge, obtained as laser induced thermal
degradation products of plattnerite, depend crucially on the laser power during the
measurement: a shift of the peaks towards lower wavenumbers and large broadening
of the Raman bands with increasing power is observed. The massicot main feature
varies from 145 to 135 cm-1 while that of litharge from 146 to 140 cm-1. When both
lead oxide species may be present, their identification is difficult if the laser power
exceeds 0.1 mW. On the contrary, analyses carried out on synthetic massicot and
litharge reveal minor changes the Raman spectra with increasing excitation power.

Figure 1: Raman spectrum of powered

synthetic plattnerite (a) and of the alteration
product on the fresco (b). The features at 82
and 231 cm-1 are found in all spectra together
with the large band at about 515 cm-1.

Figure 2: Raman spectra of litharge (L) and

massicot (M) taken with increasing laser
power on the sample: from D2 (0.05 mW) to
D0 (5 mW).

In conclusion, white lead escaped observation (a total conversion in plattnerite is

plausible) and the Raman spectrum of the degradation product, taken at very low
excitation power, shows features that do not belong to other common lead oxide
phases.

REFERENCES
1. L. Burgio, R.J.H. Clark, S. Firth, Analyst 126 (2001) 222227.