first part - Eu-ARTECH

3 th Year Interim Report
Eu-ARTECH
Access, Research and Technology for the conservation
of the European Cultural Heritage
Integrating Activity
implemented as
Integrated Infrastructure Initiative
Contract number: RII3-CT-2004-506171
Project Co-ordinator: Prof. Brunetto Giovanni Brunetti
Reporting period: from June 1 st 2006 to November 30 th 2006
Project funded by the European Community
under the “Structuring the European Research Area”
Specific ProgrammeResearch Infrastructures action
1

3 RD YEAR INTERIM ACTIVITY REPORT
1. PROGRESS REPORT
1.1 Summary of activities .............................................................................................4
1.2 Management Activity ............................................................................................4
1.2.1 Management tasks ................................................................................................ 4
1.2.2 General meetings .................................................................................................. 5
1.2.3 Other meetings………………………………………………………………… 7
1.3 Networking Activities ...........................................................................................8
1.3.1 N1-Sharing knowledge and resources .............................................................. 8
1.3.1.1 Activity progress.................................................................................... 8
1.3.1.2 Meetings and workshops ..................................................................... 13
1.3.2 N2- Materials and methods in conservation................................................... 15
1.3.2.2 Activity progress…………………………………………………. .. 15
1.3.2.2 Meetings and workshops ..................................................................... 21
1.4 Transnational Access Activities...........................................................................22
1.4.1 TA1: AGLAE...................................................................................................... 22
1.4.1.1 Description of the publicity concerning the new opportunities
for access .......................................................................................... 22
1.4.1.2 Description of the selection procedures and access activity ............ 22
1.4.1.3 Meetings and workshops .................................................................. 24
1.4.2 TA2: MOLAB................................................................................................ ….25
1.4.2.1 Description of the publicity concerning the new opportunities
for access ........................................................................................ ..25
1.4.2.2 Description of the selection procedures and access activity ............ .25
1.4.2.3 Meetings and workshops……………………………………… ... ..27
1.5 Joint Research Activities .................................................................................. 27
1.5.1 JRA1:Development and evaluation of new treatments for the
conservation-restoration of outdoor stone and bronze monuments .............. 27
1.5.1.1 Activity progress.................................................................................. 28
1.5.1.2 Meetings and workshops ..................................................................... 31
1.5.1 JRA2:New methods in diagnostics: imaging and spectroscopy .................... 31
1.5.2.1 Activity progress.................................................................................. 32
1.5.2.2 Meetings and workshops ..................................................................... 35
2. LIST OF DELIVERABLES……………………………………………………………......36
3. USE AND DISSEMINATION OF KNOWLEDGE………………………...…………… 38
ANNEXES
Annex 1 – Summary Report of the Third Interim Meeting………………………...................41
Annex 2 – Composition of the Users Selection Panel………………….……………..............50
Annex 3 – List of AGLAE and MOLAB User-Projects ……………………………...............51
Annex 4 – Standardised format for analytical procedures…………….…………. ............…..53
Annex 5 – Working group meeting on “interlaboratory comparison” (N1)................... …. ...66
Annex 6 – Presentation of N1 activity on “dyeing and dyestuffs” at DHA 25 th … .............….72
Annex 7 – Working group meeting on “electron microscopy” (N1) ……...............................75
Annex 8 – Working group meeting on “organic materials in cross sections” (N1) ..................78
Annex 9 – Discussion Panel on “treatment evaluation methods” (N2)…………….............…91
Annex 10 – Report on JRA1 (stones)…………….…………. .......................................... …..135
2

Annex 11 – Report on JRA1 (bronzes) ......................................................................... …. ..173
Annex 12 – Progress Report on JRA2 lab NMR methodologies on ceramics and stones.........195
Annex 13 – Report on JRA2 activity on portable NMR 3D methodologies ............................219
Annex 14 – Progress Report on JRA2 systems for IR multispectral imaging……… ....... …...221
Annex 15 – Progress Report on JRA2 equipment for XRD/XRF measurements…… .........…243
Annex 16 – Progress Report on JRA2 equipment for μ-Raman and μ-fluorimetry............ …..253
APPENDIXES
Appendix 1 – Letter to launch the N2 e-forum………………………………………………...255
Appendix 2 – ICOMOS announcement of the N2 e-forum ………………………………257
Appendix 3 – Summary of the e-forum ……………………………………………..………….259
Appendix 4 – Letter of withdrawal of an AGLAE project by the user……………… …..264
3

1. PROGRESS REPORT
1.1 – Summary of activities
The third year activities of Eu-ARTECH started on June 1 st 2006. All the planned tasks of
networking, access and joint research activities had their regular development, according to the
contract. After 30 months from the start-up of the project, significant progresses have been done
and all the milestones have been achieved.
The present interim report describes the activities developed during the first six month of the
third year (June 1 st - November 30 th 2006), in view of the preparation of the Third Annual
Report to be delivered at the end of May 2007.
1.2 – Management Activity
The main management activity of the period consisted of:
- final assessment of the amendments to the contract imposed by the merging of INOA
into CNR;
- distribution of the (pre)financing of the second year among the partners;
- preparation of the Second Annual Report;
- dissemination of knowledge through presentations of Eu-ARTECH activities, with
emphasis to Transnational Access, in relevant international and national conferences
and meetings;
- intensification and deepening of the relations with other I3’s or international and
national projects active in the field of research on cultural heritage.
During the period, one meeting of the Governing Board was held.
All these activities are described in the following paragraphs.
1.2.1 – Management tasks
The first management task of the third year was the final assessment of the contract amendment
of the second year and distribution of pre-financing of the second year to the partners. In fact,
as mentioned in the Second Annual Report, the second year was marked by strong accounting
delays due to a long decision-making process of the EU Contract amendment. The amendment
was imposed by the merging of one participating infrastructure (INOA, partner 13) into another
(CNR, partner 3), which automatically implied a change of the cost model from AC to FC. The
change was possible only through two lengthy steps, due to internal and national rules. In
addition, a cost model change of another participant (LNEC, partner 9), was necessary.
In response to this situation, the amendment procedure was so long that the second year budget
was available to the Consortium only after the end of the second year period. The amendment
approval by the EU was communicated on June 27 th 2006. The payment of the second year prefinancing
was dated August 14 th , with budget available in the Coordinator bank within
September 2006. The distribution of pre-financing to the partners was carried out immediately
after, with the last payment in October 2006.
After the Second Annual Meeting, held in Lisbon, PT, on May 2006, the Coordinator and
Consortium partners were also intensively engaged in the preparation of the Second Annual
4

Report. Particular efforts were dedicated to the fulfilment of the various administrative
requirements, such as correct compilation of Form C and signature of Audit Certificates. At the
deadline of July 15 th 2006, all the partners were ready, apart one because of internal specific
rules of the institution. This difficulty led to some delay in the presentation of the Annual
Report, that was finally delivered on August 21 st 2006.
Two requests of adjustments in some documents were received on September 28 th and October
27 th . After these adjustments, the Second Annual Reporting and Implementation Plan for the
Third Period were approved. Therefore, during the days of preparation of this report, the third
year pre-financing is available in the Coordinator bank and the procedure for the distribution to
the Consortium partners is started.
During the first six months of the third year, contacts were maintained with other organisations
or infrastructures active in the field of cultural heritage, with the objective to promote crossfertilisations
in order to establish a common area of encounter and interchange of knowledge.
Participation to the activities of I3-NET was continuous with positive exchange of
administrative experience in the perspective of future managerial and programme aspects of
FP7. The activities of ESFRI to produce an infrastructure road map were also monitored.
Specific contacts were maintained and deepened with LASERLAB, NMI3, and IA-SFS, as well
as COST G8, and CEN/TC 346, the European Standard Committee dedicated to the
“Conservation of Cultural Property”. Specific contacts have been also developed with ICTP,
Abdus Salam International Centre for Theoretical Physics of Trieste, an organisation dedicated
to promote education and training of young scientists, with a particular attention to those of less
developed countries..
Attention was also dedicated to Marie-Curie actions, such as ATHENA (A scientific Training
for High Education iNitiatives in Art conservation) and EPISCON (European PhD in Science
for Conservation).
During the period, the Eu-ARTECH website (www.eu-artech.org) was continuosly adjourned,
introducing new pages and links in the effort to create a friendly interface with users and
institutions external to the Consortium. A specific restricted area of the website was used for the
exchange and diffusion of internal working documents.
The Governing Board met one time during the period June 1 st - November 30 th 2006, in
Perugia, IT, in occasion of the Third Interim Meeting, held on November 20 th -21 st , 2005. A
report on this meeting is in the following paragraph.
1.2.2 General Meetings
The Third Interim Meeting of Eu-ARTECH, was held in the Sala Dessau of the University of
Perugia, UNI-PG, IT, on November 2006. The meeting coincided with the 6 th General Meeting
of Eu-ARTECH.
In Perugia, the 6 th Governing Board Meeting was also held. According to the Consortium
Agreement, this meeting was restricted to the Coordinator and one authorised representative for
each participant infrastructure.
The following GB members were present: Coordinator: B.Brunetti; UNIPG: A. Sgamellotti;
CNRS-C2RMF: M.Menu; CNR-ICVBC: M.Matteini; NGL: A. Roy; OPD: D. Pinna; BLFD:
M. Mach; OADC: S. Sotiropoulou; ICN: A. DeTagle; LNEC: J. Delgado; IRPA:
I.Vanderberghe; UNIBO: R. Mazzeo; INOA: L. Pezzati. Apologises: B. Bluemich, RWTH.
The following topics were included in the Agenda: 1-Annual reporting; 2-Amendments to the
contract; 3-Mid term review; 4-Prefinancing of the third year and administration;; 5-Date and
location of the next General Meeting
5

1-Annual reporting
The Coordinator briefly reminded to the Consortium members that the 2nd Annual Report was
delivered on date August 21 st . The first assessment from EU was received on date September
28 th with the request of adjustments for some documentation (UNI-PG, CNRS-C2RMF, CNR-
ICVBC/INOA, OPD, LNEC). The corrected documents were sent to Bruxelles on date October
27 th . A second assessment was received on November 8 th with the request of integrative
certificates. The new documents were sent on November 9 th .
After these last documents, the assessment of the 2nd Annual Report was closed.
B.Brunetti underlined how the work for second annual reporting suffered some inconvenient:
- The scientific report of the partners was, on the average, delivered to the Coordinator too late,
leaving only few days to compile the final report, which included also the usually very complex
management section. After discussion, it was decided to deliver the reports on scientific activity
of each partner to the Coordinator before the annual meeting.
- One engaging section is the “Implementation Plan for the Next Period”. The plan is discussed
by the Governing Board at each annual meeting, but very often full aspects are not yet defined
in detail. It was underlined that it is indispensable that each partner starts to plan activities and,
more relevant, detailed expenditures, at least two months before the annual meeting. The GB
agreed.
-Very relevant is the prompt delivery of Audit Certificate and associated Form C. It was
recommended to pay attention to the fact that the amount reported in last column of the first
page of Form C is identical, at the centesimal, to the budget certified by the auditor. Important
is also the “Justification of resources deployed”, where the various expenditures of the project
are described. This section is generally not enough detailed. The Coordinator recommended to
describe travels in terms of person, destination, and typology of the meeting or visit, avoiding to
write simply “ participation to conferences”.
- Within the “Justification of resources deployed” it is generally neglected the section where
justification for possible deviation from the planned budget should be written. The Coordinator
invited the Consortium members to fill in appropriately also this section.
After the presentation, the Coordinator answered to several questions and, after discussion, the
following time-schedule for the next annual deadlines was unanimously approved:
- 1 March: start preparation of the Implementation Plan by each Consortium member;
- 15 April: start preparation of Scientific Report by each Consortium member;
- 5 May: delivery of Implementation Plan and Scientific Report to the Coordinator;
- 10 May: Annual Meeting;
- 1 June: start preparation Management Report and Audit Certificate by each partner;
- 20 June: delivery of Audit Certificates to the Coordinator.
2-Amendments to the contract
In the second year amendment to the contract, the following modification was introduced on the
distribution of the total budget along the five years of the project:
1 year (month 1-12): 650.318,31 euros
2 year (months 13-24): 1.034.411,00 euros
3 year (months 25-36): 1.034.630,00 euros;
4 year (months 37-48): 1.034.630,00 euros;
5 year (months 49-60): 612.610,69 euros.
[note: the spent total budget during the first and second year was 657.892,63 and 947.888,22
euros, respectively];
The Coordinator reminded that:
a- each Consortium member should take care of the fact that the budget of each institution must
be carefully planned, in order to avoid to arrive at the last year with a too high amount of
money; this could imply the impossibility to spend the whole budget;
b- who will not be able to fully spend all the budget should declare it as soon as possible, in
order to allow the GB to carry out an amendment at the next annual reporting.
6

A discussion followed, where the Coordinator answered to several questions. At the end all the
members agreed on the necessity to carefully take care of the planning of each budget along the
next years of the project, presenting a specific plan at the next GB meeting.
3-Mid term review
The Coordinator announced that the Mid Term Review of the Consortium activities will be
carried out at the end of the third year, i.e. at the next deadline of May 2007.
The modalities of the Review are explained in the contract (Article 9. Section 1.3):
Together with the documents referred to in Article II.7.2 referred to P3 (note: end of the third
year), the consortium shall submit a “mid-term-report” covering all the work carried out since
the start of the project, objectives, intermediary results and conclusions, an updated plan for
using and disseminating knowledge, and, an update of the remaining work planned in Annex I.
These documents shall be evaluated in accordance with Article II.8.1,2,4, and 5. [art. II.8 :
Evaluation and approval of reports and deliverables].
One or two referees will be invited to participate to the Annual Meeting and analyse the Mid
Term Report.
In the Report should be clearly indicated:
-achievements of networking, access, and joint research activities;
-highlights of the activities;
-list of publications;
-list of TA’s for AGLAE and MOLAB with a synthesis of results;
-initiatives for the dissemination of knowledge.
The Coordinator recommended each Consortium member to cooperate for a complete and
detailed reporting of all the initiatives.
4-Prefinancing of the third year and administration
The Coordinator specified that each Consortium member received the second year prefinancing,
but not yet the third one. The Coordinator showed the prospect of the various
prefinancing of each institution for the second year and declared his availability to explain
details to each representative. Such explanations followed.
5-Date and location of the next General Meeting
In a previous GB meeting, it was already established to organise the Third Annual Meeting in
Munchen, DE. The assembly confirmed unanimously the location of Munchen, giving the
charge to BLfD to take care of the organisation. M.Mach, as BLfD representative, confirmed
that the meeting will be preceded by the workshop “Small samples, big objects”, also organised
by BLfD.
The following dates were unanimously approved:
- May 9: Workshop “Small Samples, Big Objects”;
- May 10-11: Third Annual Meeting.
The Coordinator reminded one more time that the Third Annual Meeting will be held at the
presence of one or two experts, selected by the EU, who will evaluate the work developed
during the first three years of the project (mid term refereeing).
After the 6 th GB Meeting, the Steering Committee Meeting was also held, where the activities
developed in the various tasks planned for the first six months of the third year were first
presented and discussed with all participants and then evaluated and finally approved by the
Steering Committee in a separate room. Details of this meeting are described in Annex I of this
report.
1.2.3 Other meetings
Eu-ARTECH representatives participated to the activities of I3-NET. In particular,
A.Sgamellotti (UNI-PG) participated to:
- I3-NET Science and Society Communications Workshop, London, UK, 6-7 November
2006; the two days meeting consisted of a meeting of I3 Coordinators, followed by a
7

conference devoted to the relevant problem of how to communicate science to the large
public.
1.3 – Networking activities
After the end of the second year, networking activities continued, articulated in two lines,
one regarding the analysis and diagnostics on artwork materials (N1), the second regarding the
materials and methods used in conservation of cultural heritage (N2). Both activities were
accomplished through continuous interactions among the responsibles of the networking tasks
and the participants. Natural coordination followed also from the Eu-ARTECH periodical
meetings, held with a semestral cadence.
Participants to N1 and N2 were all the partners, apart INOA and RWTH.
Responsible for networking was UNI-BO.
1.3.1 – N1: Sharing knowledge and resources
N1 networking specific activities of the first six months of the third year consisted of:
N1-Task 1: Analytical resources, analytical procedures and investigation strategies (task
leader: C2RMF)
-subtask 1c: Developing standardised formats for analytical techniques, devoted to the
proposition of a standardized format for describing analytical procedures for natural
organic substances investigation with non-invasive techniques and electron
microscopy;
N1-Task 2: Exchange knowledge and expertise (task leader: ICN)
-subtask2a (ICN) Reference Materials Sharing- overview on possible sharing of
reference materials among infrastructures; sharing of standards of dyed textiles and
lakes;
-subtask2b (C2RMF): Cooperation with MFA Boston on CAMEO (Conservation & Art
Materials Encyclopaedia Online);
-subtask2c (ICN). Working meeting on the inter-laboratory comparison and exchange of
analytical data on September 20 th , 2006, Suceava, Romania;
-subtask2d (ICN): Working group on electron microscopy and cultural heritage.
N1-Task 3 - Common approaches in the examination and analysis of paintings (task leader:
NGL)
N1-Task 4: Common analytical strategies (task leader: OADC)
For each one of these tasks, milestones were achieved and respective deliverables are reported
as annexes within this report.
Other tasks, already started during the previous years, had some natural continuation. These
tasks mainly regarded the dissemination of knowledge.
1.3.1.1 – Activity progress
During the first semester of the third year, a continuous effort was made to open and diversify
the distribution of information relative to networking and access activities. At the end of
October 2006, the list of institutions or companies registered in the Eu-ARTECH mail-directory
was significantly extended (209 institutions, compared to 115 registered at the end of
November 2005). According to the type of activities, they were: 57 universities or educational
institutions active in scientific and technological research, 40 public research institutes, 36
museums or galleries, 21 cultural heritage institutions, 20 universities or educational institutions
active in cultural heritage, 9 restoration workshops or experts, 6 international organisations, 4
instrumentation manufacturers, 3 local administrations, 2 libraries, 2 archaeology institutions, 2
8

associations or foundations, 2 technology research centres, 2 publishers, 1 archive, 1 religious
institution. These institutions belong to different countries – in the European Union: France 29,
Italy 28, Germany 20, United Kingdom 20, Spain 12, Greece 9, Portugal 9, Belgium 7,
Netherlands 5, Austria 3, Malta 3, Sweden 3, Czech Republic 2, Poland 2, Slovak Republic 2,
Cyprus 1, Denmark 1, Estonia 1, Finland 1, Ireland 1, Lithuania 1, Slovenia 1; – in Europe, but
outside the European Union: Turkey 6, Norway 4, Romania 4, Switzerland 4, Belarus 1, Croatia
1, Montenegro 1, Russia 1, Vatican 1; – outside Europe : United States 10, India 2 , Argentina
1, Canada 1, Cuba 1, Morocco 1, Australia 1, Syria 1.
A big effort was made by all the Consortium members to extend the list towards restoration
workshops, producers of cultural heritage materials, libraries, archives, archaeology institutions,
and manufacturers of instrumentation. Efforts were also done to involve more extensively
institutions of EU countries probably under-represented, such as Czech Republic, Denmark,
Finland, Hungary, Poland, and others.
A list of conferences of interest in the field of “science & technology for cultural heritage” was
monthly updated and distributed to all the institutions registered in the mailing list. The list of
conferences is accessible on the Eu-ARTECH website (approximately 120 conferences have
been registered, from mid 2004 to 2008). The list is available on request to be addressed to J.L.
Boutaine (C2RMF), the responsible of N1 activity.
Progresses have been done in the various tasks and the respective achievements are reported
hereby.
N1-Task 1: Analytical resources, analytical procedures and investigation strategies (task
leader: C2RMF).
-subtask 1c: Developing standardised formats for analytical techniques, devoted to the
proposition of a standardized format for describing analytical procedures for natural organic
substances investigation with non-invasive techniques and electron microscopy.
Efforts were continued to contribute to the creation of standards, to be adopted within the
Consortium and to be proposed to a larger scale of users in cooperation with CEN TC/346.
coordinated by Vasco Fassina (Note: as reported in Annex I, Vasco Fassina participated to the
Third Interim Meeting in Perugia, in November 2006, presenting the more recent activities of
CEN TC/346).
The standard format for the description of the analytical protocol followed on natural
organic dye analysis with HPLC-PDA, already developed during the second year, was
evaluated during the working meeting held in Suceava, Romania (20 th September 2006). It
emerged that the proposed format fulfilled specifications and needs and, therefore, was not
modified.
Instead, the format for reporting the analytical results of HPLC-PDA was slightly modified,
adding the name of the protocol used for each specific measurement. This specification was
considered necessary and, therefore, it was not neglected. The new format for reporting HPLC-
PDA results is in Annex 4- I.
In addition, an analytical protocol was produced for HPLC-MS which followed the same
standard format as used for HPLC-PDA. This format is reported in Annex 4-II.
As continuation of inter-laboratory comparison on natural dyestuff and organic pigment
investigations, with focus on complementary non-destructive techniques, a proposal was made
for a standard format to describe analytical procedures for natural organic substance
investigation with fibre-optic UV fluorescence spectroscopy. This proposal was discussed
during the meeting in Suceava and, under the coordination of UNIPG, the format was prepared.
A copy is reported in Annex 4-III.
Within this task, efforts will be carried out to develop analytical procedures for the
identification and quantification of metals used as mordants, both in lakes and dyed textiles.
The identification can be carried out by XRF or even on microsamples by SEM-EDS. This will
be part of a future topic.
9

N1-Task 2: Exchange knowledge and expertise (task leader: ICN).
The task was articulated in different subtasks.
-Subtask2a (task leader: ICN) - Reference Materials Sharing- overview on possible sharing of
reference materials among infrastructures, in particular on sharing of standards of dyed textiles
and lakes.
Including the materials developed during the previous period, now 12 organic pigments derived
from 7 different botanical sources and 16 dyed textiles (wool and silk) are available to the
Consortium members. These are the most appropriate reference standard materials to be
exchanged for a significant inter-comparison of analytical data. Un-dyed wool and silk are
available as well, as reference materials.
The botanical sources so far are:
- Dyer’s broom (Genista tinctoria)
- Indigo (Indigofera sp.)
- Madder (Rubia sp.)
- Mexican cochineal (Dactylopius coccus)
- Safflower (Carthamus tinctorius)
- Sappanwood (Caesalpinia sappan)
- Weld (Reseda tinctoria)
Reference material (on silk and wool and as pigment) of two other, oriental biological dye
sources Miscanthus sinensis Anderss and Chinese pagoda-tree (Sophora japonica L.), were
produced through a cooperation of KIK-IRPA and the Getty Conservation Institute. They will
be rendered available.
Issues for new reference materials, of interest within this task, are:
- organic pigments painted in different binding media (in preparation),
- new samples with mixtures of dyes (in preparation),
- dye references from MODHT (Monitoring of Damage to Historic Tapestries);
- sawwort, lac dye, young fustic and old fustic, buckthorn, sap yellow and green (only
for pigments).
The best storage conditions for the reference materials have been discussed. The proposed long
term storage conditions are:
- Textile samples: storage in acid free paper,
- Pigments: storage in Teflon vials (supplied by NGL),
The best climate conditions for storage of both textiles and pigments are: a-room temperature;
b- relative humidity 50 % .
Small amounts of the prepared reference materials are available for the European community of
scientists, when necessary for analytical purposes. The analytical protocols and the reports
obtained so far, will be available as well. These documents could contribute to homogenise
analytical procedures among the various laboratories or could help in the development and
diffusion of new techniques.
Large amounts of textiles or pigments could be prepared, according to the well-defined recipes
used for preparing the reference materials. The recipes will be also available for the European
community of users.
-subtask2b (task leader: C2RMF): Cooperation with MFA Boston on CAMEO (Conservation &
Art Materials Encyclopaedia Online).
A memorandum of agreement between the Museum of Fine Arts Boston and EU-ARTECH has
been signed. European contributors (members of EU-ARTECH plus some Spanish institutions)
should have now online access to enlarge the encyclopaedia (European languages synonyms,
European trademarks…).
-subtask2c (task leader: ICN). Working meeting on the inter-laboratory comparison and
exchange of analytical data on September 20 th , 2006, Suceava, Romania.
The results of the analyses (including the exchange of analytical data) of the well documented
reference materials have been evaluated during a one-day Eu-ARTECH working group meeting
10

held on September 20 th , 2006, in Suceava (Romania). The working meeting was held during the
days of the 25 th Dyes in History and Archaeology (DHA) Conference.
The inter-comparison of results was possible on the same common reference materials prepared
and shared in the last period (shared reference material: indigo, Mexican cochineal, dyer’s
broom, weld, redwood, safflower and madder). Analytical methods were non-invasive
techniques and HPLC-PDA.
The minute of the meeting is a “deliverable” of the period and is annexed to this report (see
Annex 5). Due to the developed standard protocols and reporting formats, it has become
possible to exchange analytical information at a very detailed level. This aspect was highly
appreciated by experts within the Eu-ARTECH consortium and by external experts (see Annex
5).
During the working group meeting, it was decided that the analytical protocols, the analytical
reports and the recipes for dye preparation will be rendered available via the Eu-ARTECH
website. A possible integration of the analytical data within the exact frame of MASC, using
JCAMP, is a step which could be developed in the future. A structure will be built in which
each result will be grouped according to their specific botanical source and application (silk,
wool or pigment). A clear explanation of the project and a summary of the results will be
produced as well, to ensure that the interpretation of the available information is correct.
A first dissemination of knowledge on this activity was done during the Dyes in History and
Archaeology 25th-meeting (September 21-23 th 2006) by J. Kirby (NGL), who gave a
presentation entitled: « Dyeing and dyestuffs revealed: the EU-ARTECH collaborative study of
reference materials ».
The abstract and the file with the .ppt presentation at the conference are added to this report in
Annex 6.
Natural organic polymers in art (NOPART) (responsible: KIK-IRPA)
Very recently, the confirmation was received, from M. Ballard from the ICOM-CC working
group on textiles, that one session of the next ICOM-CC joint interim meeting will be reserved
to the Eu-ARTECH contributions. This meeting will be a joint meeting of three ICOM-CC
working groups, 1-Textile, 2-Leather and Wood, 3-Furniture and Lacquer, all dealing with
natural organic polymers. With regard to this concrete opportunity, it will be decided, within
the next weeks, how the event will be worked out.
-subtask2d (task leader: ICN): formation of a working group on electron microscopy and
cultural heritage.
As foreseen in the implementation plan of the period, the kick-off meeting of a working group
on electron microscopy applied to cultural heritage was held in Perugia, at the end of the
Interim Meeting of November 21 st 2006.
The following Consortium members were present: M. Mach (BLFD), M. Vagnini (UNI-PG), F.
Presciutti (UNI-PG), F. Rosi (UNI-PG), S. Porcinai (OPD), B. Salvadori (OPD), D. Pinna
(OPD), S. Prati (UNI-BO), M. Spring (NGL), A. Roy (NGL), I. Joosten (ICN)
Also interested are S. Bracci (OPD) and M. Menu (C2RMF). M. Schreiner (ABK Wienexternal
expert) and A. Adriaens (University of Gent, BE-external expert) communicated their
interest to participate.
Electron microscopy is an analytical technique used by many of the Eu-ARTECH Consortium
members. For this reason, a working group on the technique and its application to cultural
heritage was formed. The objective is to initiate discussions on the subject and to share
experiences with external experts and users. The various topics proposed for discussion
included: a-interpretation of problems for the various artefact materials (paintings, metal, paper,
glass, plastic, textiles etc), b-application of innovative techniques in the field, c-exchange of
knowledge. During the Perugia meeting, the participating Consortium members introduced their
field of interest through short presentations and identified topics of common interest to be
jointly developed in the future. The working group is expected to encourage effective sharing of
knowledge and good practices in the field, as well greater awareness of new developments. A
more detailed report on the Perugia meeting is reported in Annex 7.
11

N1-Task 3 - Common approaches in the examination and analysis of paintings (task leader:
NGL).
A working group on the characterisation of organic materials (binding media, varnishes,
pigments) in paint cross-sections was proposed by R. Mazzeo (UNI-BO) at the second annual
meeting in Lisbon, with the perspective to organise of a conference on the topic in September
2007. The subject is of particular interest because the analyses directly carried out on cross
sections have good capability to identify organic and inorganic components whilst preserving
the spatial information.
The location of organic materials within paint layers is often crucial in the interpretation of
analytical results (for example determining whether the material is original or from a later
conservation treatment). However, the bulk sample analysis using chromatographic methods,
conventionally applied to the analysis of organic materials in paint, does not provide this
information. In addition, the location of the organic materials within the paint and subsequent
analysis of an area of high concentration of the component opens up the possibility of
identifying materials present even in small quantities.
Over the last few years, some innovative analytical techniques, capable of identifying organic
materials directly on paint cross sections, were introduced. Among these are
microspectrofluorimetry, new microchemical staining tests, micro FTIR mapping, SIMS, and
others. Some of these are today well experimented, while others are only at the first stage of
development. For this reason, this is the right moment to carry out a state-of-the-art study in the
area, with the goal to assess the advantages and limitations of each technique, but also having in
mind the possibility to identify other innovative methods that might also have good
applicability in the field.
During the meeting of the working group of this task, held in Perugia in November 2006, a
literature survey was presented, and further work for the next period related to preparations for
the conference (to be held in Bologna in September 2007) was discussed. A more detailed
report on the working meeting, together with a summary of the literature survey has been
compiled and is reported in Annex 8.
N1-Task 4: Common analytical strategies (task leader: OADC)
During the third year, focusing on the development of the two action lines A and C of Task 4, it
was decided to organise, jointly to the next meeting of DHA, in Vienna November 7-10, 2007,
an additional working day to discuss “ New strategies for natural dyestuff and organic pigment
analysis in art objects (paintings or dyed textiles)”.
The event will be organised by Eu-ARTECH in collaboration with the DHA organising
committee and will take advantage of the regular dissemination procedure of DHA meeting,
currently addressed to the international scientific community in the field of natural dyestuff
investigation. ICN, as co-organiser of the 26 th DHA, will act as intermediate to assure the best
preparation of the event.
The main aim is the dissemination of the Eu-ARTECH initiative among experts on natural
dyestuff and organic pigment analysis and introducing discussion topics towards a second level
of assessment of methodologies and analytical results, passing from the identification of fresh
reference materials to the investigation of real objects, establishing an integral approach and
common criteria for interpreting analytical results.
Tentative topics are proposed in two parts:
1 st part - Dissemination of Eu-ARTECH initiative, presenting N1 achievements - Assessment of
methodologies and analytical results on natural dyestuff and organic pigment characterisation
(working group ICN, KIK-IRPA, NGL, OADC, UNI-PG).
- Sharing reference materials (well-defined, prepared following well documented historical
recipes) (Task N.1.2 Deliverable)
- Sharing knowledge on natural dyestuff and pigment identification through interlaboratory
experiments and comparison of results on common reference materials (Task N.1.1
Deliverables) establishing:
- common formats for the documentation of analytical protocols,
- common formats for exchanging analytical results,
12

- common bases for interpretation of analytical results (Task N1-4).
2 nd part - Novel analytical approaches that could allow studying the organometallic complex as
a whole. In order to have information about the type of complex that a dye can form with
mordant, it would be useful to use spectroscopic methods applicable on the whole
organometallic complex without breaking the coordination bonds. Discussion will be
introduced on the development of novel analytical approaches integrating complementary or
cross-informational techniques.
A compilation of recent literature on the subject is under processing.
A first list of experts has been set, that could be invited to contribute with their knowledge on
novel approaches of dyestuff and organic pigment analysis with advanced techniques, such as:
-Fibre-optics UV-vis fluorescence spectroscopy with stationary and time resolved
methods,
-Micro-fluorimetry on cross-sections,
-Raman spectroscopy (Surface Enhanced Raman Spectroscopy-SERS; FT-Raman,
Pulsed-Raman).
All the results of N1activities of Eu-ARTECH could form a substantial base for a cooperation
with CEN in order to establish standards in Europe in cultural heritage. To this effort, contacts
are permanently established with Vasco Fassina, Coordinator of CEN TC/346 (European
Committee on Standard in Cultural Heritage).
1.3.1.2. Meetings and workshops
The Eu-ARTECH’s approach and activities on “sharing knowledge and resources” have been
diffused by the Consortium partners in relevant European conferences or meetings.
They are:
- 2 nd International School of Structural and Molecular Archaeology: How did Solid-Solid
Transformations Occur?, Erice, IT, 2-6 June 2006; at the meeting, dedicated to the memory of
the great French scientist H.Curien; several advanced physical and chemical applications to
cultural heritage were presented; B.Brunetti (UNI-PG) described Eu-ARTECH activities with
reference to the application of non-invasive analytical spectroscopic methods;
-12èmes Journées d'Etude de la SFIIC-Couleur & Temps - La couleur en conservation
restauration, Paris, FR, 21-23 June 2006; at this meeting R.Mazzeo (UNI-BO) presented the
activities developed within N1-Task3 on examination of paintings;
-XXVVII European Congress on Molecular Spectroscopy, EUCMOS, Istanbul, TU, 3-8
September 2006; at this meeting, B.Brunetti (UNI-PG) presented the N1 activities of Eu-
ARTECH in the field of analytical spectroscopy applications to cultural heritage; particular
attention was given also to Transnational Access;
- Dyes in History and Archaeology - 25 th Meeting, Suceava, RO, September 21-23 th 2006; Eu-
ARTECH partners present: J. Wouters (KIK-IRPA), I. Vanden Berghe (KIK-IRPA), J. Kirby
(NGL), C. Higgitt(NGL), D. Peggy (NGL), M. van Bommel (ICN), M. Groot Wassink (ICN),
Lemonia (OADC), C. Miliani (UNI-PG), C. Clementi (UNI-PG). Scope and results of the N1
reference materials study were disseminated. Key findings and perspectives, were presented by
J. Kirby in the communication: “Dyeing and dyestuffs revealed: the EU-ARTECH collaborative
study of reference materials” [.ppt presentation available on the website]. During the
conference, a working meeting of the Eu-ARTECH partners (OADC, ICN, IRPA, NGL, and
UNI-PG) took place in Suceava, where the progress of the work on topics of dyes have been
discussed (see previous pages of this report).
- Synchrotron Radiation in Arts and Archaeology, Berlin, 27-29 September 2006; the meeting,
organised every two years in different countries, is one of the most relevant meeting on cultural
heritage in Europe; this year was partially supported by Eu-ARTECH; the Book of Abstract is
available;
-International Seminar on Museums, Science and Technology, Rio de Janeiro, Brazil, 2-5
October 2006; this seminar was organised by the Museo Historico Nacional de Rio de Janeiro
13

and promoted by the Brazilian Ministry of Culture; at the meeting, A.Sgamellotti (UNI-PG)
presented the activities of Eu-ARTECH to an odeon composed by Latin American conservators
and curators, creating the base for an authoritative Brazilian participation to the future
conference in La Havana 2007. To the meeting participated also A. de Tagle (ICN).
- 6° Sigma Aldrich Young Chemists Symposium (6th SAYCS), Riccione (Italy), October 9-11
2006; within this meeting, E.Joseph and R.Mazzeo presented Eu-ARTECH N1 activities, with
particular reference to Task 3 on “examination of paintings”;
- Science for cultural heritage – ICTP- Trieste, October 23 th -28 th 2006; this conference was an
interdisciplinary meeting having the specific character to be open to non European countries.
Attendees were 84 from 26 countries, including less developed countries, and 3 international
organisations. S.Rohers and J.L.Boutaine (C2RMF) participated presenting the networking and
access Eu-ARTECH activities. A practical demonstration on portable instrumentation, with the
participation of the MOLAB team of UNIPG (A.Sgamellotti, C.Miliani, F.Presciutti,
A.Cosentino) was organised at the end of the conference: more than 40 participants attended
this session. Other practical demonstrations were given by the International Atomic Energy
Agency (IAEA)-Seibersdorf Laboratory- and the University of Sassari.
Dissemination of knowledge on Eu-ARTECH activities was also carried out by B.G.Brunetti
and A.Sgamellotti (UNI-PG) during a visit of some of the most relevant institutions working in
the field of artwork conservation in USA (22 August-2 September 2006).
Visited institutions were:
- the Getty Conservation Institute, Los Angeles;
- the Art Institute of Chicago, Chicago;
- the Metropolitan Museum, New York;
- the Museum of Modern Art, New York.
The agenda of each visit was articulated in:
a-general discussions on activities of the field in Europe and USA,
b-presentation of the Eu-ARTECH activities,
c-visits to the conservation and science laboratories,
d-planning for possible cooperations.
Behind the scientific personnel of the various institutions, contacted persons for future
interactions were:
-Dr. Giacomo Chiari, Director of the Scientific Laboratories of the GCI;
-Dr. Francesca Casadio, Director of the Scientific Section of the Chicago Art Institute
Conservation Laboratories;
-Dr. Marco Leona, Director of the Scientific Laboratories of the Metropolitan Museum, New
York;
-Dr. Chris McGlinchey, Scientific Director at the MoMA Conservation Laboratories, New
York.
Several N1 working meetings were held during this reporting period, such as:
- KIK-IRPA – UNI-PG Bilateral Meeting in Perugia, 10-14 July, 2006 - Participants: I.
VandenBerghe (KIK-IRPA), C.Miliani, C.Clementi (UNI-PG).
In the context of a possible application of the MOLAB equipment for the in-situ damage
assessment of historical tapestries, a preliminary study was started to investigate the efficiency
of ATR-FTIR, NMR and Raman techniques for the monitoring of fibre degradation, as well as
to study the efficiency of Raman and portable XRF for dye and mordant identification. This
study was performed on well-defined wool and silk reference samples, before and after
accelerated ageing. Out of the preliminary results of these investigations (NMR analysis are to
be continued) it was decided to concentrate more on the identification of dyes and mordants,
rather than on the monitoring of protein degradation.
- OADC – UNI-PG Bilateral Meeting in Perugia, 11-14 October 2006, Participants: C. Miliani,
C.Clementi, A.Romani, A.Cosentino (UNI-PG) and S.Sotiropoulou, A.Kapsalis (OADC).
The topics discussed during this meeting were referred to Task N1.1c and N1.4. In particular:
14

a) Non-invasive fluorescence techniques (spectroscopy and imaging) for the study of dyestuffs
and organic pigments: good parameters were defined for spectra and image recording,
determining optimum λex and emission range to be investigated. Modes for evaluation of
fluorescence spectral data have been discussed, such as the selection of spectral features for the
identification of each class/type of dye (pairs of emission – absorption maxima and shoulders);
b) Development of novel analytical strategies for natural dyestuff and organic pigment analysis
in art objects: tentative topics have been discussed for the meeting attached to the DHA
conference in Vienna, November 7-10, 2007.
During the next six months of the third year, the following meetings will be organised by Eu-
ARTECH:
-“Science and technology for cultural heritage in Europe and Latin American countries”. This
meeting, organised in cooperation with Italian CNR and ICTP of Trieste, will be held in La
Havana, Cuba on February 2007. It will be the occasion to disseminate knowledge within less
developed non-European countries and to establish significant relations with institutions of
Latin America operating in this field. The participation of several representatives from Mexico,
Brazil, Argentina, Chile, Perù, Cuba, and others, is foreseen.
-“From easel painting to music instruments - Binders, colours and varnishes”. This meeting
will be held on March 6th & 7th, 2007, at the “Cité de la Musique”, in Paris. Co-organisation :
Cité de la Musique and C2RMF. For this meeting, about 30 abstracts have been already
received. They will be reviewed by the scientific committee during December 2006. 18 will be
selected for oral presentation. A musical moment by a soloist playing a cello by Giuseppe
Guarneri del Gesù (1698-1744), belonging to the Musée de la Musique’s collection, is planned.
-“Small samples, big objects”. The seminar will focus on objects of huge physical dimensions
like monumental area sites or big statues. Examples will be given on how scientific
investigations are actually an indispensable link within the course of a typical major cultural
heritage work process: analytical findings can drastically influence the outcome and quality of
any work, can markedly contribute to our historical understanding and, last but not least, can
drastically improve the quality of the restoration procedures on the basis of a superior
knowledge.
1.3.2 – N2: Materials and methods in conservation
Planned N2 networking activities of the first six months of the third year were:
Task 1f (resp. CNR-ICVBC) - Survey on cleaning and consolidation – Collection of data
(continuation)
Task 2b (resp. OPD) – Identification of good practices in conservation: set-up of a web page
for an e-forum.
Task 2c (Resp. OADC) – Formation of a working group on evaluation of treatments – A
“Discussion panel” in Firenze, November 2006.
Task 3a (Resp. LNEC) - Adoption of a working methodology among Eu-ARTECH partners for
definition of standards. Identification of contact persons and definition of priorities.
All these tasks have been accomplished and their development is described in the following.
1.3.2.1 – Activity progress
Task 1f (resp. CNR-ICVBC) - Survey on cleaning and consolidation – Collection of data
(continuation)
and Task 2c (Resp. OADC) – Formation of a working group on evaluation of treatments – A
“Discussion panel” in Firenze, November 2006.
15

During the first semester of the third year, the activities related to the survey on “Methods and
materials for conservation” continued. The survey has the as main purpose to assess the present
practice of cleaning and consolidation of stones, metals, and paintings,
The application of scientific methodologies to verify the efficacy of the treatments is also of
interest.
The survey was developed through the diffusion of dedicated forms on the selected specific
typologies of interventions. The forms were elaborated to respond to the specific objective of
the activity, that is "to analyse the results in order to obtain statistical information" with the aim
of "exchanging of knowledge" and create a solid base for a possible definition of "good
practices in conservation" (Task 2).
The survey forms are different, according to the materials and to the conservation treatments:
stones (cleaning, consolidation, treatment of biodeterioration) paintings (cleaning, treatment of
biodeterioration) mural paintings (consolidation, treatment of biodeterioration), metals
(cleaning). In some cases, the forms are composed of two levels: level A, containing essential
information on treatments; level B, containing specific details.
The forms have been firstly written in English and then translated in Italian, Spanish, French,
Portuguese, and Dutch and diffused in Europe during the 2nd year of activity (spring 2006).
They are currently available to the public and can be downloaded from the Eu-ARTECH
website: (http://www.eu-artech.org - Documents section).
The survey has been launched sending an invitation letter to more than 1619 restorers and
conservators belonging both to private and public institutions in Europe and other countries. The
activity was also publicised during international conferences in the field of cultural heritage.
Specific agreements established that the data collected were treated anonymously, but the
results of the survey and a list of names and affiliations of the participants will be published.
The collected information are currently included in a database to allow statistical elaboration.
Long term aim of this great effort is to create a community of restorers, conservators, curators
and scientists, who could share experience (and possibly agreements) on conservation methods
and on traditional and new materials, creating a common knowledge for common diffused
“good practices”.
The phase of collection of compiled forms is still in progress and should be closed at the end of
2006. The forms collected up to now (see Fig. 1) have been inserted in an Access database. This
file has been attached to the previous report (Eu-ARTECH_N2 survey.mdb) together with the
database of compilers (Eu-ARTECH_N2 survey_Compiler.mdb). These files, although not
public, due to privacy issues, are available to possible EU reviewers in the reserved area of the
website, upon direct request to the Convenor (P.Tiano -CNR-ICVBC: p.tiano@icvbc.cnr.it).
Within this activity, a Discussion Panel has been organised in Florence by CNR-ICVBC jointly
with OPD (see: Discussion Panel, Annex 9). The meeting had two main purposes:
- to illustrate and publicise the preliminary results achieved through the collection of
survey data;
- to identify and discuss the state of the art in the methodologies followed for the
evaluation of the efficacy of conservation procedures.
Regarding the first objective, although the number of compiled forms was relatively low for a
statistical analysis, few conclusions have been drawn from the collected data and are reported in
the following:
-the female compilers/restorers are predominant; restorers are specialised in working on specific
materials or objects and, therefore, only in few cases the same restorer compiled forms for two
or more categories (particular is the case of stone restorers that have experience also in mural
paintings treatments, because the typology of the support is similar);
-more than 60% of compilers are from Italy and the rest from other 10 countries participating to
the survey (see Fig. 1), therefore a comparison between the restoration practice and materials in
use in various countries, is, for the moment, with a low significance;
-almost all objects, for which forms were compiled, are located in an “indoor” environment,
except the case of stone artifacts, where the “outdoor” locations are prevalent;
16

-as far as cleaning methods are concerned, “mechanical removal” and “use of solvents/other
chemical agents” are the most frequently reported;
-the main method to assess the effectiveness of an intervention is the “visual observation”;
-the most reported treatments against biodeteriogens are those using “biocides” and
“mechanical methods” for removing a biological growth;
-the treatments against biodeteriogens have received a good appreciation for their effects and
the usually reported method of evaluation was the “in situ observation”, followed by
“microscopic analysis”;
-for consolidation of Mural Paintings or Stone artifacts the “synthetic resins” (applied by brush,
by injection etc.) are definitely more preferred than the inorganic consolidation materials
(calcium or barium hydroxide, mortars etc.);
-the evaluation of consolidation treatments is usually done by “tactile verification of cohesion”.
No. of compiled forms, by country
(11 participating countries)
68% 14%
Bulgaria Canada Cyprus Germany
Greece Italy Portugal Romania
Spain Sweden United Kingdom
Fig. 1. The compiled forms divided by countries
The second objective of the Discussion panel was the presentation and discussion, by experts of
the various fields (stones, paintings, metal and wall paintings), of the state of the art in the use
of scientific methodologies for:
- documentation (record and control of the progressive treatment steps) and standardisation
(recommended procedures);
- evaluation of treatment (analytical measurements of optical and chemical surface properties
(colour, texture, absorbance, interaction with the surface - risk of alteration).
The essential issues were focused on: formulating requirements (protocols and diagnostic tools)
for the monitoring (control on a regular basis) of such parameters after conservation treatments.
A detailed presentation of the topics and of the discussion within the Panel are reported in
Annex 9.
In order to contact a higher number of possible compilers and increase the data necessary for a
more significant statistics, easily accessible and compilable set of survey forms has been designed
17
1%
4%
1%
5%
1% 2% 1%
2% 1%

for stone, paintings, mural paintings and metals, (see Fig. 2). These forms can be filled in,
directly on-line, at the website http://www.icvbc.cnr.it/euartech/ (first deadline on December
31 st , 2006).
Fig. 2 – Home page for the on-line compilation of the N2 survey forms
The on-line survey has been publicised among the IGIIC (Italian Group of the International
Institute for Conservation) members and the ECCO (European Confederation of Conservator-
Restorers’ Organization) associates.
Task 2b (resp. OPD) – Identification of good practices in conservation: set-up of a web page
for an e-forum
An e-forum was launched on the Eu-ARTECH website. The forum is an opportunity to achieve
a general view on possible problems regarding the interactions between restorers and scientists.
In addition, as the occasions of broad in-depth discussion between restorers and scientists are
relatively few, the forum is a chance for a constructive and potentially beneficial
communication between them.
The preliminary step of this e-forum was set up in March 2006 using e-mail, but this meant an
enormous increase of messages for all of us. Hence, it was decided to change the technical
approach, arranging it via web.
A new letter (see Appendix 1) was sent to the previously contacted people announcing that a
web page for a Bulletin Board was set up. In addition, a presentation of the e-forum was
extended to a large public in order to raise an extended participation and awareness. Among the
various initiatives, the forum was publicised at the workshops:
“Le biotecnologie nella conservazione dei beni architettonici”, Trento, Italy, June 9th 2006
“Pavimentazioni Storiche: uso e conservazione - Scienza e Beni Culturali”, Bressanone, Italy,
July 11th-14th, 2006.
This work yielded a new and longer list of interested professionals.
18

Finally, an advertising of the Eu-ARTECH e-forum was made through the ICOMOS
International Secretariat in the e-news – n°6, on date 9 November 2006 (see Appendix 2).
Today, the page of the Bulletin Board is operative (http://eu-artech.icvbc.cnr.it/bb) and many
people from various countries (Belgium, France, Germany, Great Britain, Greece, Italy,
Netherlands, Norway, Portugal, Romania, Spain, Sweden, Switzerland) are registered.
A report based on the first discussions was written (see Appendix 3). The report circulated
inside the forum website.
Task 3a (Resp. LNEC) - Adoption of a working methodology among Eu-ARTECH partners for
definition of standards (CNR-ICVBC_A.M.Mecchi)
A scientific approach is nowadays essential for the conservation of the cultural heritage as
preliminary basis to guarantee a proper planning of ordinary and extraordinary maintenance
works, and to assure their efficacy and durability.
Unfortunately the great experience developed in this field by the different European countries,
for the time being does not constitute a very solid common background, because there are too
many differences not only in the methodologies, but also in the used terminology.
A specific European standardisation activity in the field of conservation of cultural heritage is
essential to acquire a common unified approach to the problems of conservation. In addition, the
possibility to make reference to standardised methodologies or protocols would promote a more
efficient exchange of information, also fostering synergies between experts or specialists
involved in this activity in Europe.
Also, the development of standardised tests and analysis methods will provide the cultural
institutions, enterprises and laboratories with correct instruments for carrying out their work,
improving, at the same time their proficiency/competencies.
What should be standardized in the field of cultural heritage?
The standardisation activity on conservation would deal with:
1) terminology relevant to movable and immovable artefacts, and to methods and material for
their conservation;
2) guidelines for a methodological approach to the knowledge of the artefacts and of the
materials constituting the artefacts, of the deterioration processes, and of conditions of optimum
long term conservation (preservative conservation);
3) testing and analytical methods for the diagnosis and for the characterisation of the artefacts
with regards to outdoor and indoor environmental parameters;
4) testing and analytical methods (both in-situ and in the laboratory) for the evaluation of the
performances of products and methodologies in conservation (ordinary and/or extraordinary
maintenance);
5) testing and analytical methods for the evaluation of conservation conditions of indoor
cultural heritage.
6) standardisation on transportation and packaging methods for the itinerant exhibitions and
exchanges of works of art for temporary exhibitions in museums, galleries, libraries and
archives.
Such a standardisation should concern the majority of materials (natural and artificial stones,
metals, paintings, wood, paper etc.).
Standardisation in Europe is carried out through CEN TC/346
In 2003 a proposal for the establishment of a Technical Committee “Conservation of Cultural
property” was proposed by the UNI-NORMAL Italian Commission. This proposal was
approved on 12/02/2003 when CEN/TC 346 was founded and begun the work after the first
International Meeting del 21-06-2004, Roma.
All the 29 countries, presently members of CEN, take part to the standardisation activity. They
are: Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany,
Greece, Hungary, Island, Ireland, Italy, Latvia, Lithuania, Luxemburg, Malta, Holland,
Norway, Poland, Portugal, Romania, Slovak Republic, Slovenia, Spain, Sweden, Switzerland,
United Kingdom
19

CEN/TC 346 "Conservation of cultural property" is articulated in:
- a President: Dr. Vasco Fassina (Italy, Ministry for Cultural and Natural Heritage);
- a Secretary: Dr. Elena Mocchio (Italy, UNI);
- a Technical Committee (TC), formed by national delegates (no more than 3 for each country:
the head and 2 delegates) with a strategical/political function and with the task of coordination
of the Working Groups’ activities;
- 5 Working Groups (WG), operating on 5 specific themes, illustrated below, with the task of
drawing up technical documents and regulations. The WGs are guided by a Coordinator and are
composed by various experts from the members countries of CEN.
This is the present structure:
Working Group 1 " General guidelines and terminology”
Convenor: dr. Apollonia (Italy, Superintendence for Cultural Heritage, Val d’Aosta).
Participating countries: Belgium, Denmark, Estonia, Germany, France, Greece, Hungary, Italy,
Malta, Holland, Norway, Sweden, Switzerland, Czech Republic.
Proposed Scope: WG 1 has the responsibility for the drafting of guidelines on conservation
planning, including monitoring; standards on terminology dealing with moveable and
immovable components, with degradation processes and its graphic and symbolic
documentation; guidelines on security and safety conditions relating to the use of cultural
heritage by the public.
Working Group 2 "Materials constituting cultural property"
Convenor: dr. Vasilike Argyropoulos (Greece, Associate Professor of Conservation of Metal
Antiquities & Works of Art, Athens).
Participating countries: Cyprus, Denmark, France, Greece, Germany, Italy, Sweden, Norway,
Belgium, Czech Republic.
Proposed Scope: WG 2 has the responsibility for the drafting of standards on examination,
characterisation, and analysis, including eventual sampling of the materials constituting the
artefacts, and on the evaluation of the state of conservation of the artefacts.
Working Group 3 "Evaluation of methods and products for conservation works"
Convenor: dr. Vasco Fassina (Italy, Ministry for Cultural and Natural Heritage).
Participating countries: Belgium, Denmark, Estonia, Germany, France, Greece, Hungary, Italy,
Ireland, Malta, Sweden, Switzerland, Czech Republic, Norway, Croatia (observer).
Proposed Scope: WG 3 has the responsibility of drafting documents on criteria to select
methods and/or products and operating/working conditions in relation to the conservation/
restoration, repair, maintenance and preventive conservation work; and of drafting documents
on the methodologies to be used.
Working Group 4 "Environment"
Convenor: Dr. Johnsen (Denmark, National Museum of Denmark, Department of
Conservation).
Participating countries: Denmark, Italy, France, Sweden, Germany, Norway, Holland, Poland,
Greece, Czech Republic, Belgium.
Proposed Scope: WG 4 has the responsibility for the drafting of guidelines for the control of
environmental variables, and of standards on the measurement of indoor, including exhibition
and storage conditions, and outdoor environmental conditions, and on artefacts/environment
interaction.
Working Group 5 "Transportation and packaging methods"
Convenor: Dr. Anne de Wallens (France, Département des Peintures Musée du Louvre)
Participating countries: Italy, France, Denmark, Holland, Spain, Belgium, United Kingdom,
Sweden, Switzerland, Austria, Germany.
20

Proposed Scope: WG5 has the responsibility for the drafting of standards on showcases
requirements and on packaging and transportation methods.
Particularly relevant for networking activity N2 of Eu-ARTECH is the activity of Working
Group 3 “Evaluation of methods and products for conservation treatments”. The partial overlap
of interest is evident and this open possibilities of interactions and fruitful cooperation.
Within CEN WG3, the Italian Standard Document UNI 10921 “Water repellents – Application
on samples and determination of their properties in laboratory” was considered as starting point
to develop an European document on the topic.
After a long discussion, the WG3 experts agreed to divide the document into two separate
sections: one relevant to the experience in laboratory and the other one referred to in situ
measurements.
The original document was partially read and modified. Particular attention was dedicated to
the identification of the single test methods to be developed and/or used (if already existing).
At present the following tests are discussed:
1) Measurement of water absorption by capillarity (WAC)
2) Measurement of water absorption by total immersion (WATI);
3) Measurement of water absorption at low pressure (WALP)
4) Measurement of drying index (DI)
5) Measurement of contact angle (CA)
6) Measurement of water vapour permeability (WVP)
7) Measurement of colour on matt surface
8) Measurement of the gloss
The evaluation methodology of the products remains a discussion topic, mainly because of the
variety of opinions about the choice of the product’s quantity to use for experiments in the
laboratory and ways of their application.
Contributions of Eu-ARTECH to this specific WG activity and, more generally, to the activity
of CEN can be articulated in two different ways:
1- direct participation of Eu-ARTECH Consortium members to the activities of WGs, bringing
the knowledge developed within the Consortium;
2- proposition of specific documents, elaborated by Eu-ARTECH, to be submitted for
discussion and possible official adoption by CEN.
Several Eu-ARTECH members are already participating to WGs, such as A.M.Mecchi,
ICVBC; D.Pinna, OPD; J.Delgado, LNEC, etc.. Proposition of documents will be one of the
outcomes of the N1 and N2 networking activities of Eu-ARTECH.
1.3.2.2 – Meetings and workshops
The most relevant workshop on N2 activities was the Discussion Panel, already described in the
previous section (Firenze, IT, November 22 nd 2006 at the Opificio delle Pietre Dure). The event
was open to the public and had 93 attendees, therefore was also a significant occasion for
dissemination of knowledge. List of participants, presentations and general discussion at the
Discussion Panel are described in Annex 9.
Other conferences, where N2 activity was diffused, were:
-Le biotecnologie nella conservazione dei beni architettonici, Trento, Italy, June 9th 2006
-Pavimentazioni storiche: uso e conservazione - Scienza e Beni Culturali, Bressanone, Italy,
July 11th-14th, 2006.
21

1.4 Transnational Access
Access was offered by AGLAE and MOLAB. In AGLAE non-destructive elemental
composition studies were carried out, in the unique environment of the large laboratories
located in the basement of the Louvre Museum; in MOLAB access was offered to a unique
collection of portable instrumentations, that allows users to carry out non-destructive
measurements in-situ, i.e. in the same site where the artwork is located.
The milestones of both AGLAE and MOLAB for the first six months of the third year were to
ensure continuity in offering access, according to the schedules indicated in the contract and to
the implementation plan of the period.
During the first six months of the third year, both accesses have been operative and successful
measurements have been carried out, achieving the foreseen milestones.
1.4.1 AGLAE
1.4.1.1 Description of the publicity concerning the opportunities for access.
Information to users on the opportunity of access to the AGLAE facility was distributed, during
the first part of the third year, through the same ways already exploited during the first two
years of the Consortium activities, i.e.:
- the Eu-ARTECH website;
- e-mail and brochures, using the mailing list collected trough the networking activities;
- presentations at conferences and meetings;
- publications in the scientific literature.
After more than two years from the start of the project, AGLAE is certainly recognised among
the European professionals in cultural heritage as a well established opportunity for research
and innovation.
Dissemination of knowledge on AGLAE transnational access activities was carried out at the
following international conferences:
- 2 nd International School of Structural and Molecular Archaeology: How did Solid-
Solid Transformations Occur?, Erice, IT, 2-6 June 2006; at the workshop, dedicated to
the memory of the great French scientist H.Curien; M.Menu described the AGLAE
facility and projects developed though the access programme;
-12èmes Journées d'Etude de la SFIIC-Couleur & Temps - La couleur en conservation
restauration, Paris, FR, 21-23 June 2006; the activities on characterisation of pigments
were publicised ;
- Science for cultural heritage – ICTP- Trieste, October 23 th -28 th 2006; at this
conference, S.Rohers (C2RMF) presented the AGLAE access programme within the
talk on "Accelerator analysis at the Louvre Museum";
- 15 th Congress of the International Union for Prehistoric and Protohistoric Sciences,
Lisbon, PT, 4 th -9 th September 2006; at this meeting two projects developed through
AGLAE measurements were presented.
1.4.1.2 Description of the selection procedures and access activities
Proposals and their selection. At the end of the first semester of the third year (June to
November 2006), 10 proposals were received within the deadline of October 15 th . The
proposals were 3 from Italy, 2 from Belgium, 2 from United Kingdom, and 1 from Germany,
Romania and Portugal, respectively. The total beam time requested by users amounted to 44
days.
These projects were evaluated by the AGLAE Peer Review Committee by e-mail. The PR
Committee attributed a mark of high priority to projects of new users and a normal priority to
22

the others. Finally, 8 projects were accepted, among which 6 were from new users and 2 from
users who had previous experience in AGLAE.
Regarding the scheduling of the projects for the next semester, since two already accepted
projects (user group leaders: Bertoncello and Padeletti) were previously scheduled for this
period, only 6 of the 8 newly accepted projects have been planned, the remaining 2 being
shifted to the period June-November 2007.
The total allocated beam time is 24 days, i.e. 18 days for the newly accepted projects plus 6
days for the two projects previously approved.
The list of project proposals presented within the October deadline is reported in Annex 3.
Table I - Summary of the AGLAE Peer Review Committee during the
reporting period.
Date
Selection
meetings
Nov 2006 6rth AGLAE PRC
evaluation
Modality
e-mail 10
23
Projects
N° & Countries
Submitted Selected
Germany[1], United Kingdom
[2], Romania [1], Portugal [1], 8
Belgium [2], Italy [3]
According to the previous considerations, the planned experiments for the period November
2006-May 2007, in chronological order, are the following:
1- In December 2006, R. Bertoncello and co-workers from the University of Padova Italy, will
continue their investigation on the properties of sol-gel silica coatings with respect to the
protection of historical lead glasses. For their third run, they intend to study the behaviour of
coated glasses submitted to accelerated ageing in climatic chamber.
2- The new project on Roman mosaics by M. Verità from the Stazione Sperimentale del Vetro
in Venice, Italy, is scheduled in January 2007. It will be based on PIXE/PIGE analyses of glass
tesserae in view to determine the provenance of materials, including the pigments.
3- The study of archaeological obsidian samples by T. Carter from the British Archaeological
Institute in Ankara, Turkey, is also scheduled on January 2007. Based on PIXE analysis of trace
elements, it will contribute to determine the provenance of obsidian artefacts found in the
important Neolithic site of Catalhöyük in Turkey.
4-5 - Two projects have beeen scheduled in February 2007. The team of A. I. Seruya from the
Portuguese Institute for Conservation and Restoration, Lisbon, will analyse by PIXE/PIGE
several metallic components taken from the shrine of Prince Alphonse of Portugal (XVth
century) to check whether they have been manufactured locally or they have been imported
from the Flandres. The project by G. Artioli from the University of Milano Italy on the copper
metallurgy in the Alps will be carried out at the end of February. It is based on the
determination of trace element by PIXE on smelting products and archaeological objects to
infer important features of the metallurgical process.
6- In March 2007, the group of B. Kanngiesser will perform measurements by 3D µ-PIXE.
They will use their set-up to study layered systems of cultural heritage interest, such as gilded
bronzes or coloured bones.
7- The new project by J. Tate et al. dealing with the µ-PIXE study of Egyptian gold objects is
scheduled in April 2007. It will be another occasion to analyse entire museum objects with the
AGLAE external beam.
8- The team headed by G. Padelletti will get its fourth run in April 2007, for the long running
investigation on the manufacturing technique of glazed ceramics from Gubbio Italy.
A final note: one of the projects already accepted by the PR Committee has been withdrawn, on
specific written request by the user Magnus Sandström, Head of Department of Physical,
Inorganic and Structural Chemistry at the Arrhenius Laboratory of the Stockholm University.

The user had administrative difficulties to transfer the artwork from its museum to the C2RMF
laboratory (see copy of the withdrawal e-mail in Appendix 4).
Access activity results - The most significant achievements obtained by the six users who
received beam time during the 5 th semester of the access programme are summarized below.
Researchers from the Bavarian National Museum, Munich Germany, headed by R. Schwarz,
started a new project dealing with historical furniture built in Boulle-technique. A large set of
data was collected, using PIXE, on the elemental composition of about 20 metallic parts of
furniture dated from different periods. The aim of this work was to distinguish materials
originating from different casting factories and thus to attribute given pieces of furniture to
particular workshops known to be linked to those factories. This study was especially focused
on the works of Johann Puchwieser, active in Munich in the 17th century, to whom some of the
analysed objects are attributed.
Several Persian glazed tiles from the second half of the 19th century were studied by the group
headed by F.Voigt, in order to get an insight into the fabrication technique. Three days of
beamtime were allocated to this project. Four tiles from the Musée des Beaux-Arts, Lyon and
four tiles from the Musée du Louvre, Paris, were also studied by PIXE/PIGE analysis and other
analytical techniques available at the C2RMF. The data obtained are currently under
interpretation. In particular, the composition of the materials employed for making these tiles
and that of the colouring pigments will contribute to a better understanding of the
manufacturing technique of the workshop of Ali Muhammad, considered as the most important
one of 19 th century in Teheran.
The database on the IBIL spectra of materials relevant to cultural heritage was extended by A.
Quaranta and co-workers. Paper and pigments, with and without varnish, were analysed. In a
co-operation with former AGLAE users (i.e.: Golser, Wünschek, Kröpfel), IBIL spectra on
aged and non-aged paper were measured in order to achieve information on paper alteration
mechanisms.
A. Zucchiatti from the Istituto Nazionale di Fisica Nucleare, Genova, Italy, and the Morrocan
co-worker M. Haddad from the University of Meknes, came to the C2RMF in order to carry out
a study by PIXE / PIGE of ceramics and mortars from Moroccan architecture. Samples coming
from six sites, and from various periods (14 th -18 th century), were studied with particular interest
to the glaze, the ceramic bulk and the residues of fixing mortar.
Two new projects were concerned with 3D-PIXE experiments. The conventional PIXE
technique does not provide information on the depth distribution of elements, since the
collected X-rays originate from the whole path of the incident protons. The idea was to use an
X-ray confocal optics successfully applied for XRF measurements in synchrotron radiation
facilities, to select discrete emitting zones at given depths. The research group headed by B.
Kanngiesser from the Technical University of Berlin was able to define an appropriate set-up
by: 1-reducing the proton beam size to ~20 µm; 2-mounting, on the snout of the detector, a
polycapillary half lens with a nominal focal spot size of ~18 µm at 8 keV. Depth scans were
then performed on different sets of metal foils to characterise the created analytical volume.
This new technique was also applied to patinated and unpatinated bronze samples, to illustrate
its high potentiality to tackle cultural heritage issues.
The research group headed by K. Janssens from the University of Antwerp Belgium used the
same beam conditions, in combination with a polycapillary half lens with a nominal focal spot
size of about 40 µm at 8 keV in front of the Si(Li) detector. After measuring standard materials
to compare the performance of 3D-PIXE with 3D-XRF, depth scans on various layered paint
samples (modern painting, medieval painting, car paint) were carried out.
1.4.1.3 Meetings and workshops
The experiments carried out in the framework of the Transnational Access programme have
already given rise to several publications in international journals, as well as presentations to
conferences. Regarding the presentations in international meetings, are here reminded:
24

-Lugliè C., Le Bourdonnec F.-X., Atzeni E., Poupeau G., Dubernet S., Calligaro T., Moretto Ph.
& Serani L. “Early Neolithic obsidian artefacts in Sardinia: the Su Carroppu rock-shelter case”,
15 th Congress of the International Union for Prehistoric and Protohistoric Sciences, Lisbon,
PT, 4 th -9 th September 2006;
- S.Rohers, “Accelerator analysis at the Louvre Museum”, Science for cultural heritage –
ICTP- Trieste, October 23 th -28 th 2006;
- Lugliè C., Congia C., Le Bourdonnec F.-X., Dubernet S., Calligaro T., Sanna I., Poupeau G.
& Moncel M.H. “Obsidian economy in the Rio Saboccu open-air Neolithic site (Sardinia)”, 15 th
Congress of the International Union for Prehistoric and Protohistoric Sciences, Lisbon, PT, 4 th
-9 th September 2006;
1.4.2 MOLAB
1.4.2.1 Description of the publicity concerning the opportunities for MOLAB access.
The diffusion of information regarding MOLAB access continued regularly through the website
(www.eu-artech.org) where a prominent relevance was given to Transnational Acces activities.
The website was continuously updated and explanations on eligibility and information on
compilation of proposal forms were improved. The list of projects, carried out from the
beginning of the project, accompanied by Users Reports and pictures, was continuously
adjourned.
In addition, through the list of institutions and researchers collected by the networking activity
N1 (see this Report) information on MOLAB work and accessibility was also diffused.
Diffusion of information on MOLAB activity was carried out also at other relevant conferences
of the field, such as:
- 2 nd International School of Structural and Molecular Archaeology: How did Solid-
Solid Transformations Occur?, Erice, IT, 2-6 June 2006, whre B.Brunetti (UNI-PG)
described objectives and activities of MOLAB in the talk “Why a mobile laboratory for
cultural heritage?”;
- XXVVII European Congress on Molecular Spectroscopy, EUCMOS, Istanbul, TU, 3-8
September 2006, where B.Brunetti (UNI-PG) presented the MOLAB activities through
the poster “MOLAB, a European mobile laboratory for in-situ non-invasive
spectroscopical studies of cultural heritage”;
- Science for cultural heritage – ICTP- Trieste, October 23 th -28 th 2006 -a conference
with 84 attendees from 26 countries, including less developed countries, where a
practical demonstration of MOLAB performances was given by the team of UNIPG
(A.Sgamellotti, C.Miliani, F.Presciutti, A.Cosentino).
- New methods and issues in the analysis of paintings, Academy of Fine Arts, Prague,
CZ, November 7 th 2006, where C, Miliani (UNI-PG) presented MOLAB activities in
the talk “MOLAB: a transnational access for in-situ non-invasive studies of the
European cultural heritage".
1.4.2.2 Description of the selection procedures and access activities
Proposals and their selection. At the last deadline of October 31 st 2006, 7 new proposals were
received by researchers from Romania (1 proposal), UK (3 proposals), Poland (1 proposal),
Malta (1 proposal), and Italy (1 proposal). These proposals will be evaluated by the Peer
Review Committee in a specific meeting organised in Rome on date January 5 th 2007..
25

Access activities and results. At the beginning of the third year activities the list of total
proposals previously approved by the PR Committee and still to be worked out,was the
following:
1- A Technical Study of the painting Amor Vincit Omnia by Caravaggio, in the
Gemäldegaleri e- Staatliche Museen zu Berlin in Berlin, DE.
Acronym: CARAVAGGIO. Project leader: A.Contini
2- Paint on Early Meissen Stoneware, in the Staatliche Kunstammlungen Dresden, DE.
Acronym: POEMS. Project leader: A. Loesch.
3- Drawing and colour in designing a painting: Polidoro artworks, in Museo di
Capodimonte, Napoli, IT.
Acronym: POLIDORO. Project leader: N. Spinosa.
4- Casas Pintadas de Évora, in Evora, PT.
Acronym: EVORACAP. Project leader: I.Ribeiro.
5- Study of gemstones in historical jewellery by non-destructive techniques. in the
Victoria and Albert Museum, UK.
Acronym: GEM. Project leader: Lucia Burgio.
6- Study of surface layers and other substances applied in the past on the Parian and
Pentelic marbles of the Greek sculpture of Esculapio from Empúries (Girona): control
of cleaning methodologies, in the Museu Nacional d’Art de Cataluna, Barcelona, ES.
Acronym: ES.SER. Project leader: A. Masalles.
7- Art technological research toward the Victory Boogie Woogie (1942-1944) by Piet
Mondriaan in the Gemeentemuseum, Den Haag, NL.
Acronym: VBOOWOO. Project leader: H. Jansen.
8- Study of the composition and structure of lustred decorations on original Italian
Renaissance lusterware at the Wallace Collection., London, UK.
Acronym: XANTO. Project leader: S. Higgot.
During the first six months of the third year, four of these projects were carried out: 1- the
Technical Study of the painting Amor Vincit Omnia by Caravaggio, in Berlin, DE (June 2006);
2- Paint on Early Meissen Stoneware, in the Staatliche Kunstammlungen Dresden, DE (July
2006); 3- Drawing and colour in designing a painting: Polidoro artwork, in Capodimonte,
Napoli, IT (October 2006); 4- Casas Pintadas de Évora, in Evora, PT (November 2006). For the
development of these projects, 3 interventions were carried out by UNI-PG, 1 by OPD, and 1
by CNR-INOA.
Three projects still remain to be carried out. They will be accomplished during the next period.
Table II - Summary of the MOLAB Peer Review Committee activities
during the reporting period
Deadline
Selection
meetings
Date
and
Location
Projects
N° & Countries
Submitted Selected
October
31 st 2006
6 rth January
MOLAB-
PRC Meeting
5 th United Kingdom [3], Romania PRC
2007,
Rome,
IT
7
[1], Poland [1], Malta [1], Italy
[1]
meeting
on
January
5 th 2007
The projects developed during the first semester of the third year led to significant results.
Regarding the technical study of the painting Amor Vincit Omnia by Caravaggio, in Berlin, DE,
the measurements evidenced in all the regions of the painting intense signals of Pb: this
indicates a large use of biacca in the “imprimitura”. Iron was also found very diffusely,
confirming the extensive use of earth pigments by Caravaggio. Cinnabar was used only for the
realisation of some details. The combined observation of Sn and Pb in yellow and light brown
colours suggested the use of lead-tin yellow pigment, while golden details were all realised by
true gold. Copper based pigments were found in dark green shades. All these data are
compatible with the knowledge already acquired on Caravaggio’s painting technique.
26

For the study of Paints on Early Meissen Stoneware, in the Staatliche Kunstammlungen
Dresden, the pigments identified on the unfired decorations were: lead white cerussite and
hydrocerussite, cinnabar, azurite, and Prussian blue. The binding media were characterised as
lipidic and proteinaceous in nature. A terpenic resin was also found in gold decorations. Finally,
a high amount of calcium and, probably, copper oxalates have been detected on the painted
surfaces. These results significantly contribute to understand the decoration techniques used by
the masters of the Meissen stoneware. The MOLAB data will enrich the catalogue of a
forthcoming exhibition dedicated to this historical ceramic production.
In Capodimonte, the study of the paintings of Polidoro led to several high-resolution images of
the exalined paintings, which revealed details of the technique of the master as well as several
pentimenti. The analysis of the underdrawing is currently in progress.
Regarding the study of the Casas Pintadas in Evora, PT, in the upper part of the mural
paintings, signals of oxalates and restoration materials (acrylic resin) were found. In blue areas
the presence of azurite was detected, whereas in red zones the presence of kaolin was put in
evidence. In the lower part, signals of oxalates were again found, together with presence of
organic materials (possibly wax); in blue areas the presence of strong signals of Si-O stretching
was detected (but lapis was excluded); in red zones the presence of kaolin was again observed.
The fluorimetric investigation on painting in the gallery did not provide any signal of organic
binders and dyes. The emission of chlorophyll was detected in correspondence of algae
colonisations.
1.4.2.3 Meetings and workshops
The results obtained by the users through the MOLAB interventions were the subject of several
presentation in national and international meetings during the reporting period.
In particular, results were presented at the:
- 2 nd International School of Structural and Molecular Archaeology: How did Solid-Solid
Transformations Occur?, Erice, IT, June 2 nd -6 th 2006;
- XXVVII European Congress on Molecular Spectroscopy, EUCMOS, Istanbul, TU, September
3 rd -8 th 2006;
- Science for cultural heritage, Trieste, October 23 th -28 th 2006.
- New methods and issues in the analysis of paintings, Prague, CZ, November 7 th 2006.
1.5 Joint research activities
Eu-ARTECH joint research activities (JRA) continued during the third year according to the
foreseen implementation plan. It is here reminded that the first joint research, JRA1-
Development and evaluation of new treatments for the conservation-restoration of outdoor
stone and bronze monuments, has the objective to clarify and define advantages and limits of
new conservative treatments on outdoor monuments, comparing new and traditional methods.
The second joint research, JRA2-New methods in diagnostics: Imaging and spectroscopy, is
dedicated to the development of new methodologies in diagnostics and monitoring, setting-up
innovative instrumentation for in-situ non-invasive measurements.
The advancement of the two activities are discussed separately in the following sections.
1.5.1 JRA1-Development and evaluation of new treatments for the
conservation-restoration of outdoor stone and bronze monuments
According to the implementation plan of the third period, the work to be developed during the first
six month of the third year regarded:
27

Task 4 : Treatment of aged samples [stone and bronze] followed by accelerated and natural
ageing of the treated samples (Resp. BLfD), with the participation of: LNEC, CNR-ICVBC,
OPD [stones] and BLfD, UNI-BO, LNEC [bronzes];
Task 5 : Monitoring, evaluation, and comparison of treatments. (Resp. CNR-ICVBC) with the
participation of: CNR-ICVBC, LNEC, UNI-PG, OPD [stones] and BLfD, UNI-BO, LNEC
[bronzes].
1.5.1.1 Activity progress
Although not included originally in the implementation plan, some additional measurements, to
better close the previously accomplished Task 2 [stones] -Development of new treatments and
procedures (chemical processes and application protocols), were carried out.
In particular, task 2 started during the first year of the project (4 th month), and continued till the
end of the second year. Because of the uncertainty of some results, additional tests were
accomplished, mostly concerning Modified Ethylsilicate (TEOS+APS) treatments [note: the
coupling agent (APS) in solvent (ethanol) was applied as a primer, followed by application of
TEOS]. The results confirmed that APS has the capacity to increase the consolidating action of
ethyl silicate close to the treated surface.
Water absorption tests were able to discriminate the APS action as a function of the lithotype
and the APS application procedure. These results pointed out that the procedure for APS
application as primer reduces the water absorption properties, but APS when used as primer
looses its influence in the consolidation action.
Task 4 [stones] –Treatment of aged samples followed by accelerated and natural ageing after
treatment. This task started at the beginning of the third year with the ageing of several samples
(25 th month) and now will continue up to the end of the fourth year (48 th month) with the
treatment of the aged stones; finally, the accelerated ageing of the same treated stones will be
carried out.
On the basis of the outputs of Task 2 and Task 3, stone samples were first properly aged (see
2 nd Annual Report, JRA1-Task3), then were treated according to selected procedures (see 2 nd
Annual Report, JRA1-Task2).
Sandstones. During the first months of the 3 rd year (June-October 2006), CNR-ICVBC started
with the ageing, by salt crystallisation, of a defined number of samples. Specifically, 49
samples of Firenzuola sandstone and 49 samples of Santafiora sandstone were subjected to 3
steps of salination cycles: the samples were placed on glass spheres at 40°C and let to absorb a
water solution of Na2SO4 (14% w/w) through a 5x5 cm 2 face for different periods: 1- 5 hours
(impregnation depth 10 mm); 1 hour (impregnation depth 5 mm); 15 minutes (impregnation
depth 1 mm).
After each step, the temperature was reduced and the specimen maintained at 10°C for half an
hour (in order to have a good crystallisation of myrabilite). In addition, between one step and
the other, specimen were put in an oven maintained at 40°C for 24 hours.
After a 3 steps cycles, the samples were subjected to desalination by total immersion in water.
Santafiora stones underwent to 8 complete cycles, while Firenzuola stones only to 6.
At the end of salination/desalination ageing, all the stone samples, aged and not aged
(Fiorenzuola and Santafiora sandstones, but also Gioia marble) were characterised, carrying out
a series of tests devoted to define reference parameters for the evaluation of the treatments.
The measurements were the following:
- Dried weight: in order to determine the exact amount of product applied after the treatment
(and the reaction of product) by weight difference;
- Colour determination: in order to detect eventual colour changes after treatment;
- Absorption by sponge method: two measures at two different time of contact (1 minute and 2
minutes) were done on each sample;
- Capillary water absorption: two measurements were done on each sample, with 60 minutes
contact time.
28

Measurements are in progress and other test (cross sections, thin sections, drilling tests) will be
carried out in the immediate future. All the results will be included in the 3 rd Annual Report.
Limestones. In the first 6 months of Task 4, LNEC proceeded with the ageing of Ançã and
Lecce samples following the protocols previously defined. The protocol was based on cycles of
crystallisation/desalination by use of a Na2SO4 water solution. The protocol is described in
Annex 10. After ageing, stones were characterised by:
-visual observations;
-colorimetric characterisation;
-mass variation;
-water absorption by contact sponge and capillarity;
-drilling resistance (in progress);
-drying (in progress).
Note 1: the colorimetric characterisation was done to evaluate the possible colour variation
induced by the applied treatments.
Note 2: in the characterisation of water absorption by capillarity, the lateral surfaces of the
samples were previously sealed with epoxy resin (Sikadur 32 N).
The results of these measurements, on Ançã and Lecce stones, are described in Annex 10. After
ageing, both limestones showed loss of cohesion and presented powdering and flaking.
However, the water absorption by the contact sponge method seemed to be not sensitive to the
ageing action, whereas the water absorption by capillarity showed some minor but significant
changes.
The treatment of the aged samples is in progress and the conclusion of the treatments is
expected by the end of December 2006.
Specimens of Ançã and Lecce stones without any previous ageing are also currently treated.
They will be first characterised and then inoculated with microrganisms to test the bioreceptivity
of the products.
Regarding the work on charge of OPD, according to the implementation plan for protective
treatments, in the first months of the 3 rd year a consistent number of new samples was prepared
and characterised in order to have a representative series for each treatment to be subsequently
aged, either naturally or artificially.
The new specimens were prepared according to the guidelines decided with the other partners.
In addition, to test the bio-receptivity of the products, 36 specimens treated with protective
products and 27 specimens treated with consolidants will be inoculated with microrganisms.
The ageing procedure will consists of both natural (a) and accelerated ageing (b).
(a) Natural ageing will be achieved by exposing the samples to urban environment in the OPD
courtyard. The lower surface will be temporarily sealed, in order to avoid the possible loss of
salt through the untreated surface, due to the rain.
The exposure schedule is as follows:
I – 1 st December 2006 – 31 st March 2007;
II – 1 st May - 31 st August 2007;
III – 1 st October 2007 – 31 st January 2008.
(b) Accelerated ageing will consist of forcing the salt to move and observing the effect on the
surface: the untreated face of the specimens will be positioned on a pack of paper filters (1 cm
thick) soaked in distilled water; after removal from the paper filters, the samples will be
allowed to dry with the lower (untreated) surface temporarily sealed, in order to force the
evaporation through the treated face. The cycle (wet and dry) will be repeated n times until
changes on the surface are visible.
During ageing, several checks at regular intervals will be carried out on the stone samples.
The tests are different according to the type of protective treatment under evaluation:
- DMPS: permanence of performance in terms of hydrophobic behaviour and water absorption;
- AmOx: superficial aspect, presence of efflorescence, flaking.
29

- Determination of possible colour changes.
For samples subjected to accelerated ageing (salt movement), the same tests will be carried out
after appearance of changes on the surface.
JRA1-Task5 (stones) – Monitoring, evaluation, and comparison of treatments.
This task started at the beginning of the third year (25 th month) and will continue up to the end
of the fourth year (48 th month). It consists of monitoring, evaluation and comparison of
treatments exposed both in natural and artificial environment.
Exposition in natural and artificial environment is started and evaluation tests will be performed
in the next future in order to assess the evolution of efficacy, compatibility and durability of the
treatment during the ageing. A series of tests will be carried out: several parameters will be
measured concerning both the protection performance and features of the surface, such as color
change, water absorption by capillarity, morphology and chemical nature, etc. Measurements
by optical and scanning electron microscopy are also planned, together with FT-IR and NMRstudies.
For the natural ageing, two sites were chosen: a marin/urban area in Lisbon, PT, and an
urban area in Firenze (Sesto Fiorentino), IT. The urban site in Lisbon is the terrace of the main
building of LNEC, whose façade is oriented to south and faces an avenue with a great traffic.
In addition, LNEC is very near to the Lisbon airport, therefore a sophisticated meteorological
station is available to know the long term evolution of air temperature, rainfall, wind speed and
direction, relative humidity, atmospheric pressure, and other parmaterers.
The urban area in Firenze (Sesto Fiorentino) is close to the CNR-ICVBC laboratory. Also in
this case, being CNR adiacent to the Firenze airport, detailed data on long term evolution of
environmental conditions are day by day available.
JRA1-Task 3 (bronzes) – Characteristics of sample properly aged before treatments
New samples, naturally aged for a period of one year in marine environment (Genoa, IT), were
added for comparison to those already studied in the previous phase of this project. Objective
was the observation of possibly different corrosion behaviours of naturally aged patinas in two
different marine environment: Genoa, IT, and Lisbon, PT.
The patina characterisation was carried out through measurements by:
a) eddy current thickness measurements;
b) weight measurements;
c) colour measurements;
d) flatbed computer scanning;
e) FTIR microspectroscopy;
f) EIS measurements.
All the results obtained by these techniques are reported in detail in Annex 11.
JRA1-Task 4 (bronzes)– Selected treatments of aged samples.
After a preliminary evaluation of the performances of the selected treatments: 1- organic (silane
materials); 2- inorganic (a- formation of artificial copper oxalate patinas and b- formation of a
thicker cuprite layer), 3- biological (formation of artificial copper oxalate by fungi), and 4-
corrosion inhibitors, the most promising final treatments have been applied to the various aged
samples.
They were:
1-silanes F8363 (T1S) and Sivoclear (T2S), which seem to demonstrate a protective behaviour
comparable to the reference treatment (Incralac, Tref) and have no perceivable chromatic
alterations; applicatioans were carried out to all the various group of aged samples (UN, UA,
MN and QQ).
2-thick and dense cuprite layer (T3S), which is considered to be highly protective and markedly
more corrosion resistant than the bare metal. An experimental approach was to check a new
generation of copper complexing agents, the so-called TOMATS (i.e.
Trioctylmethylammoniumthiosalicylate). Those modern complexing agents can be used in
organic, e.g. alcoholic solution and therefore were considered in the beginning as an interesting
alternative to water-based reagents. But, in contrast to the tartrate complexed copper, the
30

TOMATS system is holding the copper ions much more tightly. Due to the fact that the choice
of organically soluble oxidants is limited and that strong oxidisers are not available, it was not
possible to find a suitable oxidising agent in order to re-precipitate the copper ions as cuprite.
From each group of samples (UN, UA and MN) five samples were treated three times,
according to a predefined procedure.
3-fungi (T4S), which produce oxalic acid have been used to transform existing copper
hydroxysulphates and copper hydroxychlorides into copper oxalates; a selection was made
between 5 wild strains (for most of them, determination is in progress) : n°1 (Aspergillus niger),
n°2, n°3, n°6 and n°14. The results were evaluated. Strain n°6 was the most interesting one. It
could grow on all the copper-containing mediums, and he formed plenty of oxalates in medium
with CaCO3 and medium with brochantite.
4 - 5 % limewater solution (pH=8,5), which is supposed to act as passivation agent with the
formation of basic calcium carbonate, was chosen for the capacity to control the active corrosion
and compared with traditional corrosion inhibitor benzotriazole (Iref). As far as the reference
treatment is concerned, benzotriazole (BTA) has been prepared as a 3% solution in ethanol and
applied following the normal procedure (contact time of 4 minutes). In the case of limewater, to
determine the more suitable concentration, a preliminary evaluation of the formation of calcium
carbonate using different dilutions of limewater has been performed using FTIR spectroscopy
in transmission mode with a potassium bromide pellet.
1.5.1.2 Meetings and workshops
A general working meeting has been held, with all the participating researchers (representatives
from CNR-ICVBC, LNEC, UNIPG, OPD, BLFD, UNIBO), during the Eu-ARTECH meeting
in Perugia, November 21 st 2005. During the meeting, the developed activities have ben
discussed and plans on future activities established.
The developed work has been also presented at the conference “7th European Commission
Conference Saveur Safeguarded Cultural Heritage, Understanding & Viability for the Enlarged
Europe” – Prague, CZ, May 31 st - June 3 rd 2006.
During the reporting period, two papers have been accepted for publication:
- B. Doherty, M. Pamplona, R. Selvaggi, C. Miliani, M. Matteini, A. Sgamellotti, B.G. Brunetti
–“Efficiency and resistance of the artificial oxalate protection treatment on marble against
chemical weathering”- Appl. Surf. Science, in the press.
-B. Doherty, M. Pamplona, C. Miliani, M. Matteini, A. Sgamellotti, B.G.Brunetti – “Durability
of the artificial calcium oxalate protective on two Florentine monuments”- J. Cult. Heritage, in
the press.
1.5.2 JRA2- New methods in diagnostics: Imaging and spectroscopy
By this activity, four different innovative diagnostic methodologies for artworks are developed,
assembling in parallel four new portable equipments for in-situ non destructive measurements.
In Task1, new applications of NMR techniques to artwork studies are foreseen, included the
application of the portable NMR-MOUSE; in Task2, two different and complementary methods
for imaging spectroscopy in the near IR are set-up, namely: - high resolution imaging at various
fixed wavelengths, with low wavelength resolution, - low resolution imaging at continuous
wavelengths, with high wavelength resolution; in Task3, a new method is developed and
experimented for in-situ X-ray diffraction and X-ray fluorescence measurements (XRD-XRF);
in Task4, an existing portable micro-Raman technique is joint with the VIS micro-fluorescence
for the identification of organic colorants.
31

Regarding Task1 these were the milestones:
Task 1- 1- Methodology for lab NMR on ceramics and on siccative oils [partial] (Resp. UNI-
PG)
Task 1- 2- Study of porous materials on reference treated samples [partial] (Resp. UNI-PG).
Task 1-3- Progress in NMR MOUSE 3D Imager (Resp.: RWTH).
Regarding Task2:
Task 2- Study of the IR transparency of ancient pigments. Advances on IR imaging assembling
in the two versions (Resp.: OADC, CNR-INOA).
For Task3:
Task 3- Characterisation of optimal conditions for artwork XRD studies. Progress in
XRD&XRF system design (Resp: C2RMF).
ad, finally, for Task4:
Task 4-Elaboration of the spectroscopic methods for the diagnosis of dyes and lakes on
polychrome surface (Resp.:UNI-PG).
1.5.2.1 Activity progress
The developed activity, according to the milestones established in the implementation plan of the
period 24 th -30 th months, are described in the following for each separate task.
Task1 - NMR Methodologies (Task Leaders: UNI-PG and RWTH),
The planned activities regarding the applications of NMR to the study of stones, ceramics, and
siccative oils were all accomplished.
In particular:
Task1-1 - Methodology for lab NMR on ceramics and on siccative oils (partial). Applications
to the study of ceramics aimed to the characterisation of the behaviour of clay as a function of
the oven temperature (technology of firing), as well as the study of drying oils, continued with
the developments of new measurements. Regarding ceramics, a new paper is in preparation on
the more recent results. (see Annex 12).
Task 1-2- Study of porous materials on reference treated samples (partial).
The applications of NMR techniques to the study of water absorption by stones continued with
applications on the same lithotypes used in the experiments of JRA1. Different NMR
techniques have been used to characterise:
-Gioia marble, Carrara, IT;
-Santafiora sandstone, Southern Tuscany, IT;
-Firenzuola sandstone, Firenze, IT.
The determination of capillary water absorption was carried out using the gravimetric
absorption technique, in accordance with the Normal Protocol, also used previously on other
lithotypes.
In particular, during this period, applications of Magnetic Resonance Imaging (MRI) were
experimented. Indeed, MRI is an excellent tool for visualizing the presence of mobile species in
any material. In fact, the amplitude of MRI signal is proportional to the spin density of mobile
molecules, giving a quantitative measurement of the content of the molecules confined in a
porous structure.
MR Imaging studies were successfully carried out on Gioia marble and Santafiora stones (See
Figure 3).
1 H High Resolution NMR spectroscopy was also experimented, in particular for the study of
Fiorenzuola stones (for details, see Annex 12).
Task 1-3- Progress in NMR MOUSE 3D Imager.
During the first six monthe of the third year, the NMR depth profiler, previously experimented
to non-destructively evaluate the thickness of painting layers, was applied to study in-situ the
ageing of binders. Indeed, the depth profiler can carry out NMR experiments at different depth
32

in a painting (depth resolution ~20 μm) offering more information than 1 H density, for example,
through the measurement of relaxation times (T1, T2).
In fact, relaxation times are strongly affected by the molecular mobility: as general rule, the
harder the material, the shorter the relaxation times. A fact that becomes clear by comparing the
T2 values measured on recently oil painted panels (T2=10 ms) to the ones measured on ancient
paintings executed with the same binder (T2=0.1ms). This large difference on the T2 values
(~three orders of magnitude) tells about the potential of NMR relaxometry as a very sensitive
method to study aging.
From the study it was found, as expected, that T2 decreases with increasing aging time. On the
opposite, T1 remains constant (as found on the buckthorn lake) or even increases (as found on
ultramarine blue) with the aging time.
For details on these measurements, see Annex 13.
Figure 3- Magnetic resonance image of a Santafiora
stone sample saturated with water.
JRA2-Task2 - Study of the IR transparency of ancient pigments. Advances on IR imaging
(assembling the two versions) (Task Leaders: OADC/CNR-INOA)
The last development of the work on the two planned IR-Imaging devices, were run according
to the contract.
The advancement in the work was positive also for the Ormylia system. After the assembling of
the system, already carried out up to the end of the second year, the tests of measurements were
carried out on several substances layered in different way on specific specimen.
It was found that, in the NIR spectral region (800-2500 nm), overtone and combination
vibrational modes are active, whereas in the 2500-4200 nm region some fundamental vibrations
can be observed.
Almost all the absorption bands observed in the NIR arise from overtones of functional groups
containing hydrogen atoms (C-H, N-H, O-H) or combinations involving stretching and bending
modes of vibration of such groups. A great degree of complexity characterizes the spectra
acquired in this region. As a result, spectral assignments to specific vibrational modes are not
always possible.
The spectra newly added to the collection of data already recorded by the device are in the last
pages of the OADC report in Annex 14.
The work by CNR-INOA led to obtain for the first time 14 different high-resolution images, at
different 14 wavelength in the IR range. The results clearly demonstrated the good
performances of the system, because for the first time different IR images were obtained at
different wavelength with a spatial resolution never achieved before (16 pixel/mm 2 ).
33

After this key-passage, the assembling of the final device appears relatively straightforward.
Details are reported in Annex 14.
Task 3- Characterisation of optimal conditions for artwork XRD studies. Progress in
XRD&XRF system design (Task Leader:CNRS-C2RMF)
During the reporting period, the design of the portable integrated XRF/XRD system was
definitely settled and, therefore, the 30 month milestone was fulfilled.
A laboratory mock-up of the system was then assembled and preliminary experiments provided
XRF elemental compositions data and XRD patterns for easel paintings, mural paintings, and
ceramics (as foreseen in the implementation plan).
There are still a number of operations necessary to improve the system for XRF, as well as for
XRD, however the system can be considered operative.
A picture of the assembled system is reported in the following figure:
Imaging
plate
Laser 1
EDS
Figure 4: mock-up of the portable XRF/XRD system
Experimental details of the system are reported in Annex 15.
Task 4-Elaboration of the spectroscopic methods for the diagnosis of dyes and lakes on
polychrome surface (Task Leader: UNI-PG).
The work towards the establishment of a new methodology for organic analyses of dyes and
lakes trough the coupling of micro-Raman and micro-fluorescence techniques in a unique
device, also proceeded. Three parallel subtasks where developed, according to the
implementation plan.
Subtask 4.1 - The vibrational and electronic characterisation of dyestuffs and lakes.
Several spectra of fluorescence and Raman scattering of organic substances were recorded and
the database, whose preparation already started in previous years, was extended. In particular,
the data were ordered in terms of: a-luminescence properties; b-Raman scattering yield; cexcitation
wavelength effect (Annex 16).
34
Laser 2
source

Subtask 4.2 - Elaboration of the spectroscopic methods for the diagnosis of organic matter on
polychrome surfaces.
For this aspects painting model standards were prepared by UNI-PG and OPD (or shared with
NGL). Models of dyed textiles were also prepared and their spectroscopic behaviour
characterised.
Subtask 4.3 - Assembling and lab testing of the micro-Raman and micro-fluorimetry
spectrophotometer.
Regarding this point a new laser was acquired for the portable system, characterised by high
intensity and excellent stability (785 nm). Using this laser a better Raman scattering
characterisation of organic molecules is expected.
1.5.2.2 Meetings and workshops
A general working meeting has been held with all the participating researchers (representatives
of UNIPG, RWTH, INOA, OADC, and C2RMF) during the Eu-ARTECH meeting in Perugia,
on date November 20 th , 2006.
A trilateral meting RWTH, UNIPG, and NGL was held in London, at the National Gallery,
from October 2 nd to 7 th , 2006. During the meeting, several properties of the portable NMR depth
profiler were discussed. In addition, test measurements on several paintings, already
characterised by previous measurements through other techniques, were carried out. A report on
these measurements is in Annex 13.
35

2. LIST OF DELIVERABLES
Activit
y
N1
Deliv
.
n.
Deliverable Name Task Delivered by Contractor Planned
(months)
1 REPORT ON THE
STANDARDISED FORMAT
FOR DESCRIBING UV-
FLUORESCENCE AND SEM-
EDX.
2 REPORT ON THE WORKING
MEETING ON
INTERLABORATORY
COMPARISON HELD IN
SUCEAVA, RO,
SEPTEMBER 20 TH 2006 .
3 PRESENTATION OF EU-
ARTECH AT THE DHA
MEETING
[.PPT FILE ON THE WEBSITE]
4 REPORT ON THE ELECTRON
MICROSCOPY WORKING
GROUP MEETING
(DURING INTERIM MEETING)
5 REPORT ON THE WORKING
GROUP MEETING TO
DISCUSS OUTCOMES OF
INITIAL INVESTIGATIONS OF
TECHNIQUES FOR
“CHARACTERISATION OF
ORGANIC MATERIALS IN
PAINT CROSS SECTIONS
(DURING INTERIM MEETING)
N2 6 REPORT ON CONTINUATION
OF DISTRIBUTION OF
SURVEY FORMS BY
PARTNERS (
7 SET UP OF A WEB PAGE
FOR A BULLETIN BOARD TO
LAUNCH THE E-FORUM
(RESP. OPD)
8 REPORT ON THE GROUP
FORMATION FOR
“TREATMENT EVALUATION
METHODS”
9 REPORT ON DEVELOPMENT
OF WORK FOR
STANDARDISATION (RESP.
LNEC)
TA1 10 SUMMARY REPORT ON
AGLAE
TA2 11 SUMMARY REPORT ON
MOLAB
JRA1 12 PROGRESS REPORT ON
THE AGED AND TREATED
SAMPLES
Task 1c UNIPG , OADC, ICN,
NGL, IRPA,OPD,
ICVBC, ,UNIBO,
C2RMF, LNEC, BLFD
Task 2 OADC, ICN, NGL,
IRPA,OPD,ICVBC,
UNIPG, C2RMF, LNEC,
BLFD, UNIBO
Task 2 OADC, ICN, NGL, IRPA,
UNIPG,
Task 2 ICN, UNIPG, NGL, OPD,
CNR-ICVBC, BLFD,
ICN, C2RMF
Task 3 NGL, UNIPG, UNIBO,
OADC, ICN,
IRPA,OPD,ICVBC,
C2RMF, LNEC.
Task 1f CNR-ICVBC, OPD,
IRPA,ICN,LNEC,
UNIPG, C2RMF,
BLFD,NGL, UNIBO,
36
OADC
Achieved
(months)
30 30
[Annex 4:
I, II, III ]
30 30
[Annex 5]
30 30
[Annex 6]
30 30
[Annex 7]
30 30
[Annex 8]
30 30
[this
report,
pag.16-19]
Task 2b OPD, CNR-ICVBC 30 30
[this report
pag.19 and
Appendix
2,3,4]
Task 2c OADC, CNR-ICVBC,
ICN, UNIPG, C2RMF
IRPA, OPD,
Task 3a LNEC, CNR-ICVBC,
OPD, IRPA,ICN, UNIPG,
C2RMF, BLFD,NGL,
UNIBO, OADC
30 30
[Annex 9]
30 30
[this report
pag.19-22]
C2RMF 30 30
[this
report,
pages 13-
UNI-PG, CNR-INOA,
CNR-ICVBC, OPD
Task 4 CNR-ICVBC,UNIPG,
BLFD,OPD, LNEC, and
participating partners
15]
30 30
[this
report,
pages 15-
30]
30 30
[Annex 10
(stones)
and 11
(bronzes)]

JRA2
13 PROGRESS REPORT ON
THE CHARACTERISTICS OF
THE SAMPLES BEFORE
NATURAL EXPOSURE AND
EXPOSURE SITES
14 PROGRESS REPORT ON
LAB NMR METHODOLOGY
15 PROGRESS REPORT ON
NMR MOUSE 3D
16 PROGRESS REPORT IR
TRANSPARENCY AND
SYSTEM ASSEMBLING
17 FINAL REPORT ON OPTIMAL
CONDITIONS FOR ARTWORK
XRD STUDIES AND ON
XRD&XRF SYSTEM
DESIGN AND ASSEMBLING.
18 FINAL REPORT ON THE
ANALYTICAL METHOD TO BE
BASED ON DOUBLE MICRO-
RAMAN AND MICRO-
FLUORIMETRY
MEASUREMENTS
Task 5 UNIBO, BLFD,LNEC 30 30
[Annex 10
(stones)
and 11
(bronzes)]
Task1-
Subtask
1.1 and 1.2
Task 1-
Subtask
1.3
37
UNI-PG, RWTH 30 30
[Annex12]
RWTH , UNIPG 30 30
[Annex13]
Task 2 OADC, CNR-INOA 30 30
[Annex14]
Task 3 C2RMF, UNI-PG 30 30
[Annex15]
Task 4 UNIPG, C2RMF 30 30
[Annex16]

3. USE AND DISSEMINATION OF KNOWLEDGE
Dissemination of knowledge has been carried out with the goal to extend contacts with all
potential users, such as conservation scientists, conservator, restorers, libraries, museums,
schools on conservation, cultural institutions, etc.. Having in mind the strong societal
implications of conservation of cultural heritage, public and policy makers were not neglected.
Media used to achieve this goal were numerous: internet, e-mail, conferences, contacts with
other organisations, press, etc..
The Eu-ARTECH website (www.eu-artech.org) was continuosly adjourned, introducing new
pages and links. After two years and half of existence, the Eu-ARTECH website has achieved
the respectable number of more than 47.000 visits and represents today a relevant channel for
the diffusion of knowledge on all the European activities in the field. The list of relevant
websites of interest in the conservation science and conservation/restoration of cultural heritage
was also continuously adjourned and made accessible.
A specific relevance was given to the AGLAE and MOLAB Transational Access starting from
the home page. Information on the developed projects was diffused, through the website
publication of Users Reports and related pictures.
Efforts to establish extended and fruitful interactions among the Eu-ARTECH consortium and
relevant infrastructures in the field continued. These activities are described in the section
“networking N1” of this report.
Other diffusion or dissemination of knowledge was carried out through plenary lectures, invited
conferences, seminars, or presentations of Eu-ARTECH programs and initiatives in relevant
international congresses and meetings, such as:
- 7th European Commission Conference "SAVEUR, May 31 st -June 2 nd , 2006 Prague, CZ.
(http://www.arcchip.cz/ec-conference/). Aim of this conference was the consolidation and
impact assessment of results achieved in EU research projects related to movable and
immovable cultural heritage. Eu-ARTECH was present with two presentations, one dedicated
to AGLAE and one to MOLAB activities.
- 2 nd International School of Structural and Molecular Archaeology: How did Solid-Solid
Transformations Occur?, Erice, IT, 2-6 June 2006; the importance of stationary and mobile
laboratories (AGLAE and MOLAB) for cultural heritage studies and conservation was
underlined;
-XXVVII European Congress on Molecular Spectroscopy, EUCMOS, Istanbul, TU, 3-8
September 2006: the role of spectroscopy in the studies on cultural heritage was evidenced,
through the presentation of case studies of MOLAB transnational access;
- Synchrotron Radiation in Arts and Archaeology, Berlin, 27-29 September 2006: the relevant
role of transnational access in the studies and conservation on cultural properties was put in
evidence;
- Science for cultural heritage – ICTP- Trieste, October 23 th -28 th 2006: both AGLAE and
MOLAB activities were presented to participants, largely composed by young scientists
belonging to Mediterranean countries; a MOLAB demonstration was given;
-International Seminar on Museums, Science and Technology, Rio de Janeiro, Brazil, 2-5
October 2006: Eu-ARTECH activities were presented to a Latin American public, establishing
the bases for a future meeting with the participation of both European and Latin American
scientists and conservators.
Contacts have been consolidated with organisations developing activities in the field of cultural
heritage, such as:
38

- other I3 initiatives, such as LASERLAB (http://www.laserlab-europe.net/index.html) , NMI3
(http://neutron.neutron-eu.net/n_nmi3), and IA-SFS (http://www.elettra.trieste.it/i3/), three
integrated infrastructure initiatives where studies on cultural heritage are often developed;
- infrastructures operating in the field, such as the ICTP (Abdus Salam International Centre for
Theoretical Physics of Trieste, (http://www.ictp.it/ ) or the LABEC – INFN of Florence
(http://labec.fi.infn.it/index.html) or CEDAD of Lecce (http://www.cedad.unile.it/index.htm)
having a significant competence on scientific applications to cultural heritage;
- EC projects, such as COST G8 (http://srs.dl.ac.uk/arch/cost-g8/index.htm), CEN/TC 346
(http://www.cenorm.be/CENORM/index.htm), or the recently activated COST D42- ENVIArt
(http://www.echn.net/enviart/ ), all dedicated to the conservation of cultural property;
- association of conservators, such as the International Council of Museums-Conservation
Committee, ICOM-CC (http://icom-cc.icom.museum/), the International Institute of
Conservation, IIC (http://www.iiconservation.org/index.php), the Institute of Conservation
[ICON - the lead voice for the conservation of cultural heritage in the UK]
(http://www.icon.org.uk/), and others;
- Marie-Curie actions, such as EPISCON (http://www.episcon.scienze.unibo.it/episcon/),
promoting a European PhD in Science for Conservation or ATHENA,
(http://www.lens.unifi.it/mc-est/), a high education initiative in artwork conservation;
- extra-European infrastructures operating in the field of cultural heritage, such as The Getty
Conservation Institute, GCI, USA (http://www.getty.edu/conservation/); The Canadian
Conservation Institute, CCI, Canada (http://www.cci-icc.gc.ca/main_e.aspx ); The Art Institute
of Chicago, USA (http://www.artic.edu/aic/index.php ), the Metropolitan Museum of New
York, USA (http://www.artic.edu/aic/index.php); the Museo Historico Nacional de Rio de
Janeiro, Brazil (http://www.museuhistoriconacional.com.br/ingles/index.htm ); and others.
Regarding the media, MOLAB activities within Eu-ARTECH were presented to the Italian
public through an interview of Luca Pezzati (CNR-INOA) and Cecilia Frosinini (OPD) during
the TV transmission “Uno Mattina” (RAI-TV1-national channel). The interview was dedicated
to the study of Leonardo paintings by the MOLAB IR-colour scanner.
39

ANNEXES
40

Annex 1
Summary Report of the Third Interim Meeting
Perugia, November 20 th -21 st 2006 – University of Perugia- UNI-PG
The Third Interim Meeting of Eu-ARTECH have been held in Perugia , hosted and organised
by UNI-PG, in November 20-21, 2006. It was held in the Aula Dessau of the University of
Perugia, Piazza dell’Università 1.
Attendees were: Alberto de Tagle, Ineke Joosten, Caspar Laffree, Sophia Sotiropoulou, Jean-
Claude Dran, Jean Louis Boutaine, Dominique Robcis, Michel Menu, Alessandra Gianoncelli,
Jacques Castaing, Brunetto Giovanni Brunetti, Antonio Sgamellotti, Costanza Miliani, Laura
Cartechini, Brenda Doherty, Antonino Cosentino, Alessia Daveri, Catia Clementi, Marika
Spring, Ashok Roy, David Peggie, Rocco Mazzeo, Edith Joseph, S. Prati, Luca Pezzati,
Mathias Kocher, Martin Mach, Ina Vanden Berghe, Marjolijn deSulpaep, J.Delgado Rodrigues,
Ana Ferreira Pinto, Rute Fontinha, Cristiana Nunes, Simone Porcinai, Daniela Pinna, Barbara
Salvadori, Mauro Matteini, Barbara Sacchi, Piero Tiano, Vasco Fassina, Federica Presciutti,
Valentina Manuali, Manuela Vagnini, and Maria Douka.
After a general review of the agenda of the two days, the Coordinator B.G. Brunetti presented
the main lines of Eu-ARTECH dissemination of knowledge during the period May-November
2006.
After the introductory notes, the meeting continued with the 6 th Eu-ARTECH Governing Board.
_______________________________________________________
I - Consortium Governing Board n. 6
According to the Consortium Agreement, this meeting was restricted to the Coordinator and
one authorised representative for each participant infrastructure.
The following representatives were present: Coordinator: B.Brunetti; UNI-PG: A. Sgamellotti;
CNRS-C2RMF: M.Menu; CNR-ICVBC: P. Tiano; NGL: A. Roy; OPD: D. Pinna; BLFD: M.
Mach; OADC: S. Sotiropoulou; ICN: A. De Tagle; LNEC: J. Delgado; IRPA: I. Vanderberghe;
UNI-BO: R. Mazzeo; CNR-INOA: L. Pezzati. Apologies: RWTH, B. Bluemich.
Topics of the Agenda: 1-Annual reporting; 2-Amendments to the contract; 3-Mid term review;
4-Prefinancing of the third year and administration;; 5-Date and location of the next General
Meeting
1-Annual reporting
The Coordinator briefly reminded to the Consortium members that the 2nd Annual Report was
delivered on date August 22 nd . The first assessment from EC was received on date September
28 th with the request of adjustments for some documentation (UNI-PG, CNRS-C2RMF, CNR-
ICVBC/INOA, OPD, LNEC). The corrected documents were sent to Bruxelles on date October
27 th . A second assessment was received on November 8th with the request of integrative
certificates. The new documents were sent on November 9th. With these documents, the
procedure of assessment was closed.
B.Brunetti underlined how the work for second annual reporting suffered some inconvenient.
In particular:
1- The scientific report of the partners was, on the average, delivered to the Coordinator too
late, leaving only few days to compile the final report, which included also the very complex
41

management section. It was recommended to deliver the report on scientific activity to the
Coordinator before the annual meeting.
2- One engaging section is the “Implementation Plan for the Next Period”. The plan is
discussed by the Governing Board at each annual meeting, but very often full aspects are not
yet defined in detail. It is indispensable that each partner starts to plan any activity and, more
relevant, detailed expenditures at least two months before the annual meeting.
3-Regarding the Audit Certificate and associated Form C, it was recommended to pay attention
to the fact that the amount reported in last column of the first page of Form C is identical, at the
centesimal, to the budget certified by the auditor.
4-Important is also the “Justification of resources deployed”, where the various expenditures of
the project are described. This section is generally not enough detailed. The Coordinator
recommended to describe travels in terms of person, destination, and typology of the meeting or
visit, avoiding to write simply “participation to conferences”.
5- Within the “Justification of resources deployed” it is generally neglected the section where
justification for possible deviation from the planned budget should be written. The Coordinator
invited the Consortium members to fill in also this section.
After the presentation, the Coordinator answered to questions and, at the end, after several
discussions, the following time-schedule for the next annual deadline was unanimously
approved:
- 1 March: start preparation of the Implementation Plan by each Consortium member;
- 15 April: start preparation of Scientific Report by each Consortium member;
- 5 May: delivery of Implementation Plan and Scientific Report to the Coordinator;
- 10 May: Annual Meeting;
- 1 June: start preparation Management Report and Audit Certificate by each partner;
- 20 June: delivery of Audit Certificates to the Coordinator.
2-Amendments to the contract
In the second year amendment to the contract, the following modification was introduced on the
distribution of the total budget along the five years of the project:
1 year (month 1-12): 650.318,31 euros
2 year (months 13-24): 1.034.411,00 euros
3 year (months 25-36): 1.034.630,00 euros;
4 year (months 37-48): 1.034.630,00 euros;
5 year (months 49-60): 612.610,69 euros.
The Coordinator reminded:
a- Each Consortium member should take care of the fact that the budget of each institution must
be carefully planned, in order to avoid to arrive at the last year with a too high amount of
money; this could imply the impossibility to spend the whole budget;
b- Who will not be able to spend all the budget should declare it as soon as possible, in order to
allow the GB to carry out an amendment within the next Implementation Plan;
A discussion followed, where the Coordinator answered to several questions. At the end all the
members agreed on the necessity to carefully take care of the planning of each budget along the
next years of the project, presenting a specific plan at the next GB meeting.
3-Mid term review
The Coordinator announced that Mid Term Review will be carried out at the end of the third
year, i.e. at the next deadline in May.
One or two referees will be invited to participate to the Annual Meeting and analyse the Mid
Term Report.
In the Report should be clearly indicated:
-achievements of networking, access, and joint research activities;
-highlights of the activities;
42

-list of publications (where the indication “work supported by the European Community
through the Eu-ARTECH project within the 6th FP” must not be forgotten);
-list of TA’s for AGLAE and MOLAB with a synthesis of results (with statistics, publications,
conferences, etc.);
-list of initiatives for the dissemination of knowledge.
The Coordinator recommended each Consortium member to start the collection of data and
documents to be reported.
4-Prefinancing of the third year and administration
The Coordinator specified that each Consortium member received the second year prefinancing,
but not yet the third one. The Coordinator showed the prospect of the various
prefinancing of each institution for the second year and declared his availability to explain
details to each representative.
5-Date and location of the next General Meeting
In a previous GB meeting, it was already established to organise the Third Annual Meeting in
Munchen, DE. The assembly confirmed unanimously the location of Munchen, giving the
charge to BLfD to take care of the organisation. It was confirmed to hold the Meeting in the
rooms of BLfD. M.Mach, as BLfD representative, also confirmed that the Meeting will be
preceded by the workshop “Small samples, big objects”, also organised by BLfD.
The following dates were unanimously approved:
- May 9: Workshop “Small Samples, Big Objects”;
- May 10-11: Third Annual Meeting.
The Coordinator finally reminded that the Third Annual Meeting will coincide with the Eu-
ARTECH Mid Term Meeting, i.e. with the Meeting where one or two experts, selected by the
EC, will evaluate the work developed during the first three years of the project.
With this final decision, the 6 th GB Meeting of Eu-ARTECH was closed.
II – Steering Committee Meeting.
After a short break, the General Meeting continued with the Steering Committee meeting on the
work developed during the last six months. As usual for Eu-ARTECH, the meeting was open to
all participants.
The presentation of the various activities started with the networking N1 and N2. Rocco
Mazzeo (UNI-BO) briefly introduced J.L.Boutaine (C2RMF) and P.Tiano (CNR-ICVBC), the
two Convenors.
II.1 – Networking.
J.L.Boutaine, Convenor of N1, gave a general view of N1 activities developed during the last
semester. He emphasized the continuous effort made to open and diversify the distribution of
information relative to the Eu-ARTECH activities. At the end of October 2006, the institutions
or companies registered in the Eu-ARTECH mailing list was significantly extended. A big
effort was made by all the Consortium members to extend the list towards restoration
workshops, producers of cultural heritage materials, libraries, archives, archaeology institutions,
manufacturers of instrumentation. Recommendations were done in order to involve institutions
of EU countries probably under-represented, such as Czech Republic, Denmark, Finland,
Hungary, Poland, etc.
A list of conferences of interest in the field of “science & technology for cultural heritage” was
monthly updated and distributed to all the institutions registered in the mailing list. In any case,
the list of conferences is accessible on the Eu-ARTECH website (approximately 120
conferences have been registered, from mid 2004 to 2008).
Conferences and meetings of the last six months, where Eu-ARTECH activities were presented,
included: “Science for cultural heritage” – ICTP- Trieste, October 23 th -28 th 2006; Synchrotron
43

Radiation in Arts and Archaeology, Berlin, 27-29 September 2006; , 6° Sigma Aldrich Young
Chemists Symposium (6th SAYCS), Riccione (Italy), October 9-11 2006; Dyes in History and
Archaeology - 25 th Meeting, Suceava (Romania), September 21-23 th 2006; 12èmes Journées
d'Etude de la SFIIC - Couleur & Temps - La couleur en conservation restauration, Paris,
France, June 21-23 2006.
Progresses have been done in the various tasks, hereby listed:
N1-Task 1: Analytical resources, analytical procedures and investigation strategies (task
leader: C2RMF);
N1-Task 2: Exchange knowledge and expertise (task leader: ICN)
[-subtask2a (ICN) Reference Materials Sharing- overview on possible sharing of
reference materials among infrastructures; sharing of standards of dyed textiles and
lakes;
-subtask2b (C2RMF): Cooperation with MFA Boston on CAMEO (Conservation & Art
Materials Encyclopaedia Online);
-subtask2c (ICN). Working meeting on the inter-laboratory comparison and exchange of
analytical data on September 20 th , 2006, Suceava, Romania;
-subtask2d (ICN): Working group on electron microscopy and cultural heritage].
N1-Task 3 - Common approaches in the examination and analysis of paintings (task leader:
NGL)
N1-Task 4: Common analytical strategies (task leader: OADC)
For all these tasks, main lines of developments were presented. It was shown how all the
partners contributed to the achievement of the proposed objectives.
J.L. Boutaine particularly underlined the efforts in the contributions to the creation of standards
in cooperation with the CEN TC/346 coordinated by Vasco Fassina, who was present in the
odeon.
Presentation of N1 activities were concluded with the planning of three future meetings
organised by the consortium. They are:
-“Science and technology for cultural heritage”. This meeting, organised in cooperation with
Italian CNR and ICTP of Trieste, will be held in La Havana, Cuba on February 2007.
-“From easel painting to music instruments - Binders, colours and varnishes”. This meeting
will be held on March 6th & 7th, 2007, at the “Cité de la Musique”, in Paris. Co-organisation :
Cité de la Musique and C2RMF..
-“Small samples, big objects”. The seminar will be held in Munich on date May 9 th 2007 and
will be organised by BLfD.
P. Tiano (CNR-ICVBC) introduced the discussion on the activities of N2 . In fact, CNR-
ICVBC is responsible for the whole activity and, in particular, of the survey on “Methods and
Materials for conservation”. This task has as main purpose to assess the present practice and
scientific methodologies applied to verify the treatments of cleaning and consolidation of
stones, metals, and paintings.
N2-Task1f -Survey on cleaning and consolidation- Collection of data. (Task leader: CNR-
ICVBC).
The survey was carried out through specific forms, developed through the work of the
preceding years. They have been diffused in Europe during the spring 2006. According to their
typology, the forms collected up to date are: 62 for paintings; 14 for mural paintings; 26 for
stone artefacts; 19 for metals. However, the phase of collection of compiled forms is still in
progress and should be closed at the end of 2006.
The answers of the 121 forms collected up to now have been inserted in an Access database.
Details of the preliminary analysis will be annexed to the Interim Report.
N2-Task 2b - Identification of good practices in conservation (Task leader: OPD).
An e-forum was launched in order to gather information and to point out successes and failures
of the interaction between restorers and scientists. The forum is an opportunity to better focus
the problems connected to this theme at European level. Due to the fact that the opportunities
for in-depth discussion between restorers and scientists are relatively few, the forum is a chance
for a potentially constructive and beneficial communication. A page for a Bulletin Board was
44

created (http://eu-artech.icvbc.cnr.it/bb). Many people coming from various countries
(Belgium, France, Germany, Great Britain, Greece, Italy, Netherlands, Norway, Portugal,
Romania, Spain, Sweden, Switzerland) are registered.
During the preliminary step of the e-forum in March 2006, some positive answers (about 20)
were received from scientists working in public research centres, and also private and public
restorers. Even though the answers were not numerous, they were complete, well-documented
and articulated. So it was decided to write a first report based on the answers, useful for giving
indications and stimulating discussions. The report circulated through the website.
P,Tiano closed his intervention reporting on the Discussion Panel organisation. The meeting to
be held in Firenze just after the closure of the present meeting.
To close the section on networking activities, after the lunch break, Vasco Fassina, Coordinator
of the CEN TC/346, (European Committee on Standard in Cultural Heritage) presented the
activities developed by CEN in the last year. He presented the articulation of the work
developed by the various working groups and indicated the way of possible cooperation.
II.2 - Transnational Access
Regarding the Transnational Access activities, after a short introduction on AGLAE and
MOLAB, J.C. Dran presented the work developed during the last six months through the
AGLAE access. During the reporting period, 6 AGLAE experiments have been performed for
a total of 25 days of beam time. Of these days, 11 were devoted to conventional PIXE, other 11
were used for experiments on 3D µ-PIXE (a technique derived from synchrotron µ-XRF and
newly implemented on the AGLAE facility), finally, 3 days were dedicated to IBIL (Ion Beam
Induced Luminescence).
Regarding the new proposals, 10 were presented within the deadline of October 15 th 2006. Of
them, 6 were presented by new users, while 4 were continuation of research projects by users
who already obtained beam-time in previous calls.
The Peer Review Committee agreed to evaluate the proposals by e-mail, planning to meet more
formally next semester. As result of the e-mail evaluation, 8 projects were finally accepted (6
from new users and 2 from users who had previous access).
J.C. Dran underlined how several projects by AGLAE have been already published in the
scientific literature of the field.
C. Miliani (UNI-PG) presented then the activities of the mobile facility, MOLAB, during the
last six months. She described the four projects that were carried out during the first semester of
the third year. They were: a- A Technical Study of the paintings: Amor Vincit Omnia by
Caravaggio, with in-situ measurements at the Gemäldegalerie - Staatliche Museen zu Berlin,
Berlin, DE (June 2006); b- Paint on Early Meissen Stoneware, developed in the rooms of the
Staatliche Kunstammlungen Dresden, DE (July 2006); c- Drawing and colour in designing a
painting: Polidoro artwork, carried out in Capodimonte, Napoli, IT (October 2006); d- Casas
Pintadas de Évora, with measurements carried out in Evora, PT (November 2006).
At the deadline of October 31 th 2006, 7 new proposals were received. These proposals were
briefly described. They will be evaluated in a specific Peer Review Committee meeting to be
held in Rome at the end of December 2006 or beginning of January 2007.
II.3 – Joint Research
After a short break, the Steering Committee Meeting continued with the presentation and
discussion of the two Joint Research Activities.
First started P. Tiano, introducing the work carried out by the participating institutions (CNR-
ICVBC, LNEC, BLfD, UNI-BO, UNI-PG) to develop new protective methods for stones and
bronzes. Then, B. Doherty (UNI-PG) and J. Delgado (LNEC) presented in more detail the
results on stones, while R, Mazzeo (UNI-BO) presented the work developed on bronzes by
UNI-BO, BLfD, and LNEC.
Regarding stones, a short description of the developed work follows.
45

JRA1-Task2(stones)-Development of new treatments and procedures (chemical processes and
application protocols).
This task started during the first year of the project (4 th month), and continued till the end of the
second year. Because of the uncertainty of some results, additional tests have been carried out
during the first months of the third year, most concerning Modified Ethylsilicate (TEOS+APS)
treatments [note: the coupling agent (APS) in solvent (ethanol) was applied as a primer,
followed by application of TEOS]. The results confirmed that APS has the capacity to increase
the consolidating action of ethyl silicate close to the treated surface.
Water absorption tests were able to discriminate the APS action as a function of the lithotype
and the APS application procedure. These results pointed out that the procedure for APS
application as primer reduces the water absorption properties, but APS when used as primer
looses its influence in the consolidation action.
JRA1-Task4 (stones) –Treatment of aged samples [stone and bronze] followed by accelerated
and natural ageing after treatment.
This task started at the beginning of the third year (25 th month) and will continue up to the end
of the fourth year (48 th month). On the basis of the outputs of Task 2 and Task 3, properly aged
stone samples (see 2 nd Annual Report, Task3), have been treated according to selected
procedures (see 2 nd Annual Report, JRA1-Task2).
JRA1-Task5 (stones) – Monitoring, evaluation, and comparison of treatments.
This task started at the beginning of the third year (25 th month) and will continue up to the end
of the fourth year (48 th month). It consists in monitoring, evaluation and comparison of
treatments exposed both in natural and artificial environment.
Regarding the work developed on bronzes, a short description follows.
JRA1-Task 3 (bronzes) – Characteristics of sample properly aged before treatments
New samples naturally aged for a period of one year in marine environment (Genoa, IT) have
been added for comparison with those already available. Interesting subject was to observe
different corrosion behaviours of the marine natural aged patinas in two different marine
environment, such as Genoa, IT, and Lisbon, PT. The patina characterisation was done through
measurements by several techniques, such as: a) eddy current thickness measurements; b)
weight measurements; c) colour measurements; d) flatbed computer scanning; e) FTIR
microspectroscopy; f) EIS measurements.
JRA1-Task 4 (bronzes)– Selected treatments of aged samples.
After a preliminary evaluation of the performances of the selected treatments (organic, inorganic or
biological), the most promising final treatments were experimented on the various aged samples.
They are those which involve:
I-silanes F8363 (T1S) and Sivoclear (T2S) which seem to demonstrate a protective behaviour
comparable to the reference treatment (Incralac, Tref) and have no perceivable chromatic
alterations.
II-thick and dense cuprite layer (T3S) which is considered to be highly protective and markedly
more corrosion resistant than the bare metal.
III-fungi (T4S) which produce oxalic acid have been used to transform existing copper
hydroxysulphates and copper hydroxychlorides into copper oxalate.
IV-5 % limewater solution (pH=8,5), which is supposed to act as passivation agent with the
formation of basic calcium carbonate was chosen for the capacity to control the active corrosion
and compared with traditional corrosion inhibitor benzotriazole (Iref).
With this last presentation, the presentation and discussion of JRA1 activities was closed.
After a short break, the meeting continued with the discussion of JRA2 activities. A.Sgamellotti
(UNI-PG) introduced the presentation by the responsibles of the four tasks, which are
summarised in the following.
JRA2-Task1 - NMR Methodologies (Task Leaders: UNI-PG and RWTH),
S.Cozzolino (UNI-PG) presented the developments of the activities regarding the applications
of NMR to the study of porous materials (stones), ceramics, and siccative oils. In particular:
46

JRA2-Task1-1 - Methodology for lab NMR on ceramics and on siccative oils (partial).
Applications to the study of physical and chemical transformation during ceramic firing
continued, as well as the study on drying oils. After the article published in J.Phys.Chem. B, a
new paper on ceramic firing is in preparation.
JRA2- Task 1-2- Study of porous materials on reference treated samples (partial).
The applications of NMR techniques to the study of water absorptions by stones continued with
applications on the same lithotypes used in the experimentations of JRA1. Different NMR
techniques have been used to characterise:
-Gioia marble, Carrara, IT;
-Santafiora sandstone, Southern Tuscany, IT;
-Firenzuola sandstone, Firenze, IT.
The determination of capillary water absorption was carried out using the gravimetric
absorption technique, in accordance with the Normal Protocol, also used previously on other
lithotypes.
In particular, during this period, applications of Magnetic Resonance Imaging (MRI) were
experimented.
1
H High Resolution NMR spectroscopy was also experimented, in particular for the study of
Fiorenzuola stones.
JRA2-Task 1-3- Progress in NMR MOUSE 3D Imager.
Due to the absence of J.Perlo (RWTH), A. Sgamellotti presented the developments of activities
regarding the application of the NMR depth profiler developed through the work of the
previous years. In particular, it was mentioned that the NMR depth profiler, already
successfully experimented to evaluate the thickness of painting layers, was applied to study insitu
the ageing of paint layers.
JRA2-Task2 - Study of the IR transparency of ancient pigments. Advances on IR imaging
(assembling the two versions) (Task Leaders: OADC/CNR-INOA)
L. Pezzati and S. Sotiropoulou presented the development of the work on the two planned IR-
Imaging devices, according to the contract.
L.Pezzati first presented the last developments that lead to obtain for the first time 14 different
high-resolution images at different 14 wavelength in the IR range. The results not only clearly
demonstrated the feasibility of the system but also witnessed the high quality of the different
images that can be obtained.
Then, S.Sotiropoulou presented the advancement in the work developed in Ormylia. Also in
this case, the results were extremely positive and the planned milestones achieved.
JRA2-Task 3- Characterisation of optimal conditions for artwork XRD studies. Progress in
XRD&XRF system design (Task Leader:CNRS-C2RMF)
A. Gianoncelli (CNRS-C2RMF) presented the last results obtained in the development of a new
portable device for coupled XRF-XRD measurements. She showed how the design of the
portable integrated XRF/XRD system is now definitely settled (30 month milestone fulfilled).
A laboratory mock-up of the system has been assembled and preliminary experiments provided
data of XRF elemental compositions and XRD patterns for cases relevant to the cultural
heritage, such as easel painting, mural painting, and ceramics (deliverable at 30 month). There
are still a number of operations necessary to improve the system for XRF as well as for XRD,
however, the system can be considered now substantially operative.
JRA2-Task 4-Elaboration of the spectroscopic methods for the diagnosis of dyes and lakes on
polychrome surface (Task Leader: UNI-PG).
C. Miliani (UNI-PG) presented the development of the work towards a new methodology for
organic analyses of dyes and lakes trough an equipment which couples micro-Raman and
micro-fluorescence techniques. Three parallel subtasks where developed, whose advancements
were presented.
Subtask 4.1 - The vibrational and elevtronic characterisation of dyestuffs and lakes.
Several spectra of fluorescence and Raman scattering of organic substances were recorded and
the database, whose preparation already started in previous years, was extended. In particular,
47

the data were ordered in terms of: a-luminescence properties; b-Raman scattering yield; cexcitation
wavelength effect.
Subtask 4.2 - Elaboration of the spectroscopic methods for the diagnosis of organic matter on
polychrome surfaces.
For this aspects painting model standards were prepared by UNI-PG or shared with NGL and
OPD. Models of dyed textiles were also prepared and their spectroscopic behaviour
characterised.
Subtask 4.3 - Assembling and lab testing of the micro-Raman and micro-fluorimetry
spectrophotometer.
Regarding this point a new laser was acquired for the portable system, characterised by high
intensity and excellent stability (785 nm). Using this laser a better Raman scattering
characterisation of organic molecules is expected.
With this last intervention, the presentation of the advances of the work were concluded.
Therefore, the Steering Committee met separately in another room and, after a short discussion,
approved the activity developed during the first semester of the third year.
With this decision, the first day of the meeting was closed.
The second day was open with the intervention of M. Douka, Scientific Officer of Eu-
ARTECH. on the theme “Research Infrastructures within the 7 th Framework Programme”. She
started with the definition of a Research Infrastructure (R.I.) according to the 7 th F.P. She
reminded that, as R.I. must be considered those facilities, resources, and related services, which
are used by the scientific community to carry out leading-edge research and which promote
knowledge transmission, information exchanges, and knowledge preservation. These
infrastructures include major scientific equipment, scientific collections or archives, ICT-based
infrastructures, or even entities of a unique nature, used for research.
She also mentioned that the main objectives of the R.I. programme within the 7 th F.P. will
consist of:
-optimising the use and development of the best research infrastructures existing in Europe;helping
to create in all fields of S & T new research infrastructures of pan-European interest
needed by the European scientific community;
-supporting policy development and the programme implementation.
In any case, the 7 th F.P. will continue to support the integration of existing infrastructures,
promoting their coherent use and development through both a bottom-up approach or a targeted
approach (in the latter case with topics defined in coordination with the thematic areas).
Support for the construction of new infrastructures will be also provided, in agreement with the
work developed by the European Strategy Forum on Research Infrastructures (ESFRI). In this
case the process will be developed in two stages: the first will consist of restricted calls,
targeting projects identified as having pan-European character; the second will be the
implementation phase which will occur mainly under the financial responsibility of the Member
States.
Policy development and programme implementation will occur mainly through: - ERA-NETs
for research infrastructures; -studies, conferences and coordination actions for European policy
and/or international cooperation; -network of National Contact Points (NCP); -coordination
actions for strategic needs.
The presentation of the Scientific Officer stimulated many questions from the Consortium
members and answers were given to each of them. Several interventions and discussions
followed, mainly regarding the possibility to present a new project, at the next call of 2008, as
improvement and development of Eu-ARTECH.
After the lunch, discussions continued among the Consortium members. Many hypotheses were
advanced by the partners, regarding the way to introduce effective improvements in Eu-
ARTECH. At the end, two decisions were taken: first, it was decided to present a new proposal
at the next call and, second, to better elaborate the main lines of development a specific meeting
will be dedicated to this topic.
48

The Coordinator, reminding that rooms were available to hold separate meetings of the various
working groups, summarised:
-the achievements of the Consortium activities up to the 30 th month;
-the main lines of development of the work for the remaining annual period;
-the time-schedule approved by the Governing Board for the elaboration of the Third Annual
Report.
The Coordinator finally closed the meeting giving appointment to the Consortium members for
the dates of May 10 th -11 th in Munchen, DE.
In the afternoon, meetings of the working groups were held separately. Most participants then
moved to Firenze to participate to the Discussion Panel on the N2 Survey on cleaning and
consolidation.
49

Annex 2
Components of the Peer Review International Committees
AGLAE
MOLAB
Components of the Peer Review Committee
Annemie Adriaens Department of Analytical Chemistry, University of
Ghent, Belgium
Aurelio Climent-Font Departmento de Física Aplicada, Universidad
Autónoma de Madrid, Cantoblanco, Madrid, Spain
Patrick Trocellier Research Centre of Atomic Energy Commission (CEA),
Saclay, France
Jean Claude Dran AGLAE representative
Manfred Schreiner Institute of Chemistry, Academy Fine Arts, Vienna ,
Austria
Modesto Montoto Dept. of Geology, Group of Petrophysics, University
of Oviedo, Spain
Marisa Tabasso Former Director of Laboratories of Istituto Centrale del
Restauro and ICCROM, Rome, Italy
Brunetto Giovanni MOLAB representative
Brunetti
50

Annex 3
List of new AGLAE and MOLAB User-Projects presented and
evaluated during the first six-months of the third year.
AGLAE
Applicant Institution Project title/number Time
requested
A. Adriaens University of
Ghent, BE
G. Artioli
T, Carter
University of
Milano, IT
British Archaeol.
Institute of
Ankara, UK
B. Constantinescu IFIN-HH
Bucarest, RO
K. Janssens
B. Kannigiesser
A. Quaranta
A.I. Seruya PT
L. Troalen UK
M. Verita’
University of
Antwerp, BE
Techn. University
of Berlin, DE
University of
Trento, IT
Stazione sperim.
del vetro,
Venezia, IT
In-situ corrosion monitoring of
cultural heritage alloys
Early copper metallurgy in the
Apls
Obsidian industry of the
Catalhöyük (Turkey) Neolithic site
Gold provenance studies on
Bronze Age objects and Greek and
Dacian (“koson”) coins from
Romanian museums (3)
High resolution confocal μ-PIXE
of paint layers (2)
Continuation and extension of the
study of the feasibility of 3D
Micro-PIXE (2)
Ion beam induced luminescence
analysis of painting pigments (4)
Study and conservation of the
shrine of Prince Alphonse of
Portugal (XVth century)
Micro-PIXE studies on a gold
Egyptian ring-bead, necklaces and
earrings from the late 17th
Dynasty
Wall and vault mosaics of the 5th-
12th centuries in Rome. The
secrets of the glass tesserae
technology
51
(days)
Time
allocated
(days)
New
4 4 Y
2 2 Y
5 3 Y
5 N
5 5 N
10 5 N
3 N
4 3 Y
3 2 Y
3 3 Y
Sum of days 44 18

MOLAB
Applicant Institution Project title/Acronym Techniques Appro-
val
O. Barbu National
Universityof
Arts, Bucharest,
RO
J. Rogoz Institute for the
Study,
Restoration and
Conservation of
Cult. Heritage,
PL
R.
DeAngelis
Heritage Malta,
MA
B.Ormsby Tate Britain,
London, UK
A.
Burnstock
Courtauld
Institute of Art,
London, UK
Painting technique and
influence of atmospheric
pollutants on wall painting
at the Lady’s Church from
Bucharest
(LADY)
Effects on conservation
interventions on historical
polychromies in Poland
(CONSPAINT)
52
XRF, FT-IR, Vis-NIR,
micro-Raman, UV-Vis
fluorescence,
fluorescence imaging,
NMR-MOUSE
XRF, FTIR, micro-
Raman, fluorescence
imaging, NMR-MOUSE
Investigation on the vault XRF, FT-IR, IR-colour
painting at Verdala Palace, scanner, laser micro-
Rabat, Malta
profilometry,UV-Vis
(VERDALA)
fluorescence,
fluorescence imaging,
NMR-MOUSE
Evaluation of surface
cleaning treatments on
acrylic emulsion paintings
(ESCAEP)
FT-IR, , Vis-NIR, laser
micro-profilometry
A non-invasive technical XRF, FT-IR,Vis-NIR,
study of paintings and micro-Raman,UV-Vis
works on on paper by Paul fluorescence,
Cezanne (1839-1906) NMR-MOUSE
(PAP-WORK)
D. Thickett English Heritage Susceptibility of enamels
and bronzes to showcase
environments and open
display.
(ENAM)
C. Conti Soprintendenza
Archeologica,
Roma, IT
XRF, FTIR, micro-
Raman,laser microprofilometry
Study of architectural and XRF, FT-IR, Vis-NIR,
decorative materials of the micro-Raman, UV-Vis
Domus Aurea in Rome fluorescence,
(DOMUS)
Notes
- Meeting of PR
Committee to
be held on
January 5 th
2007
- See above
- See above
- See above
- See above
- See above
- See above

Annex 4
Standardised formats to describe analytical procedures and results
(DELIVERABLE n.1)
I - A standardised format for describing analytical results by HPLC-PDA
Dyestuff analysis of “object description”
Sample
Sample number Administration purposes
description
Work number Administration purposes
Object number Administration purposes
Analytical protocol Code of the protocol used for
analysis
Sample weight Sample preparation* Hydrochloric acid extraction
Date sample* Sample dissolved in* X? ul Dimethyl formamide
Sample taken
by*
Column* Luna C18, 150x2 mm id. 3 um.
Analysis done
by*
Gradient* Water/methanol/phosphoric acid
Filename HPLC* Detection* PDA, 200-700 nm
Date of analysis* Injection volume*
Note: the fields marked with * are mandatory
HPLC-PDA Chromatogram
Two graphs, 254 nm and in the relevant visual range
Only the relevant peaks will be integrated
53

Retention PDA Match1 Spect. Name Area %
Time
Area
1 14.189 Name component 1 206352 5.32
2 15.761 Name component 2 1169314 30.16
3 17.013 Name component 3 1558973 40.21
4 18.104 Name component 4 485275 12.52
5 19.162 Etc till all components are given 155570 4.01
6 19.820 112625 2.90
7 20.488 107982 2.78
8 21.023 69664 1.80
9 21.437 11583 0.30
Integration of components performed at X? nm.
Sample number: X?
215.3 14.32 220.0
Discussion
…………………….
Conclusion
…………………….
257.8
HPLC-PDA Spectra
409.4 525.9 564.9648.2 682.5
54
16.31
262.5
210.6
338.7
18.91 253.0
677.6
314.8
366.0
Component 1 Component 2 Component 3 Component 4
19.56

II – A standardised format for describing analytical procedures by HPLC-MS
Aim of the protocol, short description
The goal of this protocol is to describe the standard procedure, followed for the
identification of natural organic dyes extracted from textile fibres. A format is presented
below to provide all the details associated with the described protocol.
Author
Ioannis Karapanagiotis, ORMYLIA ART Diagnosis Center, Sacred Convent of the
Annunciation, Greece
Date of latest version
July 25, 2006
Chemicals
¡ ¡ ¡ ¢ £ ¡ ¤ ¥ ¢ £ ¡ ¤ ¥ ¢ £ ¡ ¤ ¥ ¢ £ ¡ ¤ ¥ ¦ ¦¦ ¦¨§ ¢ © ¡ § ¢ © ¡ § ¢ © ¡ § ¢ © ¡ ¡ § ¡ § ¡ § ¡ § § © ¥ ¤ ¡ § § © ¥ ¤ ¡ § § © ¥ ¤ ¡ § § © ¥ ¤ ¡ §
¡
¨
¨
55
¨¨
¨
¨ ¨ ¨
Materials
¤ ¤ ¤ ¤ ¥ ¢ ¥ ¢ ¥ ¢ ¥ ¢
¨ ¨ ¨ ¨
¨ ¨ ¨
¨
¨

Reagent preparation
A buffer solution (pH=3) is prepared by using formic acid and ammonium salt.
Equipment
Reversed phase liquid chromatography (RPLD) is carried out using Thermoquest
(Manchester, UK) HPLC system consisted of P4000 quaternary HPLC pump, SCM
3000 vacuum degasser, AS3000 auto sampler with column oven (30 o C), Reodyne 7725i
Injector with 20 l sample loop and Diode Array Detector UV 6000LP. PDA detection
is performed by scanning from 191 to 799 nm with a resolution of 2nm.
A Finnigan AQA mass spectrometer, MS (Thermoquest, UK) is utilized, with a
negative electrospray ionization (ESI-) on a single quadropole mass filter to record ion
signals, acquired in full scan (FC) mode. The ESI probe is operated at 400 o C* and
4kV*. The cone voltage is maintained at 20 V*. Xcalibur TM data system (Thermoquest,
UK) is employed for data acquisition and processing.
* These values can be modified upon tuning. Typical ranges are: For the probe 370 -
420 o C and 3.5 - 4.3kV. The cone voltage is set either at 20 V or at 30V.
Pre-examination
Samples are examined by a microscope and digital photos are stored in a computer. The
colour of the fibers is identified. If threads with different colours are identified attempts
are performed to separate them.
Sample pre-treatment
Samples (on the order of 1-2 mg) are weighted and treated with 400ul of a solution
mixture of H2O:MeOH:37% HCl (1:1:2, v/v) for 15 minutes at 100 0 C in open small
tubes to extract organic dye molecules from their mordant metals. After cooling, the
solution is evaporated to dryness by heating (60 o C) under gentle nitrogen flow. The dry
residue is dissolved in 300 l of DMF, except the reddish materials which are dissolved
in H20:MeOH (1:2). If necessary, further dilution takes place and the sample is finally
centrifuged. A volume of 20 l is submitted to HPLC analysis.
Analysis
HPLC analysis is performed using the following gradient.
¡£¢ ¤¤ ¡ ¡£¢ ¤¤ ¡ ¡£¢ ¤¤ ¡ ¡£¢ ¤¤¦¥ § § ¢ ¥¡ ¥ § § ¢ ¥¡ ¥ § § ¢ ¥¡ ¥ § § ¢ ¥¡ ¡
¨¨ ¤¤ ¢ ¨¨ ¤¤ ¢ ¨¨ ¤¤ ¢ ¨¨ ¤¤ ¢
©© © ¡ § ¢ ¤ ¡ § ¢ ¤ ¡ § ¢ ¤ ¡ § ¢ ¤ ©
56

Blank analysis
Blank analyses are performed regularly by injecting 20 ul acetonitrile, on a regular
basis as follows: (i) Three times at the beginning of the analytical day and (ii) once after
sample (or standard) analysis.
Standards
After a preliminary examination of 1 -2 samples selected from the set of samples which
will be analyzed an appropriate reference dye is selected. This is usually cochineal,
madder or weld. The chosen reference material is analyzed once per analytical day to
record any shifts occurred in the retention times of the detected colouring compounds.
The chosen reference material is also used for the tuning procedure, performed at the
beginning of an analytical day.
Data evaluation
Chromatograms are presented at a particular m/z. The latter is usually set initially at
100 – 500. If indications extracted from the DAD data, acquired simultaneously, show
that colouring components with molecular weight higher than 500 are present the m/z
range is adjusted accordingly.
Example of analysis of a standard
An example of cochineal is provided below.
(a) Chromatogram received at m/z: 100-500.
700000
650000
600000
550000
500000
450000
400000
350000
300000
250000
200000
150000
100000
12.08
11.83
12.56
6 8 10 12 14 16 18 20 22 24 26
Retention time (min)
57
20.60

Relative Abundance
(b) Spectra.
100
90
80
70
60
50
40
30
20
10
R.T. 11.83
156.1 313.6
364.5
474.4
0
100 200 300 400 500
m/z
Unknown compound
Relative Abundance
100
90
80
70
60
50
40
30
20
10
Relative Abundance
100
90
80
70
60
50
40
30
20
10
0
100 200 300 400 500
m/z
334.6
135.7 173.2 314.3
226.1
dcVII?
244.4
Carminic acid
392.0
406.0
0
100 200 300 400 500
m/z
R.T. 12.08 R.T. 14.83
58
490.6
Relative Abundance
429.3
100
90
80
60
40
30
20
490.4
70
50
10
Relative Abundance
100
90
80
70
60
50
40
30
20
10
R.T. 15.75 R.T. 20.60
211.4
248.5
0
100 200 300 400 500
m/z
312.3
dcIV?
Flavokermesic acid
373.4
300.0
211.5 240.4 422.8 467.4
329.1
0
100 200 300 400 500
m/z
411.6
454.3

III - A standardized format to describe analytical procedures for natural
organic substances investigation by non-invasive techniques.
Proposer: UNIPG – C. Miliani and C. Clementi
Aim of the protocol
The detection of fluorescence on surface involves different and sometimes unknown
problematics related to the instrumental optical set-up used and the nature (or
morphology) of the analysed sample. The emission can be then affected by some
important spectral modifications or distortions (diffraction, reflection and refraction
phenomena) that might make the technique apparently not specific and the results not
realistic and inconsistent with those of other laboratories. In addition, the innovative
aspect of the application of spectrofluorimetry on surfaces, involves a lack of in-depth
reference literature. The aim of this protocol is to give some useful and important
guidelines to correctly collect fluorescence spectra from surfaces and then obtaining
reliable results.
1. Equipment
Bench equipment. Varian Cary Eclipse fluorimeter: emission spectra on surfaces were
obtained using a Varian Cary Eclipse spectrofluorimeter, controlled by the Cary Eclipse
spectroscopy software. Differently from other spectrofluorimeters, the excitation source is
a Xenon pulsed lamp at 80 Hz with exceptionally long lifetime (pulse width at half peak
height ~ 2 s, peak power equivalent to 75 kW). The light source is focused on a Czerny-
Turner monochromator (190-1100 nm, grating 1200 lines/mm) for selecting the excitation
wavelength. The radiation emitted from the sample, collected under 90°, passes through a
Czerny-Turner monochromator (190-1100 nm, grating 1200 lines/mm) for selecting the
emission wavelength and is then directed to a high performance R928 photomultiplier
detector. This instrument gives corrected emission spectra with wavelength accuracy of ±
1.5 nm and wavelength reproducibility of ± 0.2 nm. The Xenon flash lamp and
sophisticated signal processing give the Cary Eclipse room light immunity.
To obtain emission spectra from surfaces external to the sample holder of the
fluorimeter, measurements were also carried out using a fibre optic probe system. By
this accessory the excitation light is directed to the sample via a randomized bifurcated
fibre optic bundle. The fluorescence from the sample is collected under 45°, to avoid
scattered excitation light, and is then redirected to the right angle port in the sample
compartment. The diameter of the fibre is 4 mm allowing a 12 mm 2 area to be analysed.
The instrument is equipped with an internal set of band pass and cut-on filters.
Portable equipment. The portable fluorimeter was assembled as a prototype from
separate components (fig. 1). 1, 2, 3 The exciting light source (150 W Xenon lamp, 240-
600 nm emission), is focused on a H-10 Jobin Yvon UV-monochromator (linear
dispersion 8 nm/mm) for selecting the excitation wavelength. A fibre-optic cable directs
the excitation light on the surface under investigation. The emitted light is converged by
another fibre-optic cable to a high sensitivity Avantes CCD spectrometer (86
photons/counting, 200-1100 nm, grating 300 lines/mm). The spectral resolution is about
20 nm using a 600 μm fibre optic diameter. The instrument is interfaced to a portable
computer with a suitable software (Avasoft 5.1) to store and elaborate data. To optimise
59

and reproduce the position of the fibre on the sample, an accessory, built up by
transparent material, is used which allows the underlying surface to be seen and the
fibre position to be carefully selected. The fibre allows a surface area of 2 mm 2 to be
analysed. Interferential and cut-on filters were used. The portable instrument is totally
located in two cases (40x10x30 cm) which reach 15 kg as a total weight thus allowing
to be easily transported and even used in small rooms.
2. Filters
In order to avoid that some amount of spurious white light, coming from the lamp, is
transmitted by the monochromator, interferential or band pass filters were placed after
the excitation monochromator. Cut-on filters were used after the sample compartment
to eliminate the second order excitation light.
3. Pre-examination
UV-vis reflectance measurements were previously carried out to have an indication
about the absorbance range of the sample so that the right excitation wavelengths can
be chosen. Emission spectra were first collected in single scan mode and then in 3D
mode.
4. Analysis
- Blank analysis:
In order to evaluate possible interferences of wool or silk fibre signals on dyes emission
spectra, unmordanted and mordanted undyed fibres were previously analysed under the
same experimental conditions and following the same procedures used for dyed
samples.
- Standard:
A model sample of Bengal rose applied on canvas is used as a standard to check the
presence and the intensity of the signal that reach the detector in the portable
equipment. This procedure is necessary after any displacement or transportation of
the instrument. Europium powder is used as a standard to check if the spectral
resolution of the bench instrument is constant.
- Detection parameters:
The best compromise between high emission and spectral resolution can be
obtained by varying the following instrumental parameters: excitation and
emission slits (5-20 nm), scan rate (high: 600 nm/min, slow: 120 nm/min,
slowest 30 nm/min) and photomultiplier voltage (medium: 600 V, high: 800 V).
5.Data evaluation
Emission spectra collected in single scan mode are presented to show their entire shape
(when it is possible), maxima and shoulders included. A possible excitation wavelength
effect is evaluated on the basis of 3D fluorescence spectra and relative contour plot
diagrams. Instrumental distortions are indicated in the graphs when they are recognised
but not completely eliminated.
60

6. Example of analysis of a standard
Sample information
Non-invasive Dyestuff analysis of “object description”
Sample description* Sappanwood on silk
Measurement point ------
Date of analysis* 13 april 2006
Analysis done by* Catia Clementi
Experimental parameters
Filename FOFS* sappanwood_15_360_01
Optical geometry 45°
Scan mode Single
Excitation wavelength 360 nm
Excitation filter Varian 250-395 nm
Interferential filter -
Excitation slit 20
Emission wavelength 430-800 nm
Emission filter Varian 430-1100
Cut-on filter -
Emission slit 20
Photomultiplier voltage 600 V
Scan rate 600 nm/min
Averaging time 0.1 sec
Data interval 1 nm
Correction file No correction.ascii file
61
Sample number Administration purposes
Work number Administration purposes
Object number Administration purposes
Doc. Map Administration purposes

Emission intensity / a. u.
1.0
0.8
0.6
0.4
0.2
0.0
575
600 700 800
λ / nm
62
15-sappanwood on silk
Fig. 1 – Normalised emission spectrum of silk dyed with sappanwood ( exc: 360 nm).

Sample information
Non-invasive Dyestuff analysis of “object description”
Sample description* Sappanwood on silk
Measurement point ------
Date of analysis* 13 april 2006
Analysis done by* Catia Clementi
Experimental parameters
Filename FOFS* sappanwood_15_3D1
Optical geometry 45°
Scan mode 3D
63
Sample number Administration purposes
Work number Administration purposes
Object number Administration purposes
Doc. Map Administration purposes
Excitation wavelength 260-390 nm, increment 10 nm
Excitation filter Varian 250-395 nm
Interferential filter -
Excitation slit 20
Emission wavelength 470-800 nm
Emission filter Varian 430-1100
Cut-on filter -
Emission slit 20
Photomultiplier voltage 600 V
Scan rate 120 nm/min
Averaging time 0.5 sec
Data interval 1 nm
Correction file No correction.ascii file

Fig. 2 – Three-dimensional fluorescence spectra of silk dyed with sappanwood ( exc = 260-390 nm, em =
470-800 nm).
Z A xis
390.00 40
380.00
Intensity (a.u.)
30
370.00
360.00 20
350.00
10
340.00
330.00
320.00
310.00
300.00
290.00
280.00
270.00
260.00
Intensity Intensity Intensity Intensity Intensity Intensity Intensity Intensity Intensity Intensity Intensity Intensity Intensity (a.u.) (a.u.) (a.u.) (a.u.) (a.u.) (a.u.) (a.u.) (a.u.) (a.u.) (a.u.) (a.u.) (a.u.) (a.u.)
1000
40
50 70
40 60
40
40 50
60
800 60
40 50 60
50
30
30
40 50
600 30 40
30 40
40
30 40
20
400 20
30
20
30
30
20
20
20
200 10
20
20
10
10
500 600
Wavelength (nm)
700 800
0
400 500 450 600 500 700 550 800 600
500.00 550.00 600.00 Wavelength Wavelength Wavelength Wavelength Wavelength 650.00 (nm) 700.00 750.00 800.00
Wavelength (nm)
Fig. 3 – Contour plot diagram obtained from three – dimensional fluorescence spectra of silk dyed with
sappanwood ( exc = 260-390 nm, em = 470-800 nm).
64
75.33
69.65
63.98
58.30
52.62
46.95
41.27
35.59
29.92
24.24
18.56
12.89
7.21
1.53

Discussion
The fluorescence spectrum of silk dyed with sappanwood consists in a band with a
maximum at 575 nm, the emission intensity is very low compared to other red textile
samples.
Three-D fluorescence spectra and relative contour plot diagrams show that the position
of the band at 575 nm is independent on the excitation wavelength indicating the
presence of one emitting species.
Conclusion
Fluorescence spectrum of silk dyed with sappanwood shows the presence of one
emitting species.
Relevant literature
[1] C. Clementi, C. Miliani, A. Romani and G. Favaro, “Spettrofluorimetria UV-VIS in
riflettanza: una tecnica non distruttiva per la diagnostica dei manufatti artistici”, Proceedings
10° Congresso Nazionale sulle Prove non Distruttive Monitoraggio e Diagnostica, (2003) 110-
118.
[2] C. Clementi, C. Miliani, A. Romani and G. Favaro, “In situ fluorimetry: a powerful noninvasive
diagnostic technique for natural dyes used in artefacts. Part I: Spectral characterization
of orcein in solution, on silk and wool laboratory-standards and a fragment of Renaissance
tapestry” Spectrochimica Acta, Part A, 64 (2006) 906-912.
[3]C. Clementi, G. Favaro, C. Miliani, A. Romani, U. Santamaria, F.Morresi, K. Mlynarska,
“In-situ fluorimetry: a powerful non-destructive diagnostic technique for natural dyes used in
tapestry. Part II: Identification of orcein and indigo in some Renaissance tapestries at the
Vatican Museum” (manuscript in preparation).
[4]A. Aldrovandi, A. Casini, G. Centauro, C. Clementi, C. Miliani, and others, “Evaluation of
non invasive techniques for the identification of organic materials in wall painting”, Proceeding
of Art ‘05 Conference, (2005).
[5]G. Favaro, C. Miliani, A. Romani and M. Vagnini, “Role of protolytic interactions in photoaging
processes of carminic acid and carminic lake in solution and painted layers”, Journal of
the Chemical Society, Perkin Transaction, 2 (2002), 192-197.
[6]C. Miliani, C. Ricci, F. Rosi, A. Sassolini, F. Presciutti, C. Clementi, A. Romani, B.G.
Brunetti, A. Sgamellotti, C. Seccaroni and P. Moioli, “The Deposizione Baglioni (1507): non
invasive study of the Raphael’s palette by complementary molecular spectroscopies from X-ray
to near infrared.”, National Gallery Technical Bulletin, in press.
[7]C. Clementi, C. Cibìn, A. Romani e G. Favaro
“A spectrophotometric and fluorimetric study of Red Madder in solution and on dyed wool”,
Proceedings, DHA XXIII (accepted for publication).
[8] C. Miliani, A. Romani and G. Favaro "A spectrophotometric and fluorimetric study of
some anthraquinoid and indigoid colorants used in artistic paintings", Spectrochimica Acta Part
A, 54 (1998) 581-588.
65

Annex 5
Minute of the working meeting on the inter-laboratory comparison and exchange
of analytical data held on September 20th, 2006, Suceava, Romania.
(DELIVERABLE n. 2)
Attendees:
Eu-ARTECH consortium
Costanza Miliani UNIPG
Catia Clementi UNIPG
Ina vanden Berghe KIK-IRPA
Jan Wouters KIK-IRPA
LianaValianou OADC
Jo Kirby NGL
Catherine Higgitt NGL
David Peggie NGL (UoE/NMS till summer 2006)
Marjolein Groot Wassink ICN
Maarten van Bommel ICN
External experts
Irina Petrovisciu NRL
Anita Quye NMS
Cecily Grzywazc GCI
Nobuko Shibayama Met
Witold Nowik LRMH
The PowerPoint presentations of the meeting will be added as deliverable to the next interim
report in combination with this report. All analytical protocols and the results obtained so far
will be distributed among the participants of this meeting by ICN.
3D Fluorescence spectroscopy
Catia presented the work done with the fibre –optic UV-vis fluorescence spectrometer; her
PowerPoint will be added as well. The systems available faces problems when analysing the
surface of an object / sample rather than a sample dissolved in solutions. The problems can be
resolved selecting a proper set of filters, this allow enhancing both reproducibility and
specificity of the technique. Spectra were obtained from all pigments and dyed textiles. The
main conclusion was that for the red, the animal sources can be distinguished form the
vegetable ones. For the yellow ones, it is more difficult to determine the source. Shifts in
fluorescence are observed due to the ‘potash’ effect. The dyes interact differently on wool and
silk. In both weld and dyer’s broom, probably chlorophyll is present; this has to be confirmed
by other techniques. The chlorophyll has been identified by comparing the emission, exctitation
and absorption spectra of weld and dyer`s broom with that of standard chlorophyll A and B.
Being the spectral features very specific we are quite confident about the identification.
After presentation of the first results, the main discussion was about the protocol to use. The
automatic mode, when the combination of excitation and long-pass filters is determined
automatically does not always give the appropriate result. Besides, it is not known which filters
are used then. Particularly minor dyes with a different colour then the main colour of the
sample can be missed. However, it can be a convenient mode if it is not known what to expect
in your sample (for example when synthetic dyes are present). The analysis itself is nondestructive
and quite fast.
Therefore, two protocols will be developed by UNI-PG and KIK, one starting with the
automatic mode and the other with three filter sets suitable for yellow, red and blue dyes. UNI-
66

PG and KIK will make sure that the same format for the description of the protocol is used, so
that these can be easily compared. This approach can be very helpful for those who are new in
the field of dyestuff analysis with this technique. Please, be aware that the different partners
(KIK and UNI-PG so far) are obviously allowed to adapt their protocols specified for their main
applications, just as is the case with the HPLC protocols.
In addition to the development of this protocol, the organic pigments prepared so far will be
painted in different binding media (siccative oil, whole egg and rabbit-skin glue) on an
appropriate support (Teflon). These paints then can be used for further development of the 3D
Fluorescence spectroscopy.
To further estimate the possibilities and limitations of the non-invasive technique, new textile
samples will be prepared, in which dyes are mixed. A combination of a yellow dye and a red
dye, a red dye and a blue dye and a yellow and e a blue dye will be prepared by ICN.
Furthermore, a selection of pigments dyed will be faded (without UV in order to produce a
photochemical degradation more similar to that occurring at indoor exposition of textiles and
painting) by NGL or ICN.
HPLC-PDA
A general comment is that it must be clear which protocol was used for which result. Therefore,
the protocols will be coded and these codes will be added in the description of the analytical
results.
Indigo
- All partners are able to identify indigo (or woad) based on the presence of indigotin and
indirubin.
- It is worth noting that indigo is also identifiable by UV-vis fluorescence by the
presence of a weak but specific emission at about 745 nm.
- It is not possible to distinguish between indigo, woad and synthetic indigo. Even in synthetic
indigo, quite often a small amount of indirubin is identified.
- The spectrum of isatin is shown. This is a precursor of indigo, but is also to be believed a
degradation product of indigotin.
- In addition, two unknowns are detected with absorption at 335&385nm. These are often found
by different partners, it is unknown if these components are related to indigo or woad.
- NMS detects several other components as well, both UV absorbing and indirubin and
indigotin equivalents. However, the injected amount was relatively high. ICN detect m any
different blue and red colorants in indigo extracted from plant material, we never tested if these
components dye textiles.
- One main remaining question is how much of the dyeing components is extracted from the
dyed textiles and whether or not components are missed due to bad extraction which can be of
relevance to distinguish between woad and indigo. One option for testing this is to make
separate dye baths of both woad and indigo and analyse these dye baths. Next a large amount of
wool is dyed and the dye bath are analysed again to determine what components disappear (and
should dye wool). However, this experiment is beyond the scope of the EU-Artech project.
Cochenille
- All partners are able to detect the main components and the dc types.
- With the use of LC-MS, David Peggie identified dcII as a glycoside of flavokermesic acid,
dcIV and dcVII as carminic acid glycosides, so stereo-isomers.
- Distinguishment between ararat (Armenian cochineal) and cochineal can be done by dcII, if
calculated at the correct wavelength, 275 nm [ 1 ]
1 Jan Wouters and André Verhecken, The coccid insect dyes: hplc and computerized diode-array analysis
of dyed yarns, Studies in Conservation 34 (1988) 189-200.
67

- In wool the concentration of dcII should be 1 – 2% if cochineal is present. Interestingly, in silk
the concentration of dcII seems to be lower, so it is important to keep this in mind when
identifying.
- A component, labelled dcIII by KIK. Can be found, the same component is detected in
madder as well. It could be that this component is obtained during an ammonia treatment.
Dyer’s broom
- All partners are able to identify this colorant based on the presence of luteolin and genistein.
- All partners did find luteolin and genistein equivalents, which are likely to be glycosides.
There is one in a high concentration, which is not genistin. As this one is usually not found in
dyer’s broom, this could be an artefact. Be aware that in the lakes, this specific component is
much lower in concentration
- NGL detects more glycosides due to sample pre-treatment with BF3. Ratios between
glycosides and aglycones depend of sample pre-treatment.
- KIK detected an unknown component at 20.3 min, abs 419 nm, similar as in weld. ICN did
not detect this in the Artech samples, but in the ABEGG samples we did find such a
component, eluting prior to luteolin. This could be due to the difference in analytical column,
ICN will analyse the EU-Artech reference again and inject a higher concentration to verify this.
- There was a question whether or not it is possible to distinguish between dyers broom and a
mixture of weld and dyers broom. This is possible, when the 5,7 diglycoside of luteolin can be
identified, which is specific for weld. This is only possible with mild extraction techniques such
as BF3. (During DHA, Claude Andary presented another extraction technique which can be an
alternative)
- In some text books (e.g. Schweppe and Hofenk) it is stated that dyers broom does not contain
apigenin. Based on these results and other results at ICN and by David Peggie, this is not true.
Weld
- This dye was extensively discussed last year, to recall: All partners did detect luteolin and
apigenin and traces of equivalents. NGL, using BF3 extraction, did detect also glycosides of
luteolin and apigenin. Mainly the monoglycoside dyes, whereas in the pigments both mono-
and diglycosides were identified.
- Interestingly, Nobuko Shibayama (Metropolitan) detected a high amount of luteolin-7glucoside
in the textile sample. She does extraction with 0.001M disodium
ethylenediaminetetraacetiate in deionized water and methanol (2/3, v/v) was added to the small
test tube. The test tube was, then, heated in a dry bath incubator at 65-70ºC for 20 minutes.
Next evaporated to dryness. Analysis on XTerra C18 column with gradient of water,
acetonitrile and 0.1 % TFA. Her results will be included as well.
Redwood
- Brasilein is known to be unstable under HCl extraction condition, it also shows a broad peak
with water/methanol/PO4 gradient.
- OADC show a much better picture of brasilein as they are using water/acetonitrile/TFA.
- With BF3, extraction yield from textiles is very low (NGL).
- An unknown component, labelled type C by ICN and NGL (according to Witolds publication
[ 2 ]) and orh by KIK was found by all partners. NGL is working on identification. This
component seems to be more stable then the red components, it could be a precursor or a
degradation product.
- KIK has problems with the silk sample; NGL had problems with both textile samples due to
BF3 extraction.
- ICN and OADC detected unknown red components in the pigment, brasilein-equivalent and
possibly an anthraquinone. The identity of these components remains unclear.
2 Witold Nowik, The possibility of differentiation and identification of red and blue ‘soluble’ dyewoods:
determination of species used in dyeing and chemistry of their dyestuffs, DHA 16/17 (1997/1998) 129-
144.
68

- The graph and spectrum of brazilin is included.
- It is most likely that the component identified as brasilein is actually an elimination product.
To confirm this, brazilin will be converted into brasilein [ 3 ] and analysed directly by HPLC.
Safflower
- Nobody is able to identify, the main colouring component carthamin in the red samples, with
the exception of NGL.
- NGL identifed the carthamin by comparing published results.
- ICN has a reference labelled “fleur the carthamin” which was analysed as well (results
included). Dissolving this dye in DMF resulted in both yellow components as well as what is
believed to be carthamin. The yellow components are destroyed during HCl extraction.
- Identification of carthamin red done by KIK based on degradation products which show
absorption in the UV range. All partners will look if they detects these components.
- According to Liana, Carthamin is available as a pure component. If so, this can be used to
perform some extraction tests.
- Note: OADC, KIK, ICN and NGL detect yellow components in safflower yellow, but these
are not similar.
- KIK detected apigenin in the safflower red.
Madder
- According to literature (Schweppe and Hofenk) the ratio between alizarin and purpurin should
be 75-95% alizarin and 5-25% purpurin in the Rubia tinctoria (ignoring the other components).
In the wool samples, the ratios are different. This is also quite often found in samples from
historical objects. We all agree that this argument is not valid, the ratio’s varies a lot and is
dependent of both how the plants were grown and how the dyestuffs were extracted. Even in
wild madder (Rubia peregrina L.) up to 20% alizarin can be found.
- Rubiadin is detected if enough is injected, however there is another component identified by
all partners, with a similar spectrum, but eluting later. [ 4 ]
- OADC has a lot of unknowns; most of them can be identified based on the results from KIK.
- NGL, ICN and OADC have a very strange component (lake 2i), absorption at 514 and 550
nm. This is the component labelled ‘dcIII’ by KIK (in cochineal) and is probably due to an
ammonia treatment of the sample.
- KIK, ICN and NGL detect a lot of xantho-purpurin in lake 2i, which is probably due to the
way the pigment was prepared.
General conclusion
The exchange of information at this detailed level is very convenient. As a result, many
conclusions could be drawn or confirmed by this comparison.
JCAMP
Catherine Higgitt explained about the implementation of mass spectra in the JCAMP format
which was originally developed for FTIR. Her presentation will be included. It must be clear
what our main purpose would be if we want to continue with this database. As many different
systems were used to identify our colorants, it is not possible to exactly compare retention time
and spectra. Therefore, presentation of the results in a pdf format will be sufficient, particularly
because the idea was that other scientist who wants to compare, can have samples and basically
have to repeat the analysis with their own analytical technique. This information, both
analytical protocols and the results ca n be presented on a website.
The results have to be presented in an organised way so that it is very clear what each result
means. In addition, a clear description of our project has to be written. The results will be
presented on the EU-Artech website and the MASC website (or via a link). We need to make a
3
H. Schweppe, Handbuch der Naturfarbstoffe (1992) 413. Brasilin can be oxidised into brasilein by 20%
sodium jodate in 40% acetic acid (hot).
4
Elena Karpova showed during the DHA meeting that this unknown was identified as nordamnacanthal
69

formal decision if we want to have this information public available or protected by a password
which can be achieved after registration. This decision will be made during the next EU-Artech
meeting.
Option: it was later discussed in a small group that it might be smart to determine if the data
fields of our results can be adapted to the JCAMP format, so that we can convert it into this
format is we decide to do so in a later stage.
Storage and sharing materials
Storage of the textile samples will be in acid free paper / envelope, so example archive
envelopes. The pigments will be stored in the Teflon vials supplied by NGL. The samples will
be stored at room temperature and at 50% RH or in a textile depot. The samples need to be
protected from light.
There is enough material available to share with other for analytical purposes. For other
purposes, fading etc, new materials have to be made. The recipes are available as well.
Dissemination
Jo Kirby presented the project during the 25 th DHA meeting in Suceava. We have to decide
during the next interim meeting if we want to present this project at the IUPAC meeting in
august 2007, Torino. In September 2008, the next ICOM-CC meeting will be held. A call for
abstracts will be done in January 2007, deadline for the abstracts is April 2007, deadline for
papers is in November 2007.
New materials
The is an interest in new materials, we like to expand gradually. Black textiles are available via
MODTH. Ina vanden Berghe will prepare list with more materials available via MODTH. New
materials which are of interest are
-Sawwort
-Lac dye
-Young fustic
-Old fustic
-Buckthorn, yellow and sap green (pigments only)
Michel Garcia will be contacted if he can supply the botanical sources. ICN will dye wool and
silk with the materials mentioned above. In addition, new samples will be prepared containing
mixture for UV-vis fluorescence spectroscopy. However, no new materials will be prepared
before the dissemination of the first part of the project is done via the EU-Artech website.
New strategies
During the next meeting of DHA, in Vienna 7-10 November 2007, an additional day will be
organised to discuss new strategies. The organisers of the DHA meeting will arrange a room
and coffee, tea and lunch, Maarten will take care of that. We have to think about how we will
organise this. The most interesting topics so far are Raman and UV-vis fluorescence
spectroscopy both approaches could allow to study the organometallic complex as a whole.
Regarding the UV-vis fluorescence, currently present in the project as non-invasive fiber-optic
technique (KIK, UNIPG) would be interesting to explore the capabilities of a micro
experimental set-up as those used by Maria Joao Melo that could allow to get emission and
excitation spectra from tiny samples or cross-sections.
Quite new development in the area of Raman is SERS, Surface Enhanced Raman Spectroscopy.
Unfortunately, according the very recent literature this does not work properly on lake
probably because complex of organic-substrate is to strong and therefore to have SERS effect
the dye has to be extracted anyway. However, it would be interesting to hear potentialities and
disadvantages of the technique from expert as Marco Leona (MET) 5 or Francesca Casadio (Art
5 Kui Chen, Marco Leona, Kim-Chi Vo-Dinh, Fei Yan, Musundi B. Wabuyele and Tuan Vo-Dinh,
Journal of Raman Spectroscoy 2006, 37 520-527.
70

Institute of Chicago). Another development is FT-Raman which uses Nd:YAG laser excitation
at 1064 nm to avoid fluorescence 6 . A third technique is Pulsed-Raman.
The new strategies task, belongs to task 4 which will be discussed in more detail during the next
interim meeting of Eu-ARTECH. OADC is task leader of task 4.
So far, we will not concentrate at the inorganic constituents, since it is never clear if the
mordant is measured or a contamination (soil). In organic pigments, the substrate can be
determined by SEM-EDX. Measurements or the organic-inorganic complexes as a whole can
be of interest for the future.
6 A. Pielesza, A. Weseucha-Birczynska, Journal of Molecular Structure, 555 (2000) 325–334.
71

Annex 6
Abstract of the presentation of Jo Kirby at the DHA meeting in Suceava, RO,
September 2006.
(DELIVERABLE n.3)
Dyeing and dyestuffs revealed: The Eu-ARTECH collaborative study of reference
materials
Jo Kirby 1 , Maarten van Bommel 2 , Catherine Higgitt 1 , David Peggie 1 , Marjolein Groot
Wassink 2 , Ina van den Berghe 3 , Jan Wouters 3 , Sophia Sotiropoulou 4 , Ioannis Karapanagiotis
4 , Lemonia Valianou 4 , Costanza Miliani 5 , Catia Clementi 5 , Irina Petroviciu 6 , Cecily
Grzywacz 7 , Anita Quye 8
1
Scientific Department, National Gallery, London
2
Netherlands Institute for Cultural Heritage, Amsterdam
3
Laboratory for Materials and Techniques, Royal Institite for Cultural Heritage, Brussels
4
Sacred Convent of the Annunciation, ORMYLIA Art Diagnosis Centre
5
Centre of Excellence SMAArt and CNR – ISTM, University of Perugia, Perugia
6
National Research Laboratory for Conservation and Restoration of Movable National Cultural Heritage,
Bucharest
7
Analytical Research Team, Getty Conservation Institute, Los Angeles
8
Department of Conservation & Analytical Research, National Museums of Scotland, Edinburgh
An important activity within the framework of the Eu-ARTECH 1 project on the conservation of
European cultural heritage is the sharing and exchange of expertise and resources; cooperation
between institutions is of benefit to all. As part of this, a collaborative project on the analysis of
natural organic dyestuffs used for objects of cultural heritage is being carried out, using a wide
range of microscopical, spectroscopic and chromatographic techniques. For this comparative
exercise to be successful, it is necessary to have a set of well-defined reference materials
representative of those present on cultural heritage objects, so that, firstly, the procedures used
by the different laboratories can be assessed and compared and, secondly, the comparison
between these standards and real artefacts should be as realistic as possible. The intention is that
a ‘library’ of the reference materials and a database of the preparation and analytical data
relating to them should ultimately be available to the partners in the consortium and to other
researchers in the future.
It is not possible to study every dyestuff within the timescale of a short-term project, thus a
range of colorants representative of those used in Europe, or identified on objects of European
cultural heritage, was selected; the fact that some dyes present an analytical challenge was also
taken into account in the selection process. The dyes chosen were dyer’s broom (Genista
tinctoria L.); safflower (Carthamus tinctorius L.); sappanwood (Caesalpinia sappan L.);
madder (Rubia tinctorum L.); Mexican cochineal (Dactylopius coccus Costa); and indigo (using
indigo powder). Samples of textiles and pigments made using weld (Reseda luteola L.) were
already available; this pilot project was described at the 24th Meeting of Dyes in History and
Archaeology, Liverpool, in 2005.
The recipes used for the preparation of the dyed textiles and pigments were representative of
those used in Europe between the 15th century and the present day, modified for present-day
laboratory conditions. As practical laboratory work on the scale needed to prepare these
standards was not covered under EU-ARTECH Networking activities, they were prepared
under COST Action G8 (Non-destructive analysis and testing of museum objects) Short Time
72

Scientific Mission (STSM) Projects awarded to one of the authors (Irina Petroviciu) and hosted
by the Royal Institute for Cultural Heritage, Brussels, and the National Gallery, London.
This paper will discuss some of the findings already made during investigation of the samples.
It will also examine some of the considerations that need to be borne in mind when preparing
reference materials that are intended to be a ‘library’ for future researchers and to be
comparable with genuine artefacts. These include the ways in which recipes need to be
modified for present-day laboratory conditions; the fact that the real objects have aged; the fact
that the reference materials may be used by analysts in the future for experimental purposes we
cannot anticipate; sharing data; safe storage of the samples.
1] Eu-ARTECH - Access Research and Technology for the conservation of the European Cultural
Heritage, FP6-RII3-CT-2004-506171, (2004-2008) http://www.eu-artech.org/ .
73

Presentation of Jo KIRBY at the DHA meeting in Suceava, RO (see website).
Only the first and last slides are reported here. For the full presentation, see the Eu-ARTECH
website (Reserved Area- OTHER DOCUMENTS)
74

Annex 7
Report on the Electron Microscopy working group kick-off meeting (during Eu-
ARTECH Interim Meeting, November 21 st 2006, Perugia)
(DELIVERABLE n.4)
Present: M. Mach (BLFD), M. Vagnini (UNI-PG), F. Presciutti (UNI-PG), F. Rosi (UNI-PG),
S. Porcinai (OPD), B. Salvadori (OPD), D. Pinna (OPD), S. Prati (UNI-BO), M. Spring (NGL),
A. Roy (NGL), I. Joosten (ICN).
Not present but expressed their interest: S. Bracci (CNR-ICVBC), M. Menu (C2RMF), M.
Schreiner (ABK Wien-external expert) and A. Adriaens (University of Gent-external expert).
Electron microscopy is an analytical technique used by many of the EU-ARTECH consortium’s
members. For this reason the formation of a working group on the application on the technique
to the examination of cultural heritage was proposed. Objective of the working group is to
initiate discussions on the subject and to share experiences with external experts and users.
The various topics proposed for discussion included:
a-problems of interpretation for the various artefact materials (paintings, metal, paper,
glass, plastic, textiles etc);
b-application of innovative techniques in the field;
c-exchange of knowledge.
The working group is expected to encourage effective sharing of knowledge and good practices
in the field, as well greater awareness of new developments.
During the Perugia meeting, the participating Consortium members introduced their field of
interest through short presentations and identified topics of common interest to be jointly
developed in the future. The meeting began with a short description from a representative of
each EU-ARTECH partner of the type of electron microscopy equipment available in their
laboratory, as well as the range of samples examined and the areas of research they cover with
this analytical technique.
National Gallery, London (A. Roy and M. Spring)
The scientific department at the National Gallery, London has a conventional SEM with an
EDX analyser. It is used for analysis of pigments, as well as imaging of paint surfaces, and
investigation of pigment particle morphology. Work is carried out almost exclusively on
samples from old master paintings ranging in date from the 13 th century to the beginning of the
20 th century. The purpose of the pigment analysis carried out by SEM-EDX is to aid decisions
made during the conservation of paintings, as well as for research into pigment deterioration,
the history of pigments and for cleaning studies.
Instituut Collectie Nederland (I. Joosten)
The research department of the Instituut Collectie Nederlands have a variable pressure SEM
with an EDX analyser. It is used for a wide range of materials, metals, paint cross sections,
glass and ceramics, wood, textiles, plastics, paper and archaeological objects. The work
concentrates on semi- quantitative EDX analysis as well as imaging of the materials. Among
others, recently work has been done on the identification of mordant on textiles, cleaning
studies of painting surfaces, the deterioration of tin foil and the analysis of ink and drying
75

materials on paper. The questions asked are mainly focussed on conservation issues but
sometimes also art technological and archaeometric problems are dealt with. ICN is are now
considering the purchase of a silicon drift detector which does not require liquid nitrogen.
Bayerische Landesamt für Denkmalpflege (M. Mach)
BLFD has a conventional SEM with EDX analyser (of the type which does not require cooling
with liquid nitrogen). It is used for a wide range of materials, among which are metals
(including quantitative analysis) and paint cross-sections. BLFD possesses good standards for
quantitative analysis of metal alloys of various kinds.
Opificio delle Pietre Dure (D. Pinna)
Opificio delle Pietre Dure has a conventional SEM with EDX analyser. It is used for routine
analysis and imaging of samples from metals, stone, terracotta, paper and paint. OPD expressed
particular interest in exchanging experience of SEM examination in these specific fields,
especially in the quantitative analysis of metals and glass.
University of Bologna (S. Prati)
The Microchemistry and Microscopy Art Diagnostic Laboratory at the University of Bologna
does not have an SEM but has access to it in another department of the University of Bologna.
Analysis is carried out by a dedicated SEM technician. They examine mainly paint samples, but
also work on metals. It is used as an accessory technique to the other analytical techniques in
the laboratory.
University of Perugia (F. Presciutti)
As in the University of Bologna the Laboratory at the University of Perugia has access to SEM
with EDX in another department of the University, carrying out the analysis themselves (rather
than the work being done by a technician). They expressed an interest in exchanging experience
of the analysis of paint samples (from both wall paintings and easel paintings), ceramics and
stone. They are using the SEM for Eu-ARTECH Joint Research Activity 1, to investigate the
effect of consolidants on various types of stone.
The meeting continued with a general discussion of possible subjects of interest for the SEM
users group. Among these, were the following:
-Exchange of information on accessories for analysis, such as EBSD (Electron back-scatter
diffraction), micro-Raman, cathode luminescence, silicon drift detector (EDX without liquid
nitrogen cooling).
-Methods for sample preparation. Apart the general aspects, a particular interest is in wood
sample preparation for the identification of wood typology. OPD have experience of this. Also
the use of a focussed ion beam and a cross polisher could be interesting.
-Use of environmental SEM; eg for wood samples, identification of fungi (this is carried out
regularly by OPD). M. Mach expressed an interest in the topic of fungi identification, as this is
something that is regularly requested by restorers.
-Use of SEM for looking at whole objects in large chambers; this does not appear to be a
problem for metal objects, but for other materials such as degraded archaeological glass, SEM
analysis can causes changes such as crizzling resulting from dehydration of the silica gel layer
at the surface of the glass.
-Interpretation of results. Specialists in a certain field could give tips to users who do not
encounter regularly those materials/working conditions, such as low voltage or low vacuum and
aid them in the interpretation of results (both imaging and EDX).
-Quantitative analysis: is it possible and how should it be done preferably?
It was proposed that a SEM users workshop should be held, the aim of which would be to
exchange information and ideas on some of the specific subjects raised at the kick-off meeting.
It was agreed that the workshop should be planned for November 2007, in conjunction with the
76

interim meeting to be held at the National Gallery, London (NGL agreed). Each partner will
present some examples of work carried out in their laboratory, which will illustrate their
particular interests. One or two external speakers may be invited, chosen because they are able
to bring to the workshop information on SEM techniques or sample preparation not possessed
by the Eu-ARTECH partners. The workshop will enable subjects of mutual interest to be
identified, and will allow each partner to illustrate his competence.
77

Annex 8
Report on the working group meeting on the development of the work on
Characterisation of organic materials (binding media, varnishes, pigments) in paint
cross-sections, held in Perugia, November 21 st , 2006.
(DELIVERABLE n. 5)
The location of organic materials within paint layers is often crucial in the interpretation of
analytical results (for example determining whether the material is original or from a later
conservation treatment). However, the bulk sample analysis using chromatographic methods,
conventionally applied to the analysis of organic materials in paint, doesn’t provide this
information. Over the last few years, some research has been published on analytical techniques
that are capable of identifying organic materials directly on paint cross sections. Among these
are microspectrofluorimetry techniques, microchemical staining tests and micro FTIR mapping,
which have been applied to the analysis of binding media and varnishes in paint cross-sections.
Each of these techniques can have specific limitations - for example, fluorescence effects can be
a problem with micro Raman, as can poor spatial resolution and organic content detection limit
with micro FTIR – but developments are being made to attempt to overcome some of these
problems, and other potential methods of analysis that can analyse organic materials in paint
without sacrificing spatial information are also being tested. It was therefore thought that it
would be useful and interesting to examine the state of the art in this field and to investigate
potential new methods of analysis.
At the second annual meeting in Lisbon, Rocco Mazzeo (UniBo) proposed that a workshop
should be organised on the characterisation of organic materials (binding media, varnishes,
pigments) in paint cross-sections. In preparation for this conference, a working group meeting
was held at the interim meeting in Perugia in November 2006. At this meeting the outcome of
the initial investigations into suitable analytical techniques was discussed and presented. From
this a plan could be devised for the planned workshop in September 2007.
A ‘state of the art’ critical survey of the techniques currently being used, carried out by several
of the Eu-ARTECH partners, was presented, including evaluation of their effectiveness,
weaknesses etc. This is summarised in the table at the end of this report, and includes methods
that are already in use in the field, as well as those that are not yet routinely used. Other
analytical techniques which show potential for technology transfer were also included, as well
as new sample preparation methods for existing technology (e.g. surface-enhanced Raman for
organic dyestuffs in cross sections, or methods of treating the samples to improve the results
such as those that are already being tried for SIMS.)
The analytical techniques surveyed include:
- Micro(spectro/imaging) fluorimetry
- Micro FTIR mapping
- FTIR imaging
- Synchrotron FTIR microspectroscopy
- Imaging SIMS
- Staining techniques
- SERS (surface enhanced Raman)
78

For each technique, a summary of its essential features is included in the table, followed by its
advantages and disadvantages. Some relevant literature is also cited.
The meeting then proceeded to discuss the proposed content of the workshop in September
2007, for which the state of the art survey provided a good basis. It was proposed that the
workshop should be held over two days. Rocco Mazzeo informed the participants that a suitable
venue in the University of Bologna had been booked for 21 st and 22 nd September. It was
decided that the major analytical techniques listed above should be covered by the contributions
to the conference, which could be achieved by including five speakers on pre-specified subjects.
It was felt that for certain important techniques such as SIMS and SERS the expertise did not
exist within the Eu-ARTECH consortium and that it would therefore be appropriate to invite
external speakers to cover these subjects. Various names were proposed as possible
contributors. Possibilities for publication of the proceedings of the conference were also
discussed.
79

Summary of literature review on methods for the characterisation of organic materials
Techniques ELISA/IFM (enzyme-linked immunosorbent assay /
immunofluorescence microscopy)
Description Enzyme-linked immunosorbent assay (Elisa) and immunofluorescence
microscopy (IFM) use a immunological approach for the identification
and localization of different protein types in cross-section. The principle
is based on the exclusivity of a complex between a specific protein
extracted from the sample (antigens) and antibody (immunoglobulin
protein). The procedure can be performed by the use of different means
for the visualization of antigen-antibody complex (color reaction,
fluorescence, colloidal gold particles) and different detectors. In an Elisa
assay proteins are extracted from the sample in an aqueous solution.
The primary pre-labeled antibodies (direct method) react with the
protein. The indirect method uses a primary non-antibody and it is
detected by a second labeled antibody. With IFM the detection is
permitted using a fluorescence microscopy and secondary antibodies
that are conjugated to a fluorophore.
Application field Identification and localization of different protein types
Advantages 1. discrimination between different protein types and proteins from
different biological species.
2. extremely aged proteins can be detected
3. high sensitivity of Elisa (detection limit below one nanogram)
4. IFM can be used with conventional cross-sections and allows
the possibility of spatially resolving target proteins
5. reversibility of the reaction
6. possibility of detecting and locating different proteins
simultaneously in the same sample
Disadvantages 1. Elisa doesn’t permit the localization of proteins
2. lower sensitivity of IFM
3. difficulties in visualizing results in particular conditions (e.g.
when the color of fluorophore and natural fluorescence of the
target layer are similar)
4. non-specific absorption of antibodies by the porous sampl
5. possible dissolution of water soluble materials from the sample
during incubation in an aqueous solution
• Heginbotham, V. Millay and M. Quick, The use of immunofluorescence microscopy (IFM) and Enzymelinked
immunosorbent assay (Elisa) as complementary techniques for proteins identification in artists’
materials, WAG postprints, Portland-Oregon, 2004.
• Ramirez-Barat and S. de la Vina, Characterization of proteins in paint media by immunofluorescence. A
note on methodological aspects, Studies in Conservation 46, 2001
• L. Kockaert, P. Gausset and M. Dubi-Rucquoy, Detection of ovalbumin in paint media by
immunofluorescence, Studies in Conservation 34, 1989
80

Techniques Microspectrofluorimetry
Description The techniques of UV-VIS microspectrofluorimetry combine the potential of
spectrometry and information on stratigraphical distribution of paint layers
obtained with microscopy. The principle is based on the possibility of inducing a
fluorescent response in materials when they are irradiated with the correct
wavelengths (ultraviolet light). The procedure allows the collection of spectra for
the characterization of binding materials and varnish through the comparison
with standard references and the examination of the position of specific peak
value. A fluorescence emission spectrum is obtained for each of the layers in the
sample, which are identified with the microscope. The limit of the area selected
for the analysis depends on the microscope’s resolution.
Application field Identification of different organic materials (binders and varnish) and
fluorescent pigments.
Advantages 1. can be used with conventional embedding and polishing procedures for
the cross-section
2. possibility of combining the sensitivity of fluorescence measurement with
the spatial resolution of microscopy
3. non destructive techniques
4. can distinguish different binders used in a mixture
5. it allows stratigraphical analysis obtaining information on the distribution
within the layers
6. spectrometric analysis is possible even in focused areas of very small
linear dimension (as little as 1µm)
Disadvantages 1. longer recording time of spectra may produce photo-chemical effects
and distortions in their shape
2. non homogeneity of the sample can induce shift in the spectra
3. the position of the peaks are referable always to measurement obtained
with the same equipment
4. pigments can change the plot of the spectrum through absorption effects
and their natural fluorescence
5. fluorescent pigments can produce shoulders in the spectrum
6. non homogeneity of the sample can induce shifts in the spectra
• G. Bottiroli, A. Gallone, B. Masala, Microspectrofluorometric analysis of organic binders, Bollettino d’Arte,
Ministero per i Beni e le Attività Culturali, 2005
• G. Bottiroli, B. Masala, e A. Gallone, Contributo delle tecniche microspettro fluorimetriche allo studio ad
alla conservazione dei Beni Culturali, Istituto Lombardo di Scienze e Lettere, 2001
• G. Bottiroli, e A. Gallone, Studio stratigrafico della pellicolo pittorica: caratterizzazione di pigmenti e
leganti, in L’affresco di Sant’Agata al Monte di Pavia. Ricerche ed analisi per il restauro, Memorie
dell’istituto Lombardo di Scienze e Lettere, 1996
• G. Bottiroli, A. Gallone, E. Bernacchi, Micospectrofluorimetric techniques as applied to the analysis of
binding media and varnish in color samples taken from paintings, in Scientific methodologies applied to
works of art, proceeding of the symposium, Florence 1984
81

Techniques micro-Raman spectroscopy
Description Raman spectroscopy is a technique used in studies of vibrational, rotational, and
other low-frequency modes in a system. It depends on the inelastic scattering of
the laser beam (from the visible, near infrared, or near ultraviolet range) by the
irradiated sample. The Raman signal is detected by a CCD detector. With micro-
Raman it is possible to focus the laser on grains of binding media, using
different objectives allowing a spatial resolution down to 1μm. Fluorescence
background is minimized by the use of a near-infrared laser. This technique has
been used for the identification of inorganic materials and it has been introduced
also for the analysis of organic pigments.
Application field Identification of different organic and inorganic materials
Advantages 1. can be used with conventional embedding and polishing procedures for
the cross-section
2. Non destructive technique
3. High spatial resolution
4. discrimination between different binding materials used as mixture
5. possibility of identifying characteristic peaks related to aging and
degradation effects
6. protective action of the binder on the pigments, that can be analyzed
with higher intensity of excitation
Disadvantages 1. Interference caused by the fluorescence background
2. laser energy can produce degradation effects on the sample
3. low quantum efficiency of CCD
• P. Vandenabeele, B. Wehling, L. Moens , H. Edwards, M. De Reu, G. Van Hooydonk, Analysis with micro-
Raman spectroscopy of natural organic binding media and varnish used in art, Analytica Chimica Acta 40,
2000
• G.Buffarato, M. Calabrese, A. Cosentino, A. M. Gueli and S. O. Troja, A. Zuccarello, ColoRaman project:
Raman and fluorescence spectroscopy of oil, tempera and fresco painting, Journal of Raman
spectroscopy 35, 2004
• Ohlidalova M., Kucerova I., Novotna M., Identification of acrylic consolidants in wood by Raman
spectroscopy, Journal of Raman Sepctroscopy, 2006, 37, pp. 1179-85.
82

Techniques micro-Raman Spectroscopy: SERS (Surface-Enhanced Raman
Spectroscopy)
Description Many of the natural dyestuffs found in lake pigments are extremely fluorescent
at the excitation wavelengths used for conventional Raman spectroscopy. SERS
is a micro-Raman technique that has proved to have the potential to overcome
this problem. Deposition of a rough metal surface (support), usually silver,
enhances the Raman emission and quenches the fluorescence. The SERS
support can be deposited onto the surface of the sample by various means; Ag
colloids obtained by reduction with sodium citrate, silver films applied by
chemical deposition and silver nanoisland films by vacuum evaporation have all
been tried.
Application field Identification of organic pigments and dyes
Advantages 1. Direct information on dyestuff components
2. High spatial resolution
3. High sensitivity
4. Can be carried out directly on the cross section
5. Non destructive
Disadvantages 1. So far demonstrated successfully only on dyestuff standards, dyes on textiles
or modern lake pigments
2. Solution-reduced Ag colloids used as a support, but adsorption of natural
dyes to this is variable
3. Hydrolysis of pigment needed to allow adsorption of the dye onto the support
• Guineau B. and Guichard V., Identification des colorants organiques naturels par microspectrophotmetrie
raman de resonance et par effect Raman exalte de surface (SERS), ICOM Committee for Conservation:
8th Tirennial meeting, Preprints, Vol. 2, Getty Conservation Istutute, California 1987, p. 659
• Leona M., Stenger J., and Ferloni E., Application of surface-enhanced Raman scattering techniques to
the ultrasensitive identification of natural dyes in works of art, Journal of Raman Sepctroscopy, 37, 2006,
pp. 981-92.
• Whitney A.V., Van Duyne R.P., Casadio F., An Innovative surface-enhanced Raman spectroscopy
(SERS) method ofr the identification of six historical red lakes and dyestuffs’, Journal of Raman
Sepctroscopy, 2006, 37, pp.993-1002.
• M.V. Canamares, J.V. Garcia-Ramos, C. Domingo and S. Sanches Cortes, ‘Surface-enhanced Raman
Scattering study of the anthraquinone red pigment carminic acid’, Vibrational spectroscopy, 40, 2006, pp
161-7.
83

Techniques FTIR microspectroscopy: ATR / ATR mapping
Description ATR mapping - FTIR microspectroscopy performs molecular vibrational
spectroscopy (4000-650 cm -1 ) in reflectance mode. An infrared transparent
crystal is brought into close contact with the sample’s surface and a spectrum is
collected at the interface. Most organic and inorganic substances can be
detected. The x-y-z motorized stage with incremental steps of 1 um permits the
collection of a large number of FTIR spectra on a surface and a distribution map
of the identified compounds to be produced.
Application field Identification of different organic and inorganic materials
Advantages 1. can be used with conventional embedding and polishing procedures for
the cross-section
2. High quality spectra similar to transmittance spectra. Good S/N
3. Mapping results as false-color plots with the localization of the different
mixed compounds
4. non destructive technique
5. adjustable aperture to select the investigated area
6. reasonable time of analysis (1 to 3 hours)
Disadvantages 1. strong contribution of embedding resin
2. Opacity of silicon crystal
3. Detector limit 650 cm -1
4. Contact with surface important and can be problematic. Sample
preparation critical
• E. Joseph, Young chemists' workshop on chemistry for the conservation of cultural heritage: present and
future perspectives, CERC3, Perugia, I - March 20th-22nd 2006 (unpublished).
• R. Mazzeo, E. Joseph, The use of FTIR micro-ATR spectroscopy and FTIR mapping for the surface of
bronze corrosion products, 8 th International conference on “Non destructive investigation and
microanalysis for the diagnostic and conservation of the cultural and environmental heritage”, Lecce, 2005
84

Techniques FTIR microspectroscopy: FTIR imaging
Description The main difference between ATR-mapping and FT-IR imaging is the use of
different acquisition modes. FTIR reflection imaging provides the spatially
resolved acquisition of infrared spectra with a resolution of about 7μm. The
technique is able to obtain information on the organic functional group
distribution. The Kramers-Kronig transformation algorithm provides to transform
the specular reflectance to absorbance spectra.
Application field Identification of different organic and inorganic materials
Advantages 1. high spatial resolution related to the pixel dimension of about 6, 7μm
2. fast data collection
3. non destructive technique
Disadvantages 1. difficult to obtain a good S/N ratio
2. low reflectance of IR radiation
3. need to have a very reflective surface
• J. Van der Weerd, H. Brammer, J.J. Boon and R. M. A. Heeren, Fourier transform infrared microscopic
imaging of an embedding paint cross-section, Applied spectroscopy 53, 2002
• A. van Loon, K. Keune and J.J. Boon, Impruving the surface quality of paint cross-section for imaging
analytical studies with specular reflection FTIR and static-SIMS, 8th International conference on “Non
destructive investigation and microanalysis for the diagnostic and conservation of the cultural and
environmental heritage”, Lecce, 2005
• A. van Loon and J.J. Boon, ‘Identifying and localising proteinaceous compounds in paint samples using
reflection infrared spectroscopic techniques’, Proceedings of the Sixth Infrared and Raman Users group
conference (IRUG 6, March 2004), M. Picollo ed, 2005, pp.130-136.
85

Techniques FTIR microspectroscopy: Synchrotron-FTIR
Description Synchrotron radiation Fourier transform infrared spectroscopy gives molecule
specific information. The instrument is equipped with a spectrometer system,
which consists of a standard Fourier transform infrared spectrometer followed by
a confocal microscope system and a synchrotron radiation source. SR-FTIR
gives spectra in transmission or reflection mode.
Application field Identification of different organic and inorganic materials
Advantages 1. can be used with conventional embedding and polishing procedures for
the cross-section
2. non destructive technique
3. smaller spot size analyzed
4. high intensity of light source and collimators allow a good S/N ratio
Disadvantages 1. low reflectance of IR radiation
2. difficult interpretation of data where the signal to noise ratio is too low
3. the quality of the spectrum in reflection mode is lower than in
transmission
4. high number of scans required with long acquisition time
5. Only available at synchrotron facility – ie no direct fast access
• N. Salvadò, S. Butì, M.J. Tobin, E. Pantos, A.J. Prag and T. Pradell, Advantages of the use of SR-FTIR
microspectroscopy: application to cultural heritage, Analytical chemistry 77, 2005
• I. De Ryck, A. Adriaens, E. Pantons and F. Adams, A comparison of microbeam techniques for the
analysis of corroded ancient bronze objects, Analyst 128, 2003
• M. Cotte, P. Dumas and P. Walter, ‘Analysis of Ancient Biological and Cosmetic material using
Synchrotron Infrared Microspectroscopy’, Proceedings of the Sixth Infrared and Raman Users group
conference (IRUG 6, March 2004), M. Picollo ed, 2005, pp.75-82.
86

Techniques Imaging SIMS (secondary ion mass spectrometry)
Description A high energy primary ion beam generates secondary ions from the surface of
the sample which are then analysed by mass spectrometry. Information on
inorganic materials is obtained (including trace elements), as well as molecular
information on organic components such as the binding medium or products of
pigment-medium interaction. Scanning of the focused ion beam produces an
entire mass spectrum for each pixel in the image. A map or image can be
generated by selecting a mass of interest, which then gives information on the
spatial location of the components in the paint cross-section. This is a surface
sensitive technique probing only the uppermost atomic layers.
Application field Identification of different organic and inorganic materials
Advantages 1. Spatially resolved information on inorganic and organic components in a
single measurement
2. High spatial resolution of 1 micron
3. Detailed molecular information
4. Non-destructive – the sample can still be analysed by other techniques
afterwards.
Disadvantages 1. Variable ionisation efficiency – good for some materials, poor for others.
Detection limits depend on the components and their environment in the
sample.
2. Matrix effects
3. Low organic yields. Can be dominated by inorganic components of the paint,
so that in practice in some cases the binding medium cannot be detected.
4. Sample preparation is critical
• K. Keune and J.J. Boon, ‘Imaging secondary ion mass spectrometry of a paint cross section taken from an
early Netherlandish painting by Rogier van der Weyden’, Analytical Chemistry, 76, 2004, pp.1374-85.
• K. Keune, ‘Binding Medium, pigments and metal soaps characterised and localised in paint cross
sections’, Molart Report, PhD thesis, Archetype publications 2005.
• K. Keune, E. Ferreira and J.J. Boon, ‘Characterisation and localisation of the oil binding medium in paint
cross setions using imaging secondary ion mass spectrometry, Preprints of the 14th Triennial Meeting of
ICOM-CC, The Hague 2005.
• A. van Loon, K. Keune and J.J. Boon, Improving the surface quality of paint cross sections for imaging
analytical studieswith specular reflection FTIR and static-SIMS, Conference Proceedings, Art 2005, Lecce
May 2005.
• K. Keune and J.J. Boon, ‘Enhancement of the static SIMS secondary ion yields of lipid moieties by
ultrathin gold coating of aged oil paint surfaces’, Surface and interface
analysis, 2004, vol. 36, n o 13, pp. 1620-1628
87

Techniques LD-MS (laser desorption mass spectrometry)
Description A focused laser beam is used to ionise/volatilise the sample material, and the
ions produced in the ionisation chamber are then analysed by Mass
Spectrometry. The characteristic fragments detected allow detailed molecular
information about the sample to be obtained. In this technique a UV laser is
used, and can be directed at different areas of a sample. The technique has
been used experimentally (and successfully) for the characterisation of modern
organic pigments, as well as indigo and the dyestuffs for certain lake pigments.
However, it has certain limitations; it cannot distinguish between dyestuff
components as effectively as HPLC and detects only the major components.
Application field Identification of organic pigments
Advantages 1. Detailed molecular information
2. Non destructive
3. Has shown potential as a useful tool for analysis of flavonoid and
anthraquinone pigments, as well as indigo
4. Can be carried out directly on the cross section, thereby preserving spatial
information
Disadvantages 1. Poor spatial resolution (spot size < 40 micron)
2. Yield dependent on ionisation efficiency, which is highly dependent on the
environment, therefore results are variable
3. Has limitations when used on cross sections
4. Sensitive to surface texture and morphology therefore preparation very
important
• N. Wyplosz, ‘Laser Desorption Mass Spectrometric Studies of Artists Organic pigments’, Molart Report,
PhD thesis, Archetype publications 2003.
• N. Wyplosz, R.M.A. Heeren, G. van Rooij, J.J. Boon, Analysis of Natural Organic Pigments by Laser
Desorption Mass spectrometry: A preliminary study to Spatially resolved Mass Spectrometry, Dyes in
History and Archaeology 16/17, 2002, 187-98.
• Boon, Jaap J. and Learner, Tom. Analytical mass spectrometry of artists' acrylic emulsion paints by
direct temperature resolved mass spectrometry and laser desorption ionisation mass spectrometry,
Journal of analytical and applied pyrolysis 64, (2002), pp. 327-344.
88

Techniques Laser– Pyrolysis/GC-MS
Description The Py.GC-MS instrument comprises a gas-chromatograph interfaced to a
mass selective detector and to a Olympus BX60M microscope with laser
chamber. The laser beam was directed at different spots within paint layers. The
instruments are able to select different spot areas in a sample and obtain
information on the different molecular compositions of pyrolysis products. The
laser employed for the heat decomposition was the Laser Applications 50W
continuous wave Nd-YAG infrared laser at 1064 nm. The possibility of
employing a different system such as LZH CO2 laser micropyrolysis can help to
select a smaller spot size. The use of a beam splitter window allows better
control of the spot size. For the outermost layer the use of a CO2 laser is able to
pyrolyse a small part of the layer by approaching ablation from the resin. The
signal from the resin can be then subtracted as background.
Application field Analysis of organic substances
Advantages 1. It can be used with conventional embedding and polishing procedures
for the cross-section
Disadvantages 1. the sample is ablated, making it impossible to repeat and confirm the
analysis
2. strong contribution of embedding resin
3. difficult control of the laser shot size
Until now, no publications in this field
89

Techniques MALDI Tof-MS (matrix assisted laser desorption and ionisation
mass spectrometry)
Description The high energies used in LD-MS can in some cases result in too much
fragmentation of the organic components so that they are no longer
characteristic enough to be useful for identification, or the ionisation yield may
be poor. In MALDI a matrix consisting of a strong chromophore is used, which
controls the energy deposited in the sample by absorption of sufficient laser
radiation to reduce fragmentation. The result is that the fragments then detected
after ionisation by mass spectrometry are mainly pseudo molecular ions, which
are more useful for characterisation of the material.
Application field Identification of organic pigments and binding media
Advantages 1. Detailed molecular information giving the potential for good characterisation
of organic pigments and medium
2. Non destructive since only the very surface of the sample removed
3. Can be carried out directly on the cross section, preserving spatial information
about the material analysed
Disadvantages 1. Matrix needed
2. Surface treatment necessary due to polymerisation
3. Spatial resolution relatively low at 20 micron
4. Ionisation variable, depending on the environment
• N. Wyplosz, ‘Laser Desorption Mass Spectrometric Studies of Artists Organic pigments’, Molart Report,
PhD thesis, Archetype publications 2003.
• O. F. van den Brink, Boon, J. J., O'Connor, P. B., Duursma, M. C., and Heeren, R. M. A, MALDI-FTMS
analysis of oxygenated triglycerides and phosphatidylcholines in egg tempera paint dosimeters used for
environmental monitoring of museum display conditions. Journal of Mass Spectrometry
• O.F. van den Brink, P.B. O'Connor, M. Duursma, R.M.A. Heeren, S. Peulvé and J.J. Boon, Analysis of
oxygenated egg lipids in tempera paint by MALDI FT-ICR-MS(MS).(Poster C05 TUPO076) Advances in
Mass Spectrometry, Vol. 14, E.J. Karjalainen, A.E. Hesso, J.E. Jalonen and U.P. Karjalainen eds
(Proceedings of the International Mass Spectrometry Conference, Tampere, Finland, 1997, available on
CD-ROM only.)
• Digney-Peer, Shawn; Burnstock, Aviva; Learner, Tom; Khanjian, Herant; Hoogland, Frank; and Boon,
Jaap J., The migration of surfactants in acrylic emulsion paint films, in Modern art, new museums:
contributions to the Bilbao Congress, 13-17 September 2004, Roy, A and Smith, P eds., International
Institute for Conservation of Historic and Artistic Works (2004), pp. 202-207.
• Ku ková, Štépánka; Hradilová, Janka; Grygar, Tomáš; Bezdi ka, Petr; and Hradil, David, Moderní postupy
v mikroanalýze organických pojiv (Recent methods in organic binder microanalysis.), Sborník z konference
konzervátor¡ a restaurátor¡ (2005), pp. 25-29.
90