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LIBS-LIF-Raman: a new tool for the future E-RIHS
Conference Paper · July 2017
DOI: 10.1117/12.2272027
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LIBS-LIF-RAMAN a new tool for the future E-RIHS
Vincent Detalle, Xueshi Bai, Elsa Bourguignon, Michel Menu, Isabelle Pallot-Frossard
C2RMF, Palais Louvre, 14 quai F. Mitterand 75001 Paris
Abstract
France is one of the countries involved in the future E-RIHS - European Research Infrastructure for Heritage
Science. The research infrastructure dedicated to the study of materials of cultural and natural heritage will
provide transnational access to state-of-the-art technologies (synchrotron, ion beams, lasers, portable methods,
etc.) and scientific archives. E-RIHS addresses the experimental problems of knowledge and conservation of
heritage materials (collections of art and natural museums, monuments, archaeological sites, archives, libraries,
etc.). The cultural artefacts are characterized by complementary methods at multi-scales. The variety and the
hybrid are specific of these artefacts and induce complex problems that are not expected in traditional Natural
Science: paints, ceramics and glasses, metals, palaeontological specimens, lithic materials, graphic documents,
etc. E-RIHS develops in that purpose transnational access to distributed platforms in many European countries.
Five complementary accesses are in this way available: FIXLAB (access to fixed platforms for synchrotron,
neutrons, ion beams, lasers, etc.), MOLAB (access to mobile examination and analytical methods to study the
works in situ), ARCHLAB (access to scientific archives kept in the cultural institutions), DIGILAB (access to a
digital infrastructure for the processing of quantitative data, implementing a policy on (re)use of data, choice of
data formats, etc.) and finally EXPERTLAB (panels of experts for the implementation of collaborative and
multidisciplinary projects for the study, the analysis and the conservation of heritage works).Thus E-RIHS is
specifically involved in complex studies for the development of advanced high-resolution analytical and imaging
tools. The privileged field of intervention of the infrastructure is that of the study of large corpora, collections
and architectural ensembles.
Based on previous I3 European program, and especially IPERION-CH program that support the creation of new
mobile instrumentation, the French institutions are involved in the development of LIBS/LIF/RAMAN portable
instrumentation. After a presentation of the challenge and the multiple advantages in building the European
Infrastructure and of the French E-RIHS hub, the major interests of associating the three lasers based on
analytical methods for a more global and precise characterization of the heritage objects taking into account their
precious characters and their specific constraints. Lastly some preliminary results will be presented in order to
give a first idea of the power of this analytical tool.
1/ Introduction
Tangible cultural and natural heritage are key components of the European identity. The study and preservation
of cultural and natural heritage is a global challenge for science and the European society at large. The European
Research Infrastructure for Heritage Science (E-RIHS) supports research on heritage interpretation, preservation,
documentation and management. State-of-the-art tools and services will be provided by cross-disciplinary groups
of researchers to cross-disciplinary users and scientific communities working to advance knowledge about
heritage and to devise innovative strategies for its preservation. E-RIHS connects researchers in the humanities
and natural sciences and fosters a trans-disciplinary culture of exchange and cooperation. E-RIHS pursues the
integration of European world-class facilities to create a cohesive entity playing a connecting role in the global
community of heritage science.
Optics for Arts, Architecture, and Archaeology VI, edited by Luca Pezzati,
Piotr Targowski, Proc. of SPIE Vol. 10331, 103310N · © 2017 SPIE
CCC code: 0277-786X/17/$18 · doi: 10.1117/12.2272027
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Fragmentation, duplication of efforts, isolation of small research groups put at risk the competitive advantage of
European heritage science research, spearheaded so well in the past by its unique cultural heritage. The
longterm tradition of this field of research, the ability to combine with innovation, and the integration promoted
by EUfunded projects such as EUARTECH, CHARISMA and IPERION CH in conservation science, and
ARIADNE in archaeology represent the background of E-RIHS. E-RIHS exploits the synergy of the cooperation
among the academy, research centres and cultural institutions. Both the scientific and the socioeconomic
importance connected with heritage science are nowadays evident. The research community has achieved the
maturity necessary to make the leap towards a permanent European research infrastructure that will impact
broadly on society and economy.
E-RIHS is a pan-European distributed infrastructure supported by 13 Member States – potential founders of the
E-RIHS consortium – and participated by six more EU and associated countries. E-RIHS star-design structure
has its Central Hub and headquarters in Florence (IT) and comprises National Hubs – possibly organised in
Regional Hubs in some countries – encompassing specialised knowledge, fixed and mobile national facilities of
recognized excellence, physically accessible collections/archives and remotely accessible heritage data.
In this paper we will first describe more precisely the ERI-HS idea and we will focus on a specific development
that is directly link to it around the creation of a new instrumentation, LIBS/LIF/Raman, that will take place
inside this next European infrastructure.
2/ E-RIHS, a future infrastructure for cultural heritage
Heritage Science provides knowledge and evidence in support of heritage management, conservation,
interpretation and documentation. E-RIHS will represent a significant step beyond the sum of its parts, with the
mobile instrument fleet taking knowledge and skills beyond traditional laboratory boundaries, and the hubs
representing a link between the scientific and heritage communities, the public and industry. E-RIHS pursues a
unique and cohesive entity of European world-class facilities and fosters an integrated platform in the global
community of Heritage Science.
E-RIHS will integrate research on four access platforms:
(i) MOLAB: access to advanced mobile analytical instrumentation for non-invasive or minimally invasive
measurements on valuable, fragile or immovable objects, archaeological sites and historical monuments. The
MObile LABoratories will allow its users to carry out complex multi-technique diagnostic projects, allowing
effective in situ investigation.
(ii) FIXLAB: access to large-scale and specific facilities with unique expertise in Heritage Science, for
sophisticated scientific investigation on samples or whole objects, revealing micro-structures and chemical
composition, giving essential and invaluable insights into historical technologies, materials and species, their
context, chronologies, alteration and degradation phenomena.
(iii) ARCHLAB: physical access to archives and collections of prestigious European museums, galleries,
research institutions and universities containing non-digital samples and specimens and organized scientific
information.
(iv) DIGILAB: virtual access to organized knowledge and scientific information in heritage data hubs –
including multidimensional images, analytical data and documentation – from large academic as well as research
and heritage institutions.
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E-RIHS Headquarters will coordinate access, research and training across E-RIHS and provide peer review
facilities as an access point to the distributed infrastructure. The current infrastructural project ARIADNE has
already started developing a framework for archaeology that could be extended to cover Heritage Science as a
whole. The ARIADNE gateway will offer a Resource Discovery facility based on a Resource Registry.
Research supported by E-RIHS will span several areas, including:
(i) Materials: Whether in collections, buildings or sites and landscapes, the behavior of materials is at the
heart of many questions in the heritage and archaeology sector, whether involving questions about the origin of
an artefact, the decay of a building or the history of a site. Development of novel sensors, devices and techniques
suitable for application to a wide range of characterization and measurement problems will address issues around
non-invasive or minimally invasive analysis of artefacts, informing the preservation of inherently unstable
materials, and allowing meaningful conclusions about the behavior of the people and the ecosystems of the past
to be drawn.
(ii) Environments: All materials, building and sites have an environment surrounding them – whether that is
indoors or outdoors. These environmental conditions will have varied dramatically – for example on excavation,
on transfer to a museum, or as a result of soil erosion, changing air quality and/or climate change. Environmental
research will focus on questions about materials: environment interrelationships in all settings (indoor, outdoor,
buried, surface, submerged), and with the risks and opportunities posed by environmental change and
conservation interventions.
(iii) Digital: Challenges of developing new techniques, integrated into a workflow from data capture,
through extraction, representation, organization, analysis and dissemination to academia, creative and cultural
professionals and the wider public will be addressed. The underpinning data assets generated will also support
development of knowledge through novel research methods. The research areas include handling spatial,
temporal and geometric data; knowledge representation, language engineering, pattern recognition and big-data
analytics; image processing, computer graphics and interactive techniques for cultural heritage; ICTs in crowd-
sourcing and citizen science.
With its strong basis in digital technologies and Virtual Research Environments, open data access, data sharing,
processing and simulation in a digital framework will be based on standardization, common protocols and a
shared knowledge base. This will represent a shift from traditional research methodologies to a virtual
distributed infrastructure.
E-RIHS access and networking will be accompanied by high-level actions for training, dissemination,
communication and knowledge/technology transfer aimed at the global heritage community, with special
attention paid to SMEs competitiveness and growth, and to social and cultural innovation.
3/ Integration of laser based spectroscopic technics
In the framework of Iperion-Ch a specific work package is dedicated to the development of new instrumentation
and more specifically to the creation of advanced mobile instruments for coupling point analytical and imaging
methods
The ability to move instruments to where objects are located, carrying out analytical campaigns at museums,
excavation sites and historical monuments, indoors or even outdoors, offers huge advantages to the study of
cultural heritage. Instrument size, mobility and straightforward operation (often in a poorly controlled
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environment, at high or low temperatures, under high humidity, dust or varying lighting conditions, etc.) are
requirements of cultural heritage studies that must be taken into account together with the vast diversity of
objects and materials examined and are critical factors in mobile and in situ analysis. It should also be noted that
typically a combination of techniques is needed to obtain a set of data valuable for interpreting the objects,
paintings, monuments. However, multitechnique studies are largely conducted by combining data obtained from
individual instruments, whether stationary or mobile. Ongoing technological advances are making it possible to
use compact equipment (for instance powerful lasers, highresolution spectrometers or sensitive detectors) that
are suitable for adaptation to new enhanced instrumentation concepts. Such developments open up exciting
prospects for advancing the stateoftheart by combining complementary techniques in customdesigned
mobile/portable hybrid instruments, enabling scientists to effectively pursue multianalytical campaigns with a
single instrument.
Among these possibilities, one is focus on the development of mobile LIBSLIFRaman instrumentation [1-2].
The work has to ensure the design and development a multianalytical prototype instrument capable of
combining three laserbased spectroscopic techniques, laserinduced breakdown spectroscopy (LIBS)[3-4], laser
induced fluorescence (LIF)[5] and Raman spectroscopy, to create a hyphenated LIBSLIFRaman technique that
provides complementary elemental and molecular analytical information. Laser sources, appropriate optics and
detection modules has to be integrated on a mobile platform capable of supporting conservation campaigns at
archaeological and historical monuments, in which highthroughput measurements and on site decisionmaking
are needed.
The first step is to define these different parameters. In order to develop this new instrumentation an integrated
work has been implemented by different groups, i.e. in Greece (Forth), Spain (CSIC), Italy (CNR). Difference
steps have been defined, in terms of the choice of excitation wavelength to generate the 3 kinds of
spectroscopies. The notion of compromise is of course necessary, but the possibility to finally get in the same
location three spectroscopies information will be a huge gain for the characterization of material.
3.1 Experimental set-up
At the C2RMF, laboratory located at the Louvre Palace, a specific set-up have been implemented. The Figure 1
describes the experimental set-up developed during the last three years.
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This set-
u
laser
p
ul
s
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d
spectro
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3.2 Res
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LIBS di
a
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impleme
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etection sy
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y
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rference with
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duration of
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ation has to b
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ocus on the
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Figure 1:
L
rking with 4
usted in ord
e
s
tems integr
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ime resolved
e
can be im
p
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uous mode,
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ented, the L
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a
our laser (U
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aboratory L
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h
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ting Czern
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ut in order t
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rometer [1-
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enerally this
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n
als.
r
ization of
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need high
induces a
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t the total
t
h our se
t
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For the
L
techniqu
e
Three w
a
LIBS ex
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(betwee
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inding medi
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m
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2
/
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nd that finall
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r, in order to
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lytical purp
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b
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Table 1.
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m
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ave been tes
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of the wave
l
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r
a
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er to evaluat
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ly used as c
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we used Cze
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s adjusting t
h
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t
f
or general id
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esco” sample
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fy that LIBS
l
ength will n
o
n
sparent mat
e
e
the impact
o
o
nsolidate pr
o
u
e to ensure a
r
ny-Turner s
p
a
ba
r
p
repares
o evaluate th
e
h
e energy of t
h
t
he same inte
n
e
ntification.
at 3 excitati
o
spectra coul
d
o
t be highly
d
e
rial, the choi
c
o
f the wavele
n
o
duct in cultu
r
good identifi
c
p
ectrometer c
o
at “a fresco
e
relative effi
h
e different
w
n
sity. Finally
t
o
n wavelengt
h
d
be recorded
d
ependent on
c
e of UV ligh
t
n
gth on Ram
a
r
al heritage a
p
c
ation and fl
u
o
upled with I
C
painting
c
iency for
w
avelength
t
he results
h
s
with good
the LIBS
t
has to be
a
n and LIF
p
plication.
u
orescence
C
CD. The
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,nm
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u
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5
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u
re 3 presents
the resolutio
n
u
orescence r
e
f
luorescence l
e
i
gnal, but it
w
t
o account th
a
s
ults illustrat
e
the instrume
n
Figure 3:
C
e
length soluti
o
e
the best
p
ar
a
a
ser waveleng
3
2
6
6
5
5
Table 1: Exp
the result w
e
n
is increased
.
e
sponse of ou
r
e
vels are not
e
w
ill induced
d
a
t we will pre
s
e
perfectly th
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tal solution h
a
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omparison
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o
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h
a
meters for th
th (nm)
erimental co
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e
.
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e
r
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h
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5
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s to be caref
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a
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h
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e
o
f the materi
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e
we face in
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lly evaluate
d
ectrum of Pa
r
b
e deal and w
e
r
umentation.
m
2
) G
r
30
18
18
a
man / LIF e
x
f
ferent config
u
a
rly that the d
e
ce signal hid
e
e
r, increasing
t
a
l. The adjust
m
i
mpact of the
R
trying to im
p
d
.
r
aloid B72 at
3
e
will now co
n
r
ating (l/mm)
0
00
00
x
perimentatio
n
u
rations. The
e
ep UV wave
l
e
s the Raman
t
he energy w
i
m
ent of the
e
R
aman spect
r
p
lement multi
-
3
excitation
w
n
tinue the wo
r
n
less is the w
a
l
ength, 266 n
m
information
a
i
ll probably i
n
e
nergy have
b
r
oscopy exper
-
technique e
x
w
avelengths
r
k in order to
a
velength,
m
induced
a
t 266 nm
n
crease the
b
een done
i
ment.
x
periments
finally
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4/ Conclusion
The challenge and the multiple advantages in building the European Infrastructure and of the French E-RIHS
hub have been presented. The major interests of associating the three lasers based analytical methods for a more
global and precise characterization of the heritage objects taking into account their precious character and their
specific constraints. This work has been supported by the French Ministry research Program EquipEx
PATRIMEX and by IPERION CH project funded by the European Commission, H2020- INFRAIA-2014-2015,
Grant No. 654028.
[1] D. Anglos, V. Detalle, Cultural Heritage Applications of LIBS, Laser-Induced Breakdown Spectroscopy,
Volume 182 of the series Springer Series in Optical Sciences (2014) 531-554.
[2] R. Bruder, V. Detalle, and C. Coupry, An example of the complementarity of laser- induced breakdown
spectroscopy and raman microscopy for wall painting pigments analysis, J. Raman Spectrosc. 38 (2007)
909-915.
[3] S. Gregoire, M. Boudinet, F. Pelascini, F. Surma, V. Detalle, and Y. Holl. Laser- induced breakdown
spectroscopy for polymer identification. Anal. Bioanal. Chem. (2011).
[4] S. Duchêne, V. Detalle, R. Bruder, and J.B. Sirven, Chemometrics and laser induced breakdown
spectroscopy (libs) analyses for identification of wall paintings pigments, Current Anal. Chem. 6 (2010)
60-65.
[5] A. Pelagotti, L. Pezzati, N. Bevilacqua, V. Vascotto, V. Reillon, C. Daffara, A study of UV fluorescence
emission of painting materials, Conference: 8th Int. Conf. on "Non-Destructive Testing and
Microanalysis for the Diagnostics and Conservation of the Cultural and Environmental Heritage", January
2005
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... Two different spectrometer-detector combinations -Czerny Turner spectrometer with ICCD camera, echelle spectrometer and photodetector arrays for LIBSwere used to record the different spectral data. [156] Syvilay et al. [2] have described the evaluation of LIBS, Raman, and LIF for analysis of cultural heritage materials. The molecular and elemental analysis of the material is obtained regardless of its inorganic or organic nature, without any preliminary preparation, on the surface, and in depth. ...
Article
This review discusses the importance of hyphenating different laser-based techniques such as Laser-Induced Breakdown Spectroscopy (LIBS), Raman spectroscopy and Laser-Induced Fluorescence spectroscopy (LIF) and the applications of the hybrid systems. These spectroscopic techniques, in single and multi-modes, are widely accepted as an efficient tool to retrieve information from atomic and molecular systems such as knowledge on chemical bonds, molecular structure and geometry, interactions and related mechanisms etc. Analytical capabilities of such systems which combine LIBS, Raman, and LIF are highly desirable since one can acquire complementary information from the same sample enabling a remarkable potential for various applications in diverse fields like archeology, mineralogy, planetary explorations, clinical chemistry, biomedical and environmental monitoring etc to extract more information. In this review, attention has been devoted to the works of combined LIBS-LIF-Raman technique in different fields and its significance, along with brief discussions on other combinations like LIBS-Raman, LIBS-LIF, and Raman-LIF.
... Of particular interest is the possibility of combining various laser spectroscopy in the same portable instrument. A network of European groups is currently working to develop a prototype coupling Raman, LIBS, and Laser-Induced Fluorescence (LIF) in a single apparatus [105] and to address the many instrumental challenges related to the choice of laser sources, collection optics, and experimental configurations ensuring the best compromise for the three techniques [106,107]. ...
Chapter
The potential of Laser-Induced Breakdown Spectroscopy (LIBS) for micro-destructive analysis of cultural heritage objects has been widely demonstrated, and the technique is now ready to be integrated in the permanent instrumentation of conservation laboratories. This chapter presents a review of recent results obtained by LIBS researchers with a focus on three main applications that exemplify the most representative contributions of this technique to cultural heritage science: noninvasive stratigraphic analysis of multilayered samples; feasibility and field studies with portable instrumentation; and underwater LIBS of submerged samples. An overview on the principles of LIBS and employed instrumentation is also provided, together with a discussion on its advantages and drawbacks as compared to well-established techniques for the analysis of cultural heritage.
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1. The properties of plastics make them highly useful for various purposes in modern life. But the impact of waste produced from the same is raising serious environmental concerns because most of the plastic in use are non-biodegradable. Though there are attempts to develop plastics that are eco-friendly, the production of the same is in the initial stages only. There is thus an urgent need for efficient methods for retrieval and reprocessing of different plastic types from the domestic and industrial waste to be recycled for further use. This review focuses on four major spectroscopic methods, infrared (IR) spectroscopy, Laser induced breakdown spectroscopy (LIBS), Laser Induced Fluorescence spectroscopy (LIF), and Raman spectroscopy, highly suitable for the plastic identification and sorting because of their speed, specificity and need of only minimal human involvement for routine use. The present status of the application of these spectroscopic methods and their scope in developing an industry-oriented plastic sorting system for recycling of plastic waste is discussed.
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Laser-induced breakdown spectroscopy (LIBS) of organic materials is based on the analysis of atomic and ionic emission lines and on a few molecular bands, the most important being the CN violet system and the C2 Swan system. This paper is focused in molecular emission of LIBS plasmas based on the CN (B2Σ–X2Σ) band, one of the strongest emissions appearing in all carbon materials when analyzed in air atmosphere. An analysis of this band with sufficient spectral resolution provides a great deal of information on the molecule, which has revealed that valuable information can be obtained from the plume chemistry and dynamics affecting the excitation mechanisms of the molecules. The vibrational emission of this molecular band has been investigated to establish the dependence of this emission on the molecular structure of the materials. The paper shows that excitation/emission phenomena of molecular species observed in the plume depend strongly on the time interval selected and on the irradiance deposited on the sample surface. Precise time resolved LIBS measurements are needed for the observation of distinctive CN emission. For the organic compounds studied, larger differences in the behavior of the vibrational emission occur at early stages after plasma ignition. Since molecular emission is generally more complex than that involving atomic emission, local plasma conditions as well as plume chemistry may induce changes in vibrational emission of molecules. As a consequence, alterations in the distribution of the emissions occur in terms of relative intensities, being sensitive to the molecular structure of every single material.
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Interest in mass spectrometry with an inductively coupled plasma as an ion source and its association with laser ablation as a sample introduction technique (LA-ICP-MS) has steadily increased during the past few years. After a description of the analytical procedure and the calculation method, we show the potential of this technique to characterize non destructively archaeological artefacts. A comparison is made between the results obtained with LA-ICP-MS and those obtained on the same objects with other analytical methods. A large variety of archaeological materials such as obsidians, glasses, glazes and flints are studied.
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A versatile spectrochemical technique enabling nearly instant, multi-element analysis of materials, LIBS is increasingly employed in studies of archaeological and historical objects, monuments and works of art. The development of several mobile LIBS instruments opens a lot more possibilities for analytical campaigns on site: at museums, conservation laboratories and even outdoors at excavation sites or historical monuments. The basic concepts underlying the use of LIBS in the context of cultural heritage studies are briefly reviewed along with technical and instrumentation aspects. Selected examples of analytical studies are discussed with emphasis on cases that demonstrate the use of mobile LIBS instruments.
Article
Laser ablation molecular isotopic spectrometry (LAMIS) was recently reported for rapid isotopic analysis by measuring molecular emission from laser-induced plasmas at atmospheric pressure. With C-13-labeled benzoic acid as a model sample, this research utilized the LAMIS approach to clarify the formation mechanisms of C-2 and CN molecules during laser ablation of organic materials. Because the isotopic ratios in the molecular bands could deviate from statistical distribution depending on their formation pathways, the dominant mechanism can be identified through a comparison of the experimental observed isotopic patterns in the molecular emission with the theoretical statistical pattern. For C-2 formation, the experimental (CC)-C-12-C-12/(CC)-C-13-C-12 ratios not only support a recombination mechanism through atomic carbon at early delay time but also indicate the presence of other operating mechanisms as the plasma evolves; it is proposed that some of the C-2 molecules are released directly from the aromatic ring of the sample as molecular fragments. In contrast, the temporal profiles in the C-12/C-13 ratios derived from CN emission exhibited opposite behavior with those derived from C-2 emission, which unambiguously refutes mechanisms that require C-2 as a precursor for CN formation; CN formation likely involves atomic carbon or species with a single carbon atom.
Article
Laser Induced Breakdown Spectroscopy (LIBS) in the last decades has been more and more applied to the field of Cultural Heritage with great results obtained either alone or in combination with complementary laser techniques. Its ability to analyze, with a minimal loss, different kinds of materials in laboratory, in situ and even in hostile environments has been highly appreciated. The main aim of this paper is to present a review of LIBS applications in the interdisciplinary field of archeometry. The LIBS technique is shortly described both from a theoretical and practical point of view, discussing the instrumental setup, also in comparison with typical features of laser induced fluorescence (LIF) and Raman spectroscopy apparata. The complementary with multivariate analysis, a method that can help in reducing data set dimensions and in pulling out effective information, is stressed. In particular the role of LIBS in Cultural Heritage material characterization, recognition of fakes and indirect dating is described, reporting general considerations and case studies on metal alloys, mural paintings, decorated ceramics, glasses, stones and gems.
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The results of measurements of diffuse reflectance over the wavelength range 200 < λ < 2500 nm are reported for sphalerite, cinnabar, alabandite, chalcopyrite, bornite, orpiment, stibnite, bismuthinite, enargite, and pyrargyrite, and for eight pyrite-type and four NiAs-type compounds. Some spectral assignments have been made. Optical properties are related to the absorption spectrum (and through this to composition and structure) in a rational way. Absolute reflectances tend to increase with mean atomic number (z) through the operation of the ‘z-sum rule’, and at constant z they decrease as the band gap increases. Bireflectance is structurally controlled, being weak in derivatives of the cubic sphalerite and pyrite structures, moderate in derivatives of wurtzite and NiAs, and strong in anisodesmic structures such as that of stibnite. Extreme bireflectance occurs in anisodesmic structures with strong dichroic absorption bands in the visible (molybdenite, covelline). The dispersion of reflectance (dR/dλ) depends on the position of the centre of the main absorption envelope in relation to the visible spectrum. For λ > , dispersion is normal ( R blue > R red , d R /dλ negative), the streak is light or coloured, and polished surfaces tend to be bluish. For λ < , dispersion is reversed ( R red > R blue ), the streak is dark, and polished surfaces are yellowish. Polished surfaces are white or grey if absorption varies little through the visible or strongly coloured if it varies rapidly (covelline, chalcopyrite).
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The applicability of laser-induced fluorescence (LIF) spectroscopy as a nondestructive analytical technique for artwork diagnostics is investigated. In this work, LIF is employed in the examination of a set of cadmium sulfide- and cadmium selenide sulfide-based pigments in a series of oil painting test samples. Fluorescence spectra of the oil colors are recorded upon pulsed laser excitation at 532, 355 (Nd:YAG), and 248 nm (KrF excimer). The technique is shown to be suitable for differentiating among the various cadmium pigments used in this study and, furthermore, to be capable of identifying individual components in mixtures of these pigments on the basis of their characteristic fluorescence emission. Future prospects and the potential for the extension of LIF from a research laboratory technique into a conservator's tool for artwork diagnostics are discussed.
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This study examines the materials of a contemporary pictorial artwork, belonging to the Macedonian Museum of Contemporary Art in Thessaloniki (Greece), and needing conservation. The combined use of micro-FTIR and micro-Raman spectroscopy allowed the identification of almost all painting materials. Moreover, the stability of a series of synthetic pigments towards accelerated ageing is investigated in applications using the contemporary binding medium styrene-acrylic copolymer. The pigments in question are: Hansa yellow PY3 and PY74, quinacridone PV19 and PR122, naphthol AS PR112, phthalocyanine green PG7 and blue PB15, dioxazine PV37, van Dyck brown PBk11, ivory black PBk9, and titanium dioxide PW6. The organic pigments were applied alone or mixed with titanium dioxide, in rutile form or as a mixture of rutile/anatase. The experimental swatches were subjected to ageing tests, and subsequently studied as to colour changes by means of colorimetric measurements, and as to the molecular structure differentiations by infrared spectroscopy in reflectance mode. The ageing tests included exposure to high temperature and humidity (90°C, 60% RH) and to ultraviolet radiation (350nm, 30°C and 50% RH, with a substantial temperature increase at 90°C for 3 days). The greater colour difference is caused by high temperature and humidity, whereas paint layers containing TiO2, and especially the mixture of the forms rutile/anatase, prove very susceptible to ultraviolet radiation, demonstrating a significant colour difference and extended molecular changes.
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The use of remote sensing techniques for the monitoring of historical buildings is attractive, since it can allow a fast monitoring of large surfaces without the use of scaffolding and, in addition, a thematic mapping which is easier to read. The studies on fluorescence lidar monitoring of buildings started a few years ago and are still in progress. Interesting results were obtained in biodeteriogen monitoring and in the identification of stones. The possibility of detecting fluorescence thematic images of large areas was demonstrated on both artificial targets and historical buildings. This paper describes the current state of the art on fluorescence lidar monitoring of buildings and the research trends for the near future.