Nuclear Instruments and Methods in Physics Research B 267 (2009) 36943697

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Nuclear Instruments and Methods in Physics Research B

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

Nanosecond Neutron Analysis for the search of the lost Leonardos masterpiece,
the Battle of Anghiari
A.V. Kuznetsov a, I.Yu. Gorshkov a, A.V. Evsenin a, O.I. Osetrov a, D.N. Vakhtin a, A. Cosentino b,*, M. Seracini b
a
Applied Science and Technology Center (APSTEC Ltd.), Ofce 213, Gzhatskaya, 27, Saint-Petersburg 195220, Russia
b
CISA3, Center of Interdisciplinary Science for Art, Architecture and Archaeology, University of California, San Diego, 9500 Gilman Dr. La Jolla, CA 92093-0436, USA

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

Article history: Between 1505 and 1506 Leonardo Da Vinci painted his masterpiece, the Battle of Anghiari, in Palazzo
Received 31 July 2009 Vecchios Hall of 500 in Florence. The unnished mural remained visible until 1563, when architect Gior-
Received in revised form 19 August 2009 gio Vasari undertook a renovation of the Hall and all traces of the Battle of Anghiari were lost. However,
Available online 11 September 2009
scholarly interpretation and scientic evidence suggest that the mural could be on the eastern wall, hid-
den behind a brick wall built in 1563 by Vasari. This paper discusses the possibility of using NNA/APT
PACS: (Nanosecond Neutron Analysis/Associated Particle Technique) to establish the presence of the master-
82.80.Jp
piece by identifying behind the Vasaris wall chemical elements from the gesso preparation layer of
25.40.Fq
the mural and possibly from its pigments. This paper reports on the experiments run with a simple
Keywords: NNA/APT system and the Monte Carlo simulations that have been carried out in order to outline the
Artwork experimental setup of an advanced NNA/APT able to detect and locate the tiny amount of gesso and
Leonardo Da Vinci pigments.
Search 2009 Elsevier B.V. All rights reserved.
Neutron

1. Introduction appropriate technologies. Starting from 2000 further research was

The mural, the Battle of Anghiari (BoA), if nished, would have
been Leonardo Da Vincis largest work, about three times the size
of the famous Last Supper he painted in Milano in 1495. Contem-
poraries describe the painting as Da Vincis most magnicent work
ever. In 1503, the chief magistrate of the Republic of Florence com-
missioned Leonardo to paint a large mural on a wall of the Hall of
500 in Palazzo Vecchio to commemorate the historic Battle of
Anghiari, in which the Florentine army defeated the Milanese
one in 1440. Work began presumably in June 1505 but it was never
completed. The unnished mural was visible in the Hall of 500 un-
til 1563 when the architect and painter Giorgio Vasari undertook
renovation of the space. The ceiling and the walls were raised
and Vasari himself covered the new walls with paintings and fres-
coes and all traces of the Battle of Anghiari were lost. Some schol-
ars believe that Vasari was a far too great admirer of Leonardo Da
Vinci to have destroyed the artwork and that it would have been a
simple enough matter to have built a new wall over the work of
Leonardo, as was sometimes done in those days. In 1975 Seracini,
Newton and Asmus carried out a rst investigation to determine if
the BoA were behind one of the walls, using a variety of introspec-
tion methods but the research was inconclusive due to the lack of
* Corresponding author.
E-mail address: tonycosentino@yahoo.it (A. Cosentino).
done by Seracini using laser scanning, thermography and ground
penetrating radar [1]. This phase of the research made possible
to reconstruct the architecture layout of the Hall of 500 before
the remodeling by Vasari (15631572). In addition, the results pro-
vided by the research based on historical documents contributed to
dene the area on the east wall where Leonardo could have
painted the BoA. This area corresponds to the one with an air
gap identied with the radar scanning. At this point, there was a
need to identify a non-invasive technology to detect and locate
chemical elements whose presence could hint unambiguously to
the gesso and the pigments Leonardo could have used for the mur-
al. Neutron Nanosecond Analysis/Associated Particle Technique
(NNA/APT) could be used to detect the elemental composition of
materials behind the Vasaris brick wall.
2. Experimental method
2.1. Materials and methods
The main idea of any neutron-in, c-out technique is to
irradiate the object with neutrons and measure the second-
ary c-radiation induced by these neutrons. Many chemical
elements produce characteristic c-rays following scattering or cap-
ture of neutrons. The most important advantage of the method is
that neutrons and high-energy c-rays have very high penetration

0168-583X/$ - see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.nimb.2009.09.006
 A.V. Kuznetsov et al. / Nuclear Instruments and Methods in Physics Research B 267 (2009) 36943697 3695

ability, and chemical elements of interest can be detected through elements of interest, and produces a 3D elemental image of the
thick barriers: soil, bricks, concrete, metal, etc. Efforts to develop investigated volume.
devices based on the neutron-in, c-out method have been made
since 1970s mainly for the purposes of homeland security and land 3. Experimental results
mine detection [2,3]. However, wide application of this potentially
very powerful and universal technique has been hindered by the 3.1. Detecting the gesso
fact that different factors make the c-ray background in the detec-
tor very high, leading to prohibitively long identication times. To Between August 1504 and April 1505 Leonardo bought around
overcome this problem NNA/APT has been proposed [4,5]. This 220 kg of gesso (calcium sulfate semi-hydrated, CaSO4 + H2O),
technique is based on irradiation of the inspected object with fast which should have been spread over the original wall in order to
neutrons and detection of secondary c-rays in narrow (nanosec- have a suitable smooth and white surface to paint the mural. Gesso
ond-range) time intervals counted from the moment of emission is rich in sulfur and, therefore, the goal of the experiment was to
of each neutron from the source. The latter is determined by detect and locate sulfur contained in plasterboard (120 
detecting an associated particle, which accompanies neutron emis- 100  1 cm) placed into a 5 cm-wide air gap between two
sion. All c-rays that originate from inelastic scattering of fast neu- 12 cm-thick bricks walls (Fig. 1).
trons on the nuclei, which comprise the analyzed material, arrive The version of SENNA implemented for the detection of sulfur
into the detector within a well-dened time interval, which is consisted of a D-T neutron generator producing 107 n/s about 1%
determined by the time-of-ight of neutrons from the source to of which formed a narrow (20 opening angle) tagged neutron
the reaction point, plus the time-of-ight of c-rays from the reac- beam, and four BGO crystal-based detectors with time resolution
tion point to the detector. All c-rays that do not t into this nano- that translates into the possibility to make 15 cm-wide slices
second-wide time interval are rejected, since they originate from of the cone of tagged neutrons. The depth proles for oxygen, sil-
external sources: cosmic radiation, natural background, reactions icon and sulfur produced in a 30 min-long measurement are
with neutrons that have lost their energy in multiple collisions shown in Fig. 2. The right graph shows distributions of oxygen
with the surrounding matter (thermalized neutrons), etc. Thus,
for each c-quantum that arrives into the detector two parameters
are measured: its energy and time-of-ight relative to the moment
of emission of the associated particle.
Nanosecond timing information allows to almost completely
(more than by two orders of magnitude) suppress the uncorrelated
background in the spectra of c-rays, while keeping all useful
events intact. Reduction of the background in the spectra of c-rays
leads to respective reduction of the identication time. Furthermore,
a neutron source based on a portable D-T neutron generator with
built-in position-sensitive detector of accompanying a-particles
introduces position sensitivity, which allows one to select which
area of space to investigate [6]. This becomes possible since in a neu-
tron generator neutrons are emitted in the reaction d + t ? a + n at
about 180 with respect to a-particles, so the ight direction and
time of emission of each neutron can be xed by detecting the
associated a-particle by a position-sensitive detector. Another
Fig. 1. Experimental geometry and structure reproducing the eastern wall of the
advantage is that neutron generator can be switched off, making it
Hall of 500. The goal of the experiment was to detect and locate sulfur contained in
safe during transportation and storage. Combining position sensitiv- plasterboard (120  100  1 cm) placed into a 5 cm-wide air gap between two
ity of the a-detector with time-of-ight analysis one can obtain a 3D 12 cm-thick bricks walls.
image of elemental composition of the inspected volume.

2.2. Experimental device: SENNA

with without
Amount of material, arb. units

SENNA (Sensor for Explosives detection based on Nanosecond 25 sulfur sample sulfur sample 25
Neutron Analysis) was developed by APSTEC, in cooperation with
Applied Physics Laboratory of the V.G. Khlopin Radium Institute 20 20
oxygen
(Saint-Petersburg, Russia), and was initially designed for the detec-
silicon
tion of concealed explosives. A semiconductor detector of accom- 15 sulfur 15
panying a-particles has been developed and then installed into a
portable sealed neutron generator [7]. This detector consists of 10 10
nine 1 cm  1 cm segments arranged in a 3  3 matrix. On-board
electronics provides timing signal for each arriving a-particle, 5 sulfur 5
and identies which segment of the detector has been hit.
This technology selects for inspection only material that is lo-
0 0
cated within the cone of tagged neutrons, while ignoring the
material that is outside. Furthermore, the cone of tagged neu- 20 40 60 80 20 40 60 80
trons is sliced along the depth coordinate, and chemical compo- Distance from the NG target, cm
sition is determined for each slice independently. SENNA uses for
identication not individual c peaks, but the whole response Fig. 2. Elements in depth prole. Distributions of oxygen (red), silicon (green) and
sulfur (blue) detected with SENNA in 30 min on the structure reproducing the east
function of the device to a chemical element. It uses PLS (partial wall of the Hall of 500. Left graph, with plasterboard; right graph, without
least squares) algorithm to decompose experimental secondary plasterboard. (For interpretation of the references to color in this gure legend, the
c-ray spectra into about 30 response functions of all chemical reader is referred to the web version of this paper.)
3696 A.V. Kuznetsov et al. / Nuclear Instruments and Methods in Physics Research B 267 (2009) 36943697

0.020

Bricks
Cu
0.015
Yield / 10keV Pb

0.010

0.005

0.000
0 500 1000 1500 2000 2500 5000 6000
E [keV]

Fig. 3. Spectra of c-rays measured separately for a brick wall (black), copper (red) and lead (green). (For interpretation of the references to color in this gure legend, the
reader is referred to the web version of this paper.)

100

90
bricks without sample
80 bricks with Cu
70

60
Counts

50 excess due to Cu

40

30

20

10

0
300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
E [keV]

Fig. 4. Spectra of c-rays measured in coincidence with one of the 9 pixels of the a-detector for depth 20 cm inside the brick wall with and without the Cu sample.

(red), silicon (green) and sulfur (blue) for the structure without the
plasterboard while the left graph shows the same distributions but
for the case, in which the plasterboard is between the two brick
walls. SENNA detected the sulfur of the plasterboard and located
it at distance 48 cm from the target of the neutron generator.
Although the excess of sulfur on the left graph may seem small,
it is actually determined quite reliably, i.e. the error bars (not
shown) correspond to 95% condence level. As expected for such
a weak neutron source, the residual activation of the wall after
inspection was negligible.
3.2. Detecting the pigments
On the ground layer Leonardo must have painted a prime layer
with Alexandrian white (tin white) on which pigments mixed with
linseed and walnut oils were applied. The only pigment used with-
out doubt is lead white, bought with the last documented supply.
Then, it is likely that Leonardo applied the pigments he was used to
work with. Among them the most responsive to a NNA/APT analy-
sis are copper-based pigments (azurite and verdigris) and cinnabar
(mercury). So the elements to look for are copper (azurite and ver-
digris), lead (lead white), mercury (cinnabar) and tin (tin white).
Pigments are difcult to detect since their quantities should be
very tiny in the mural. BGO-based c-detector with its poor time
resolution will therefore fail to detect them.
The choice of an optimal detector for this search is dictated by
the need to resolve very close lines in the energy spectra of c-rays,
the need to distinguish between the layer containing pigments and
the surrounding bricks (good time resolution, translating into good
position resolution along the depth coordinate), and the
 A.V. Kuznetsov et al. / Nuclear Instruments and Methods in Physics Research B 267 (2009) 36943697
importance of high efciency to high-energy c-rays that can pene-
trate the brick walls. Recently, a new c-ray detector based on LaBr3
crystal became available. Due to its superior energy resolution, a
wide dynamical range of about 100, measuring c-rays with ener-
gies ranging from about 100 keV to 10 MeV and high light output,
LaBr3-based detector can be successful to detect tiny quantities of
pigments in the mural.
Advanced calculations with MCNP5 for the SENNA imple-
mented with a LaBr3 detector have been run. In these simulations
the amount of powder pigment was assumed to be 500 g/m2. Cal-
culations suggested that elements of interest that can be detected
are copper and lead.
An experiment was run to conrm or reject the possibility of
detecting copper and lead in a mural behind a brick wall.
SENNA was implemented with a 300  300 LaBr3 c-detector and
the samples, 1 kg of metallic Cu and Pb, were inserted in the gap
between the front and back brick walls as in the experimental set-
up in Fig. 1. A series of 30 min measurements was carried out.
Fig. 3 shows response functions for bricks, copper and lead mea-
sured with SENNA equipped with one LaBr3 detector. One can
see that spectral shapes for these substances differ considerably.
Fig. 4 shows an example of spectra measured with and without
a Cu sample in coincidence with one out of the 9 pixels for the
depth corresponding to the location of the sample inside the wall.
The arrows show the regions where c-rays from Cu are expected,
and indeed there is a slight increase of the number of counts there.
Although when the measurement is done through a thick wall low
energy lines are strongly attenuated, with long enough measure-
ment (few hours), presence or absence of Cu and Pb and their loca-
tion inside the wall can be reliably established.
4. Proposed Improvements
The mass of the used samples (1 kg) was a factor of 10 larger
than what is expected to be found in pigments. However, experi-
ments and calculations suggest, that the detection of pigments
could be carried out with a modied SENNA (M) that is going to
be implemented:
The solid angle covered by the associated a-particle detector
(and consequently the opening angle of the tagged neutron
beam) will be a factor of 6 higher.
Two instead of one LaBr3 detectors will be used to improve
measurement statistics and the uniformity of the coverage.
The overall improvement expected for the proposed SENNA (M)
compared to the system that was used to obtain the spectra in
Fig. 4 will be 6  2  0.1  910. Therefore, with the proposed
SENNA (M), an hour-long measurement will be enough to deter-
mine the presence of copper and lead for the realistic amount in
the mural (100 g spread over 0.25 m2) under a layer of bricks. Mea-
suring at several points will allow to obtain the distribution of
these (and other) elements along the scanning line, and to sense
the borders of the hidden Leonardos mural.
The same can be said for the detection of the gesso. The back-
ground can be further suppressed by reducing the mass of bricks
within the slice of the tagged neutron cone containing the plas-
ter. This can be achieved by making thinner slices by taking
advantage of superior time resolution of LaBr3 detectors.
3697
Finally, the existing software that was originally tuned for auto-
matic detection of explosives should be modied to be able to ex-
tract depth proles for tiny amounts of key chemical elements in
presence of large masses of parasitic materials (stones, bricks
and mortar).
5. Conclusions
A simple NNA/APT system could be useful for the detection of
the large amounts of sulfur associated to the gesso preparation
layer of the Leonardos mural and the method does not constitute
any risk neither to the existing Vasari paintings nor to the public in
the Hall. Experiments and Monte Carlo simulations show that the
detection and localization of the tiny amounts of copper and lead
based pigments could also be addressed if an appropriate NNA/
APT experimental set up would be realized.
Acknowledgments
We thank Prof. DuVarney, Emory University, Department of
Physics, for suggesting the use of neutron techniques to detect
the presence of pigments behind the masonry front wall in 2005.
Prof. DuVarney has been a consultant to the project since then.
The University of California starting from 2007 has supported Prof.
Seracinis efforts to pursue the search for the lost mural with neu-
tron techniques after appointing him Scientic Director of CISA3:
Center of interdisciplinary Science for Art, Architecture and
Archaeology.
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