Journal of Cultural Heritage 61 (2023) 188–193

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Journal of Cultural Heritage

journal homepage: www.elsevier.com/locate/culher

VSI: LACONA XIII

A new underwater laser cleaning tool for large bronze artefacts

Giovanni Rotondi a,1,∗, Annalena Brini a, Francesco Cantini b,c,d
a
MIBACT - Opificio delle Pietre Dure di Firenze (OPD), Firenze, Italy
b
Università degli Studi di Firenze, Dipartimento di Fisica e Astronomia, Sesto Fiorentino, Italy
c
Consiglio Nazionale delle Ricerche, Istituto di Fisica Applicata Nello Carrara (CNR-IFAC), Sesto Fiorentino, Italy
d
Istituto Nazionale di Fisica Nucleare, Laboratorio di Tecniche Nucleari per i Beni Culturali (INFN-Labec), Sesto Fiorentino, Italy

a r t i c l e i n f o a b s t r a c t

Article history: A group of twenty-eight fragments of monumental bronze statues from the Roman Age, recently under-
Received 8 February 2023 went a series of conservation treatments at the Opificio delle Pietre Dure (OPD) in Florence, Italy. These
Accepted 31 March 2023
fragments had never been investigated or cleaned before. During this restoration, supported by an exten-
sive diagnostic campaign, an attempt was made to understand the conservation issues of each fragment
Keywords: and to identify the most suitable cleaning treatment in order to guarantee the removal of concretions
Laser ablation and alteration products without damaging these precious artworks.
Underwater irradiation In particular, two large scale fragments, depicting the two sides of a horse’s maned neck, and identi-
Methods in conservation fied as part of an equestrian monument, showed traces of gilding emerging from a thick layer of mineral-
Gilded bronzes
ization and sand encrustations. The bronzes were then subjected to cleaning tests by means of laser abla-
tion to reveal any further remains of gilding. Among the different application methods of laser cleaning,
irradiation in water has demonstrated its effectiveness in this case, offering operational advantages due
to cavitation-mediated processes. Due to the size and shape of the artefacts (characterized by protruding
details such as the mane, etc.), and the general state of conservation, it was impossible to submerge them
completely or apply plastic films on their surface to create “pocket pools” filled with deionized water.
In this paper we present a new tool for underwater laser cleaning application based on the modi-
fication of a water brush pen capable of creating an extremely localized water vesicle, avoiding placing
any containment system on the surface. This method has proved to be very powerful in removing the
mineralized layer without affecting the underlying gold leaf, leaving only a few traces of the deposits.
© 2023 Consiglio Nazionale delle Ricerche (CNR). Published by Elsevier Masson SAS. All rights reserved.

1. Introduction
Laser ablation is one of the most important cleaning methods in
the field of cultural heritage conservation. This method, which has
been the state of the art for more than two decades, has seen an
exceptional evolution from the pioneering studies of the 70 s, until
it became one of today’s most successful examples of technology
transfer, bringing from research laboratories directly into hands of
conservators and restorers all over the world a practical, versatile
tool for surfaces cleaning [1,2].
Furthermore, the systematic application of laser ablation in the
field of Cultural Heritage (CH) has favoured the development and
evolution of its application. Indeed, as each work of art inevitably
represents a case study itself, each conservation intervention must
be shaped on the specific characteristics of the artefacts, forcing
the restorers to adopt a trial-and-error approach to find the most
∗ facts usually relies on little information about the archaeological
Corresponding author.
E-mail address: giovanni.v.rotondi@gmail.com (G. Rotondi).
1
Present address: Via Felice Fontana, 42, 50144 Firenze, FI, Italy.
effective and least invasive cleaning system. Among the recent ap-
plications on historical metal artefacts, underwater irradiation has
been successfully tested with positive results [3].
This method, based on cavitation-mediated processes, provides
numerous advantages particularly required in the CH field, such as
faster cooling of irradiated area, a small focal spot size, the induced
water explosive evaporation that helps to carry debris away, etc.
[4–8].
From a conservation point of view, ancient bronzes artefacts,
due to their centuries-old burial and/or immersion, often consti-
tute, from diagnostics to conservation, complex and problematic
study cases. Today, only very few ancient bronze honorary mon-
uments, which formerly crowded cities, survive, and often not in
their entirety, due to iconoclasm and the recycling of their precious
material. Testifying to their grandeur are often the surviving frag-
ments occasionally found during excavations or from chance recov-
eries from the seabed. The preservation of these large metal arte-
context. The restoration of surfaces and of the artworks themselves
therefore remains one of the most important sources of knowl-

https://doi.org/10.1016/j.culher.2023.03.012
1296-2074/© 2023 Consiglio Nazionale delle Ricerche (CNR). Published by Elsevier Masson SAS. All rights reserved.
G. Rotondi, A. Brini and F. Cantini
Fig. 1. The two horse neck fragments (inv. No. 22.S155–18.196 SABAP Firenze) before the conservation treatment (A fragment I, B fragment II). Gilding emerging from a thick
layer of mineralization and encrusted sandy deposits on fragment II (C).
edge. Conservation and cleaning interventions are often carried out
by mechanical and chemical means; in some cases, laser ablation
is used, especially in the presence of residues of gilding.
In this work, which was developed as part of the conserva-
tion project of a group of twenty-eight fragments of bronze stat-
ues from the Roman era [9], the results of the laser cleaning of
two large fragments will be presented. The two fragments (Fig. 1A,
B) (size: ∼ 14 × 58 × 68 cm and 10 × 55 × 48 cm; W-L-H) repre-
sent the two mating sides of a maned horse’s neck and have been
identified as part of an equestrian monument. Both showed traces
of leaf gilding emerging from a thick layer of mineralization and
sandy concretions. (Fig. 1C).
Due to conservative issues and to the size of artefacts, their
complete immersion is not always possible. A strategy that helps
to overcome this limitation consists in creating water-filled “pock-
ets” on the surface of the artwork exploiting adhesive tapes and a
transparent plastic film [10].
Although our restoration group has already successfully applied
this method in other interventions [11,12], for this specific case,
some risks (such as the application of adhesives on the surface of
the artefacts with the risk of damaging the gold leaf) and problems
(due to the difficulties of creating "pocket pools" on complex and
irregular surfaces), prompted us to look for an alternative way to
apply laser cleaning in water.
As simple as it may seem, efficiently bringing the right amount
of water to the surface of the artefact remains one of the most
complex practical problems in using underwater laser cleaning.
Furthermore, water should only be conveyed to the areas to be
cleaned, avoiding stagnation, infiltrations and wetting sensitive ar-
eas of the specimen due to fragility or pathology. A striking exam-
ple is the gilding cover an archaeological bronze artefact which can
very easily be affected by active chloride corrosion (bronze cancer)
[13].
Here we present a laser cleaning approach that easily and ef-
fectively overcome these practical limitations by modifying a water
brush pen capable of creating an extremely localized water vesi-
cle, avoiding the placing of any containment system on the sur-
face. The presented method is able to provide the same benefits as
underwater irradiation without exposing the artefacts to prolonged
immersion in water [3], and without applying adhesives [10–12] to
a sensitive surface. This process also avoided many physical inter-
actions with the artwork, leaving only the removal of thicker sandy
crusts and mineralized residues to mechanical tools.
2. Research aim
The case study we present therefore required us to adapt the
established procedure for the application of laser ablation in water.
189
Journal of Cultural Heritage 61 (2023) 188–193
Our goal is to propose a tool that allows you to apply underwater
laser cleaning, with effective results, even on surfaces with delicate
gilding and a complex morphology.
3. Material and methods
Before approaching the cleaning process, numerous samples of
surface material were investigated by SEM-EDS analysis at the OPD
Scientific Laboratory. SEM-EDS analyses were performed with the
OXFORD Instrument Zeiss EVO® MA 25 with Oxford EDS X-MAX
equipped with 80 mm2 probe for microanalysis. The analysis of
samples taken from the surface provided us with details on the
technique used for the gilding (gold leaves without mercury amal-
gam) and the composition of the surface concretions. The thick en-
crustations consisted mostly of silica and silicates, iron compounds
and a layer of cuprite (Fig. 2).
Initial cleaning tests, performed by mechanical means, showed
that the cuprite patina covered other gilded areas. However, scalpel
removal of large cuprite flakes also caused the gilding parts to peel
off in many cases, as shown in the SEM-BSE image of a sample
(Fig. 2). The bare cuprite layer was also too thin to be removed by
other mechanical means, such as the piezoelectric ultrasonic de-
vice or the pneumatic engraver, without affecting the underlying
gold leaf.
Chemical cleaning capable of completely dissolving the crusts
was not advisable as it would have been too aggressive.
Given the nature of the gilding, laser ablation tests were per-
formed using a Short Free Running Nd:YAG laser system [14,15],
moistening the surface of the artwork with deionised water us-
ing various systems. These included brushes, bricks made of gellan
gum and, given the large size of the artefacts that prevented them
from being completely immersed, water-filled “pockets” made of
adhesive tapes and transparent plastic films, as initially realised by
Mignemi [10].
Some tests were also conducted by applying ion exchange
resins (mixture of cationic and anionic resins, as detailed below)
before laser ablation, to weaken the concretions and facilitate the
removal. The same products were effectively used on other, non-
gilded, fragments prior to the mechanical removal of the concre-
tions. The use of this kind of product was preferred over other
chelating compounds due to the non-saline nature and the self-
inactivation of the ion exchange resins, ensuring lesser risks for the
leaf gilding if residues were left on the surface [15].
After testing various alternatives, an attempt was also made to
create “boxes” consisting of a plastic frame, a deformable neoprene
seal on the back (to be placed on the surface of the bronze) and
a transparent film on the front. This was done in order to fix such
“boxes” onto the work by means of the pressure exerted by a few
G. Rotondi, A. Brini and F. Cantini
Fig. 2. SEM-BSE image (A) of a patina sample from one of the fragments and corresponding SEM-EDX spectrum (B). Elemental analysis and semi-quantitative results (C)
showing a composition compatible with cuprite. A fragment of gilding (small flakes in light grey) is also visible in the SEM-BSE image (A).
Fig. 3. One of the tests carried out for the creation of “pockets” without adhesives: gellan gum ring gasket and plastic film shown here both in photos (A) and with a graphic
diagram (B).
straps tied to the artwork. Alternatively, it was possible to cre-
ate a self-supporting “pocket”, made with a gellan gum ring gas-
ket and transparent plastic film, (without the use of any adhesive),
by exploiting the suction arising from the pulling force exerted on
the container (see Fig. 3 and video n. 1). However, all these ap-
proaches still presented serious implementation and operational
problems.
For this reason, it was decided to modify a water brush pen
(commercially available brush, 5 mm diameter) by inserting a
pipeline (internal diameter 4 mm) behind the bristles. The pipeline
was connected to a water tank, equipped with a tap, and posi-
tioned higher than the working surface; this would let the water
flow into the brush by gravity. A transparent film flap was then
applied to the outside of the bristle. Two different materials were
tested for this component, and both proved to be suitable: the
plastic film of the VELOXY® System from RGI bioSteryl Tech® and
a commercially available transparent polyethylene foil (150 gr/m2
wt). The whole process is based on a simple yet effective phe-
nomenon: when the water is released by the brush, a water drop
is trapped between the flap and the surface of the artwork. Laser
ablation can then take place through the flap and the underlying
“water pad”, as seen in the picture (Fig. 4).
The brush can be easily moved over the artwork, smoothly fol-
lowing all three-dimensional shapes (Fig. 4C), therefore resulting
in a versatile and adaptable tool.
During treatment, the artwork was positioned appropriately to
allow the excess water to run off by the shortest path, and the
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Journal of Cultural Heritage 61 (2023) 188–193
residual water was then removed from the workstation and col-
lected (Fig. 5A).
Our method also allows to tune the thickness of the “water
pad”, by changing the distance of the flap from the surface by
applying more or less pressure; the flap can either be folded or
removed in order to brush the surface just like a standard water
brush pen, but without the need to squeeze the handle, as the wa-
ter flux is provided by the internal pipeline.
The mechanical effects generated during laser ablation in wet
conditions usually cause water spreading, and also lead to the de-
position of soiling on the protective goggles, and on the optical
components of the irradiation apparatus handpiece. Our method,
thanks to the presence of the transparent flap, confines all the tur-
bulence within the “water pad”, preventing water spreading and
limiting to the minimum the emission of fumes.
A definitive cleaning protocol was then benchmarked. The main
passages of the process were carried out as follows:
1) Application of CTS® Ionex H® strong cationic ion-exchange
resin and CTS® Ionex OH® strong anionic ion-exchange
resin in a 40/60% by weight. The resins were applied af-
ter imbibition with demineralised water in form of com-
presses supported by Japanese paper. The application was
maintained for 45 min, slowing down the evaporation of wa-
ter by covering the poultice with a polyethylene film.
2) Laser ablation: a pulsed short free running Nd:YAG laser
was employed (El.En.® Smart Clean II®, source: Nd:YAG,
G. Rotondi, A. Brini and F. Cantini Journal of Cultural Heritage 61 (2023) 188–193

Fig. 4. Modified water brush pen diagram (A), showing the formation of the “water pad” that allow for a local underwater laser cleaning without submerge the work of art.
Close-up detail of the pen brush tip (B). The actual instrument in situ application (C).

Fig. 5. Fragment I during the cleaning process. It is possible to appreciate the exceptional state of preservation of the gilding, which is still reflecting. The setting of the
workstation can also be seen (A). After the cleaning it is also possible to recognize the overlapping edges of the different gold leaves (B) and other details related to
production and possible destruction of the artwork.

Fig. 6. SEM-EDS Analysis of dark flakes removed from the gilded surface by laser cleaning. Back scattered electron (BSE) image of the "flakes" (A). Microchemical analysis of
one of flakes showing the presence of copper oxides and some silicate and iron residues (B, C). Small fragments of gilding (small areas in white∼ 450 μm) are also visible in
SEM-BSE image (A).

λ: 1064 nm, pulse duration 20 – 130 μs). This laser sys-
tem allows energy, frequency and spot size to be selected,
while the pulse duration is automatically set by the instru-
ment within the defined range. Cleaning took place in two
stages. The first one with a lower fluence (parameters: flu-
ence 2,4 J/cm2 ; spot width 4 mm; frequency 6 Hz; energy
300 mJ, pulse duration ∼ 50 μs) to remove most of the con-
cretions; the second one with a higher fluence (parameters:
fluence 3,2 J/cm2 ; spot width 4 mm; frequency 6 Hz; energy
400 mJ, pulse duration ∼ 60 μs) to remove almost all the re-
maining cuprite (see video n.2). Large spot sizes were cho-
sen because they were more effective in removing the min-
eralized crusts. Spot size was calculated by measuring the
spot diameter on irradiated “laser burn paper”.
3) The removed material was mostly washed away by the wa-
ter flowing from the brush exploiting, whenever needed,
a weak jet of demineralised water. The surface was then
promptly dehydrated using sprayed acetone. Any residue
was removed with a soft brush.
4) Remaining adhering mineralization spots, together with
thicker sandy crusts that the laser could not remove, were
taken away by mechanical means.
The effectiveness of the treatment was checked using both op-
tical and electron microscopy. The cleaned surface of the artworks
was observed with an optical microscope, using a Carl Zeiss® OPMI
1-FC with S21 articulated stand apparatus.

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G. Rotondi, A. Brini and F. Cantini Journal of Cultural Heritage 61 (2023) 188–193

Fig. 7. Fragment I before (A), during (B) and after (C) the conservation treatment.

Fig. 8. Fragment II before (A), during (B) and after (C) the conservation treatment.

Electron microscopy was, however, only used to analyse the
cuprite flakes (Fig. 6) removed during the cleaning, since the two
fragments (68 cm and 55 cm maximum respectively), were too
large to enter the SEM measurement chamber. Furthermore, sam-
pling the gilding from the artefacts to check the result of the clean-
ing should be considered an operation that is too invasive and far
from modern conservation principles.
4. Results and discussion
The small areas of gilding visible before cleaning turned out to
be part of a larger, incredibly well-preserved gilding (Figs. 7, 8),
protected over the centuries by the mineralized layer described
above. In fact, with the exception of a heavily corroded strip run-
ning across one of the fragments, the gilding was almost com-
pletely preserved.
Visual inspection and observation by optical microscopy did not
show any modification, or damage of the cleaned gold leaf surface.
On the contrary, the gilding retained its brilliance and the original
processing marks were still visible, including the overlapping edges
of the different gold leaves. (Figs. 5, 7, 8)
The cleaning process residual material was analysed by means
of SEM-EDS, highlighting how almost exclusively the cuprite-based
mineralization layer was removed by the treatment. In very few
cases some traces of gold leaf have been identified among the re-
moved material, probably already fragmented by corrosion (Fig. 6).
5. Conclusions
The work presented here, developing a new alternative tool for
laser ablation in underwater conditions, allows for an appropri-
ate and effective conservative treatment for gilt bronze surfaces. In
fact, the modified water brush pen has proved to be efficient and
precise for wetting only the surface to be treated, avoiding expos-
ing the artefact to prolonged immersion in water. Furthermore, this
tool does not require the use of any adhesives applied on a sen-
sitive foil-gilded surface and can easily overcome the difficulty of
cleaning artefacts with complex geometries and rich in reliefs and
protrusions.
The cuprite-layer that hid the gilded surface was removed ef-
fectively and selectively without affecting the underlying gold leaf,
leaving only very few traces of the mineralized layers. Strong phys-
ical interaction with the artwork was also avoided, leaving only the
removal of the thicker sandy crusts and the cuprite residues to me-
chanical tools. This method can be easily replicated and adapted to
other case studies as well as improved with further research.
The tuning of a system able to solve most of the issues related
to perform underwater laser cleaning can provide a small but in-
cisive contribution to develop a conservative treatment in the best
operating conditions and with the utmost respect for the artefact.
Funding
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
The project was part of the internship for a master’s thesis
carried out at “Scuola di Alta Formazione e di Studio” (SAFS) of
Opificio delle Pietre Dure (OPD) in Florence (Italy) in cooperation
with Superintendence of Archaeology, Fine Arts and Landscape for
the metropolitan city of Florence and the provinces of Pistoia and
Prato.
Acknowledgements
The authors would like to thank the management of the OPD,
especially M. Ciatti (former Superintendent of OPD), E. Daffra (Su-
perintendent of OPD), L. Speranza (Director of the conservation

192
G. Rotondi, A. Brini and F. Cantini
of bronzes and ancient weapons OPD), A. Patera (associate direc-
tor of OPD Scuola di Alta Formazione e di Studio), M. Salvini and
A. Vernillo (officer of the Superintendence of Archaeology, Fine
Arts and Landscape for the metropolitan city of Florence and the
provinces of Pistoia and Prato) for making this work possible. We
would also like to thank the staff of the OPD scientific laboratory
for their precious collaboration, and A. Mignemi for the valuable
suggestions.
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.culher.2023.03.012.
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