ree's to distinguish source origin of main white marble in the mediterranean basin
TRANSCRIPT
fL-A Ilt -bull c 1
PROCEEDINGS
41h International Congress oo
uscience and Technology for the Safeguard ofCultural Heritage in the
Mediterranean Basin
VOL II
Cairo Egypt 61h gth Oecember 2009
l
t
PROCEEDINGS
4th Intemational Congress on
Science and Technology for the Safeguard of Cultural Heritage in the
Mediterranean Basin
Cairo Egypt
6th- gth December 2009
VOL II
Session B
Editor Angelo Ferrari
Finito di stampare prima edizione giugno 20 l O dalla laquoGrafica Elettronicaraquo srl Napoli te +390815595114 middotfax +390815597681 infoautorineditiit middot wwwautorineditiit
Publishing coordinati an and realization Angelo Ferrari - CNR Inst of Chemical Methodologies Italy
Digitai Editing and Data Processing Stefano Tardiola Secretariat Enza Sirugo - CNR Inst of Chemical Methodologies Italy Elvira Possagno Manuela Manfredi AIC Secretariat Italy
Session B2 - Evaluation of damage restoration and conservati an ojmonuments buildings and historical gardens
REES TO DISTINGUISH SOURCE ORIGIN OF MAIN WHITE MARBLE IN THE MEDITERRANEAN BASIN
ODDONE MASSIMO National Research Council (CNR) Institute for Energetics and Interphases (IENI) Department ofPavia Generai Chemistry
Department University ofPavia viale T Taramelli 12 27100 Pavia (Italy) Fax -39-382- 528544 -mai oddonealunipvit
Abstract Many investigations ha ve been reported in the literature on the provenance of a number of stone materials used to manufacture artifacts of archaeological or historical interest with special reference to marble Some of these investigations dea with geologica (ie geochemical mineropetrographic) parameters or have a physical approach (Cathodoluminescence ESR-EPR spectrometry etc) In other cases a chemical approach is followed involving the determination of the elemental composition with different techniques X-ray fluorescence Spectrophotometry Plasma Spectrometry Atomic Absorption Spectrometry or Neutron Activation Analysis (NAA) as in the present case Attention was then addressed to the rare-earth elements (REEs) which usually are useful in a number of geochemical studies such as those conceming the formation evolution and classification ofa number ofrocks and soils as well as in archaeometric studies REEs were determined by neutron activation analysis in the 250 Kw Triga Mark II reactor of the University of Pavia and radiochemical separations based on the precipitation and purification ofREEs fluorides For ali samples showing a light REE (La-Eu) enrichment compared to the heavy ones (Gd-Lu) ali of them show also the soshycalled Eu negative anomaly The intensity ofthis anomaly is evaluated in terms ofdepth expressed as the ratio EuEu ofthe normalized Eu content to the one Eu obtained as the geometrica mean of the normalized content of the adjacent elements Sm and Gd Discriminant power of REEs to distinguish the source origin of white marble in the Mediterranean basin had been evidentiated The results are presented discussed and compared
Keywords White marbles Neutron Activation Analysis Rare Earth Element Provenance
l Introduction Many papers have been devoted to the characterization of marbles in generai (in particular white marbles) from important ancient quarries using mainly petrographic and geochemical parameters 1 15 but a Iso other techniques including cathodoluminescence16bull17 electron spin resonance (ESR) 18 and light diffusion 19 The same parameters have been applied to the provenancing of archaeological marbles0 Marbles were derived from the metamorphic recrystallisation of carbonate-dominant protoliths (mainly limestones magnesian or dolomitic limestones) containing also minor silicate minerals as accessory The accessory minerals have recently been shown21 to be important in the discrimination of Mediterranean marble quarries and so they may a iso be used in the provenancing ofarchaeological marbles alone or in combination with the routinely applied parameters From a compositional point or view the distribution ofthe rare earth elements (REE) was found to be significant 2223
In order to verify these hypotheses attention has been addressed to rare-earth elements (REE) Usually in geochemical studies REE are useful to elucidate rock forming processes and to classify rocks and soils of different origin As it is well known carbonate rocks have a poorer REE content than silicate rocks 24 Radiochemical Neutron Activation Analysis (RNAA) is at the moment the most used analytical technique for the determination poor REE abundance in geologica samples on account of its high sensitivity ofthe possibility of determining all the elements and ofthe undisputed accuracy and reliability ofits results 25
2 Experimental
21 Analysed materials The investigated middotmarble samples were ali relative to quarry materials sampling by Manna et al26 Italian marble from Carrara Greek marbles from Hymettus Naxos Paros Penteli and Thasos and Turkish marbles from Afyon Aphrodisias Denizli Marmara and U~ak (Fig 1) Their choice has been made as for marble specimens in relation to the common varieties employed in monuments and considering mostly the facies of larger diffusion in the quarrying districts and with common contents of accessory minerals (silicates sulphides oxides etc) were here considered for investigation of REE Marble samples (10-20 g) were ground (l 00 mesh) and homogeneised Randomly collected subsamples in the range 01-1 g were then submitted to homogeneity tests according to Jaffrezic27 The variance analysis taken as an evaluation of the sample variability due to sampling provides evidence that aliquots of 400 mg or greater are homogeneous and representative of the investigated marble sample Usually 05 g of marble sample were inserted into polyethylene vials for irradiation
424
Sessi an B2 - Evauation of damage restoration and conservation of monuments buildings and historical gardens
Fig 1- Map ofthe marble quarries
Table l- REEs Nuclear data Statue LREET (jgg) LREEL (lgg) LREEH (jgg) L RE EL l EuEu
L RE EH C1 60plusmn007 535plusmn009 063plusmn002 85plusmn04 076plusmn003
C2 59plusmn03 53plusmn03 064plusmn004 82plusmn01 066plusmn008
22 Reference standards A synthetic reference standard was prepared by adding known amounts of the REE to pure CaC03bull In addition NIST SRM1633a Coal Fly Ash 2 was used in marble analysis
23 Irradiations and cooling Marble samples and reference standards were irradiated in the 250 Kw TRIGA MARK II reactor of the University ofPavia at a thermal neutron flux of about lxl0 12 n cm-2smiddot Irradiation time was 20 hours a second irradiation of 15 minutes was carried out at a thermal flux ofabout 2xl0 12 n cm-2s1 after the radiochemical separation step for the determination of short-lived radionuclides and the evaluation ofthe chemical yield After the flrst irradiation samples and reference standard were left to decay for 3 days before being processed after the second irradiation samples were left to decay for l hour before being submitted to y-spectrometry
24 Radioactivity measurement Induced radioactivity was measured by y-ray spectrometry using a HP-Ge detector coupled to a computer assisted OR TEC spectral analysis system The y-rays utilized in this work are reported in Table l
25 Radiochemical procedure After the decay period the irradiated samples were transferred to a beaker and known amounts (lO mg) of Se and REE (except La Nd Pr Dy and Er) added as carriers The mixture was then submitted to an acid attack with 4M CH3COOH solution The precipitation of REE-fluorides was carried out by adding a mixture of 50 HF and 10 NH4F solutions together with La+3 carrier solution The fluorides were separated dissolved with a HN03 solution and borie acid saturated solution and again precipitated as described above without La+3 carrier addition The
425
Session B2 - Evaluation of darnage restoration and conservation ojrnonurnents buildings and historical gardens
fluorides were then dissolved as described and brought to a 1 O cm3 volume a 9 cm3 aliquot was used for radioactivity measurement and the remaining 1 cm3 was re-irradiated together with REE reference standard for the determination of N d Pr Dy Er and the evaluation of the chemical yield The latter resulted to be throughout the present investigation equa to 98plusmn225
Table 2- Average and standard deviation REE content (pg1) ofthe investigated samplesfrom different quarries ltalian Greek Turkish
Element
Carrara (80) Hymetto(10) Naxos (10) Paros (25) Pentelico (30) Thassos (10) Afyon(10) Aphrodisias (25) Denizli (20) Maramara (30) U~ak (10)
La 089plusmn008 132plusmn007 209plusmn005 154plusmn008 149plusmn007 1239plusmn0002 0701plusmn0002 244plusmn005 147plusmn009 169plusmn009 0140plusmn0009
Ce 106plusmn004 170plusmn005 414plusmn009 246plusmn006 1413plusmn0006 2033plusmn0001 108plusmn004 299plusmn003 167plusmn009 205plusmn007 0214plusmn0005
Pr 016plusmn006 051plusmn003 0376plusmn0007 026plusmn001 0222plusmn0007 0222plusmn0002 0111plusmn0004 087plusmn002 0381 plusmn0009 0425plusmn0007 0018plusmn0006
N d 056plusmn007 0334plusmn0008 110plusmn007 0956plusmn0007 106plusmn008 0992plusmn0001 0563plusmn0005 289plusmn006 0964plusmn0006 197plusmn004 0086plusmn0001
Sm 0171plusmn0008 0271plusmn0004 0096plusmn0003 0170plusmn0006 017plusmn003 0278plusmn0001 0157plusmn0003 0265plusmn0007 0178plusmn0005 0211plusmn0006 0184plusmn0002
Eu 0026plusmn0005 0041plusmn0005 0025plusmn0002 0052plusmn0003 0047plusmn0003 0043plusmn0003 0049plusmn0001 0071plusmn0004 0038plusmn0009 0487plusmn0004 0031plusmn0005
Gd 0163plusmn0003 0266plusmn0002 0146plusmn0005 0145plusmn0005 0150plusmn0005 0345plusmn0003 020plusmn001 0261plusmn0005 0161plusmn0003 0195plusmn0009 0240plusmn0005
Tb 0030plusmn0008 0043plusmn0003 0030plusmn0003 0026plusmn0002 0021plusmn0002 0042plusmn0008 0030plusmn0004 0052plusmn0003 0025plusmn0004 0035plusmn0004 0038plusmn0001
Dy 0169plusmn0009 0294plusmn0004 0199plusmn0009 0119plusmn0004 021 0plusmn0003 0250plusmn0005 0179plusmn0009 0324plusmn0003 0141plusmn0005 0217plusmn0014 0229plusmn0002
Ho 0045plusmn0005 0052plusmn0001 0030plusmn0003 0033plusmn0002 0033plusmn0004 0063plusmn0001 0039plusmn0006 0247plusmn0004 0035plusmn0003 0035plusmn0003 0049plusmn0001
Er 0117plusmn0004 0145plusmn0003 0079plusmn0011 0110plusmn0007 01 00plusmn0005 0156plusmn0002 0095plusmn0001 0202plusmn0007 0069plusmn0004 0087plusmn0005 0121plusmn0002
T m 0021plusmn0008 0022plusmn0001 0014plusmn0002 0017plusmn0002 0018plusmn0004 0025plusmn0001 0015plusmn0003 0024plusmn0001 0012plusmn0004 0009plusmn0002 0019plusmn0008
Yb 0115plusmn0041 0133plusmn0004 0072plusmn0008 0064plusmn0004 0073plusmn0006 0164plusmn0002 0097plusmn0001 027plusmn004 0053plusmn0005 0035plusmn0005 0122plusmn0007
Lu 0017plusmn0005 0021plusmn0001 0011 plusmn0001 0014plusmn0002 0021plusmn0004 0025plusmn0002 0015plusmn0002 001 0plusmn0001 0008plusmn0001 0004plusmn0001 0017plusmn0004
Table 3- REE abundances Lgg) ofthe investigated NIS T SRMJ633 C l Fl A h a o a ty s
NBS SRM 1633a This work Found
Element Rif 28 Rif 29 La 82plusmn02 791plusmn01 Ce 1755plusmn04 180 1683plusmn16 Pr 201plusmn09 - -N d 767plusmn03 - 757plusmn20 Sm 176plusmn02 - 1683plusmn020 Eu 367plusmn004 4 358plusmn007 Gd 169plusmn03 - -Tb 240plusmn004 - 238plusmn007 Dy 156plusmn06 - -Ho 381plusmn004 - -Er 83plusmn04 - -T m 123plusmn004 -Yb 768plusmn005 - 750+013 Lu 1190plusmn0006 - 1075plusmn0013
Table 4- Some useful parameters based on REEfor the different w h bl h u d b zte mar e quarnes in t e e iterranean asin
Quarries LREEr (1-gg) LREEL (1-gg) LREEH (1-gg) ~REE l ~REEH EuEu
Carrara 352plusmn009 283plusmn008 073+001 401plusmn009 030plusmn004 Hymetto 51+03 41plusmn02 102+001 40plusmn02 037plusmn006 Naxos 84 + 04 78 plusmn 04 060 plusmn 002 131 + 04 045plusmn008 Paros 60 plusmn 02 54 plusmn 02 064 + 002 84 plusmn 02 046plusmn005 Pentelico 51 + 04 44 + 04 068 + 001 65 plusmn 04 UogravetgtplusmnUU~
Thassos 588 plusmn 001 4764 + 0005 1113 plusmn 0008 428 + 003 032plusmn004 Afyon 333 plusmn 007 261 + 005 072 + 002 235 plusmn 009 055+007 Aphrodisias 106 + 06 95 + 02 110plusmn003 859 + 004 066plusmn005 Denizli 52 + 01 47+01 055 plusmn 001 92 + 01 044plusmn003 Marmara 75 + 02 63 + 03 11 plusmn 01 56 + 02 512plusmn009 U~ak 150 plusmn 007 064 plusmn 004 087 plusmn 004 074 + 009 032plusmn004
3 Results and discussion
REE contents of the investigated marbles are reported in Table 2 Samples have been grouped according to the quarry and reported values are the averages and the standard deviations often or more independent determinations for all samples ofthe same site Analytical precision is usually below 8 An evaluation ofthe accuracy ofthe method can be obtained by looking at the data on NIST Standard Reference Materia 1633a Coal Fly Ash reported in Table 3 and comparing them with existing values in the literature2829
The data being the average of20 independent runs agree very well and validate the reliability ofthe method More information is obtained if some parameters based on REE concentration for all samples are considered the sum ofmeasured REE concentrations (IREEr) the sum ofthe concentrations oflight REE (IREEL) the sum ofthe concentrations of heavy REE (IHREEH) the ratio of REEL to REEH All samples showing a light REE (La-Eu) enrichment compared to the heavy ones (Gd-Lu)
426
Sessi an 82 - Evaluation of damage restoration and conservati an of monuments buildings and historical garden s
Discriminant power of REEs to distinguish the source origin of white marble in the Mediterranean basin had been evidentiated to compute Hotellings (T2 test) for matched group designs using the RELIABILITY routine of SPSS30
Differences in the values of LREEr a statistica meaningful differences were obtained in 95 confidence leve of cases in the values of L REE L a statistica meaningful differences were obtained in 93 l confidence leve of cases the values of REEH a statistica meaningful differences were obtained in 89 confidence leve of cases and the values of LREEdLREEH a statistica meaningful differences w ere obtained in 90 confidence leve of cases Ali of them show also the so-called Eu negative anomaly the intensity of this anomaly is evaluated in terms of depth expressed as the ratio EuEu of the normalized Eu content to the one Eu obtained as the geometrica mean of the normalized content of the adjacent elements Sm and Gd as shown in Table 4 Not is a good discriminate parameter for quarries because depend the redox conditions This result therefore aimed to apply experience in marble provenancing by RNAA acquired to study the marble provenance of veiled Aphrodite statue of the Palazzo Ducale in Mantua (Italy) one of the few pieces not sold to Charles I of England (1627-1628) and one of the few to escape the dispersion following the sack of the Lanzichenecchi in 1630 and 1631 31
The samples were provided inthe form of small fragments from two areas of a sculpture (C1 and C2) and about 800 mg of powdered marble was obtained from them usually by drilling using a standard 5 mm masonry (tungsten carbide) bit The initial drillings were discarded to avoid materia that may have been modified by weathering processes Marble samples were ground (SI 00 mesh) and homogeneised and 05 g w ere submitted to RNAA REE content are given in table 5 A close examination of the REE data allows the identification of some parameters that can be used t o discriminate the white marble quarries ofthe Mediterranean basin (Table 6) The values ofthis quantity for the marble samples from the veiled Aphrodite are very similar to the one ofthe Paros quarrying
Table 5- Average and standard deviation REE conteni (pglg) ofthe veiled Aphrodite
ttemem 1(1 IC2
La 147plusmn009 146plusmn006 Ce 25plusmn01 24plusmn01 Pr 026plusmn001 027plusmn001 N d 095plusmn001 096plusmn002 Sm 017plusmn001 017plusmn002 Eu 0056plusmn0006 0061plusmn0002 Gd 015plusmn001 015plusmn001 Tb 0025plusmn0002 0025plusmn0001 Dy 019plusmn001 019plusmn001 Ho 0033plusmn0002 0033plusmn0002 Er 0098plusmn0003 0099plusmn0003 T m 0016plusmn0002 0016plusmn0002 Yb 0063plusmn0002 0065plusmn0004 Lu 0013plusmn0002 0014plusmn0001
Table 6-Statue EuEu
C1 076plusmn003 C2 066plusmn008
4 Conclusions
The routine neutron activation analysis of marble standard samples within a given irradiation batch has demonstrated the stability of the counting system and the reproducibility of the neutron activation technique The severa batch es of samples were analysed over the course of about 25 years The replicate analysis of the quarries samples some ten years apart also confirms the reproducibility of the technique In conclusion some basic provenancing procedures by the evaluation ofthe distribution ofthe REE especially may be confidently used
427
Session B2 - Evaluation of damage restoration and conservation ofmonuments buildings and historical gardens
5 References l Manfra L Masi U Turi B (1975) Archaeometry 17215-221 2 Herz N Dean NE (1986) Applied Geochemistry l 139-151 3 Herz N(l987) Archaeometry 2935-43 4 HerzN(l992)Archaeometry 34185-194 5 Dean NE (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 315-323 p 6 Germann K Gruben G Knoll H Valis V Winkler FJ (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 251-262 p 7 Lazzarini L Mariottini M Pecorara M Pensabene P (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 399-410 p
8 Lazzarini L Masi U Tucci P (1995) in The Study of Marble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd Londonl61-169 p
9 Moens L Roos P De Rudder J De Paepe P Van Hende J Waelkens M (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 243-250 p
10 Roos P Moens L De Rudder J De Paepe P Van Hende J Waelkens M(l988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 263-272 p
llMeloni S Oddone M Zezza U (1995) in The Study of Marble and other Stones used in Antiquity (Y Maniatis N Heamp Y Basiakos eds) Archetype Publications Ltd Londonl81-186 p
12Asgari N Matthews KJ in The Study ofMarble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd Londonl23-129 p
13 Jongste PFB Jansen JB Moens L De Paepe P(l995) in The Study of Marble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd London 143-150 p
14 Lapuente P Turi B (1995) Science and Technology for Cultura Heritage 4 33-42 15 Castorina F Preite Martinez M Turi B (1997) Science and Technology for Cultura Heritage 6145-150 16 Barbin V Zezza U Pardo E S (1995) in The Study ofMarble and other Stones used in Antiquity (Y Maniatis
N Herz Y Basiakos eds) Archetype Publications Ltd London 131-135p 17 Blanc P (1995) in The Study ofMarble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos
eds) Archetype Publications Ltd London137-14lp 18 Attanasio D Brilli M Bruno M (2008) Archaeometry 50 747-774 19 Biricotti F Severi M Valeri C (2000) Abstract from ASMOSIA 2000 Venice 15-18 June 2000 20 Van der Merwe N Herrmann J Newman R Tykot R and Herz N (1995) in The Study of Marble and
Other Stones Used in Antiquity Asmosia 3 Athens (Y Maniatis N Herz and Y Basiakos eds) Archetype Publications Ltd London 187-198p
21 Capedri S Venturelli G Photiades A (2004) Joumal ofCultural Heritage 5 27-47 22Barbin V Bums S Decrouez D Oddone M Zezza U (1991) in the 2nd Intemational Symposium for the
Conservation of Monuments in the Mediterranean Basin (D Decrouez J Chamay and F Zezza eds) Gegraveneva Ville de Gegraveneve 47-62 p
23 Meloni S Oddone M Zezza 0(1995) in The Study ofMarble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd London 181-186 pp
24 Rollinson HR(l993)Using geochemical data Evaluation presentation interpretation Longman Harlow (UK) 51 O 25 Oddone M Meloni S Genova N (1984) Inorganica Chimica Acta 94 283-290 26 Monna D Pensabene P Sodini JP (1985) Studi Miscellanei26 28-29 27 Jaffrezic H (1976) Talanta 23 497-501 28 National Bureau of Standard Certificate of analysis SRM 1633a Trace Elements in Coal Fly Ash
Gaithersburg MD (USA) 1985 29 Korotev RL (1987) J Radioanal Nucl Chem 110 179-189 30 SPSS 17 for Windows SPSS Inc 2009 31 Gorrini ME (2008) Flos Italiae 8 333-358
428
l
t
PROCEEDINGS
4th Intemational Congress on
Science and Technology for the Safeguard of Cultural Heritage in the
Mediterranean Basin
Cairo Egypt
6th- gth December 2009
VOL II
Session B
Editor Angelo Ferrari
Finito di stampare prima edizione giugno 20 l O dalla laquoGrafica Elettronicaraquo srl Napoli te +390815595114 middotfax +390815597681 infoautorineditiit middot wwwautorineditiit
Publishing coordinati an and realization Angelo Ferrari - CNR Inst of Chemical Methodologies Italy
Digitai Editing and Data Processing Stefano Tardiola Secretariat Enza Sirugo - CNR Inst of Chemical Methodologies Italy Elvira Possagno Manuela Manfredi AIC Secretariat Italy
Session B2 - Evaluation of damage restoration and conservati an ojmonuments buildings and historical gardens
REES TO DISTINGUISH SOURCE ORIGIN OF MAIN WHITE MARBLE IN THE MEDITERRANEAN BASIN
ODDONE MASSIMO National Research Council (CNR) Institute for Energetics and Interphases (IENI) Department ofPavia Generai Chemistry
Department University ofPavia viale T Taramelli 12 27100 Pavia (Italy) Fax -39-382- 528544 -mai oddonealunipvit
Abstract Many investigations ha ve been reported in the literature on the provenance of a number of stone materials used to manufacture artifacts of archaeological or historical interest with special reference to marble Some of these investigations dea with geologica (ie geochemical mineropetrographic) parameters or have a physical approach (Cathodoluminescence ESR-EPR spectrometry etc) In other cases a chemical approach is followed involving the determination of the elemental composition with different techniques X-ray fluorescence Spectrophotometry Plasma Spectrometry Atomic Absorption Spectrometry or Neutron Activation Analysis (NAA) as in the present case Attention was then addressed to the rare-earth elements (REEs) which usually are useful in a number of geochemical studies such as those conceming the formation evolution and classification ofa number ofrocks and soils as well as in archaeometric studies REEs were determined by neutron activation analysis in the 250 Kw Triga Mark II reactor of the University of Pavia and radiochemical separations based on the precipitation and purification ofREEs fluorides For ali samples showing a light REE (La-Eu) enrichment compared to the heavy ones (Gd-Lu) ali of them show also the soshycalled Eu negative anomaly The intensity ofthis anomaly is evaluated in terms ofdepth expressed as the ratio EuEu ofthe normalized Eu content to the one Eu obtained as the geometrica mean of the normalized content of the adjacent elements Sm and Gd Discriminant power of REEs to distinguish the source origin of white marble in the Mediterranean basin had been evidentiated The results are presented discussed and compared
Keywords White marbles Neutron Activation Analysis Rare Earth Element Provenance
l Introduction Many papers have been devoted to the characterization of marbles in generai (in particular white marbles) from important ancient quarries using mainly petrographic and geochemical parameters 1 15 but a Iso other techniques including cathodoluminescence16bull17 electron spin resonance (ESR) 18 and light diffusion 19 The same parameters have been applied to the provenancing of archaeological marbles0 Marbles were derived from the metamorphic recrystallisation of carbonate-dominant protoliths (mainly limestones magnesian or dolomitic limestones) containing also minor silicate minerals as accessory The accessory minerals have recently been shown21 to be important in the discrimination of Mediterranean marble quarries and so they may a iso be used in the provenancing ofarchaeological marbles alone or in combination with the routinely applied parameters From a compositional point or view the distribution ofthe rare earth elements (REE) was found to be significant 2223
In order to verify these hypotheses attention has been addressed to rare-earth elements (REE) Usually in geochemical studies REE are useful to elucidate rock forming processes and to classify rocks and soils of different origin As it is well known carbonate rocks have a poorer REE content than silicate rocks 24 Radiochemical Neutron Activation Analysis (RNAA) is at the moment the most used analytical technique for the determination poor REE abundance in geologica samples on account of its high sensitivity ofthe possibility of determining all the elements and ofthe undisputed accuracy and reliability ofits results 25
2 Experimental
21 Analysed materials The investigated middotmarble samples were ali relative to quarry materials sampling by Manna et al26 Italian marble from Carrara Greek marbles from Hymettus Naxos Paros Penteli and Thasos and Turkish marbles from Afyon Aphrodisias Denizli Marmara and U~ak (Fig 1) Their choice has been made as for marble specimens in relation to the common varieties employed in monuments and considering mostly the facies of larger diffusion in the quarrying districts and with common contents of accessory minerals (silicates sulphides oxides etc) were here considered for investigation of REE Marble samples (10-20 g) were ground (l 00 mesh) and homogeneised Randomly collected subsamples in the range 01-1 g were then submitted to homogeneity tests according to Jaffrezic27 The variance analysis taken as an evaluation of the sample variability due to sampling provides evidence that aliquots of 400 mg or greater are homogeneous and representative of the investigated marble sample Usually 05 g of marble sample were inserted into polyethylene vials for irradiation
424
Sessi an B2 - Evauation of damage restoration and conservation of monuments buildings and historical gardens
Fig 1- Map ofthe marble quarries
Table l- REEs Nuclear data Statue LREET (jgg) LREEL (lgg) LREEH (jgg) L RE EL l EuEu
L RE EH C1 60plusmn007 535plusmn009 063plusmn002 85plusmn04 076plusmn003
C2 59plusmn03 53plusmn03 064plusmn004 82plusmn01 066plusmn008
22 Reference standards A synthetic reference standard was prepared by adding known amounts of the REE to pure CaC03bull In addition NIST SRM1633a Coal Fly Ash 2 was used in marble analysis
23 Irradiations and cooling Marble samples and reference standards were irradiated in the 250 Kw TRIGA MARK II reactor of the University ofPavia at a thermal neutron flux of about lxl0 12 n cm-2smiddot Irradiation time was 20 hours a second irradiation of 15 minutes was carried out at a thermal flux ofabout 2xl0 12 n cm-2s1 after the radiochemical separation step for the determination of short-lived radionuclides and the evaluation ofthe chemical yield After the flrst irradiation samples and reference standard were left to decay for 3 days before being processed after the second irradiation samples were left to decay for l hour before being submitted to y-spectrometry
24 Radioactivity measurement Induced radioactivity was measured by y-ray spectrometry using a HP-Ge detector coupled to a computer assisted OR TEC spectral analysis system The y-rays utilized in this work are reported in Table l
25 Radiochemical procedure After the decay period the irradiated samples were transferred to a beaker and known amounts (lO mg) of Se and REE (except La Nd Pr Dy and Er) added as carriers The mixture was then submitted to an acid attack with 4M CH3COOH solution The precipitation of REE-fluorides was carried out by adding a mixture of 50 HF and 10 NH4F solutions together with La+3 carrier solution The fluorides were separated dissolved with a HN03 solution and borie acid saturated solution and again precipitated as described above without La+3 carrier addition The
425
Session B2 - Evaluation of darnage restoration and conservation ojrnonurnents buildings and historical gardens
fluorides were then dissolved as described and brought to a 1 O cm3 volume a 9 cm3 aliquot was used for radioactivity measurement and the remaining 1 cm3 was re-irradiated together with REE reference standard for the determination of N d Pr Dy Er and the evaluation of the chemical yield The latter resulted to be throughout the present investigation equa to 98plusmn225
Table 2- Average and standard deviation REE content (pg1) ofthe investigated samplesfrom different quarries ltalian Greek Turkish
Element
Carrara (80) Hymetto(10) Naxos (10) Paros (25) Pentelico (30) Thassos (10) Afyon(10) Aphrodisias (25) Denizli (20) Maramara (30) U~ak (10)
La 089plusmn008 132plusmn007 209plusmn005 154plusmn008 149plusmn007 1239plusmn0002 0701plusmn0002 244plusmn005 147plusmn009 169plusmn009 0140plusmn0009
Ce 106plusmn004 170plusmn005 414plusmn009 246plusmn006 1413plusmn0006 2033plusmn0001 108plusmn004 299plusmn003 167plusmn009 205plusmn007 0214plusmn0005
Pr 016plusmn006 051plusmn003 0376plusmn0007 026plusmn001 0222plusmn0007 0222plusmn0002 0111plusmn0004 087plusmn002 0381 plusmn0009 0425plusmn0007 0018plusmn0006
N d 056plusmn007 0334plusmn0008 110plusmn007 0956plusmn0007 106plusmn008 0992plusmn0001 0563plusmn0005 289plusmn006 0964plusmn0006 197plusmn004 0086plusmn0001
Sm 0171plusmn0008 0271plusmn0004 0096plusmn0003 0170plusmn0006 017plusmn003 0278plusmn0001 0157plusmn0003 0265plusmn0007 0178plusmn0005 0211plusmn0006 0184plusmn0002
Eu 0026plusmn0005 0041plusmn0005 0025plusmn0002 0052plusmn0003 0047plusmn0003 0043plusmn0003 0049plusmn0001 0071plusmn0004 0038plusmn0009 0487plusmn0004 0031plusmn0005
Gd 0163plusmn0003 0266plusmn0002 0146plusmn0005 0145plusmn0005 0150plusmn0005 0345plusmn0003 020plusmn001 0261plusmn0005 0161plusmn0003 0195plusmn0009 0240plusmn0005
Tb 0030plusmn0008 0043plusmn0003 0030plusmn0003 0026plusmn0002 0021plusmn0002 0042plusmn0008 0030plusmn0004 0052plusmn0003 0025plusmn0004 0035plusmn0004 0038plusmn0001
Dy 0169plusmn0009 0294plusmn0004 0199plusmn0009 0119plusmn0004 021 0plusmn0003 0250plusmn0005 0179plusmn0009 0324plusmn0003 0141plusmn0005 0217plusmn0014 0229plusmn0002
Ho 0045plusmn0005 0052plusmn0001 0030plusmn0003 0033plusmn0002 0033plusmn0004 0063plusmn0001 0039plusmn0006 0247plusmn0004 0035plusmn0003 0035plusmn0003 0049plusmn0001
Er 0117plusmn0004 0145plusmn0003 0079plusmn0011 0110plusmn0007 01 00plusmn0005 0156plusmn0002 0095plusmn0001 0202plusmn0007 0069plusmn0004 0087plusmn0005 0121plusmn0002
T m 0021plusmn0008 0022plusmn0001 0014plusmn0002 0017plusmn0002 0018plusmn0004 0025plusmn0001 0015plusmn0003 0024plusmn0001 0012plusmn0004 0009plusmn0002 0019plusmn0008
Yb 0115plusmn0041 0133plusmn0004 0072plusmn0008 0064plusmn0004 0073plusmn0006 0164plusmn0002 0097plusmn0001 027plusmn004 0053plusmn0005 0035plusmn0005 0122plusmn0007
Lu 0017plusmn0005 0021plusmn0001 0011 plusmn0001 0014plusmn0002 0021plusmn0004 0025plusmn0002 0015plusmn0002 001 0plusmn0001 0008plusmn0001 0004plusmn0001 0017plusmn0004
Table 3- REE abundances Lgg) ofthe investigated NIS T SRMJ633 C l Fl A h a o a ty s
NBS SRM 1633a This work Found
Element Rif 28 Rif 29 La 82plusmn02 791plusmn01 Ce 1755plusmn04 180 1683plusmn16 Pr 201plusmn09 - -N d 767plusmn03 - 757plusmn20 Sm 176plusmn02 - 1683plusmn020 Eu 367plusmn004 4 358plusmn007 Gd 169plusmn03 - -Tb 240plusmn004 - 238plusmn007 Dy 156plusmn06 - -Ho 381plusmn004 - -Er 83plusmn04 - -T m 123plusmn004 -Yb 768plusmn005 - 750+013 Lu 1190plusmn0006 - 1075plusmn0013
Table 4- Some useful parameters based on REEfor the different w h bl h u d b zte mar e quarnes in t e e iterranean asin
Quarries LREEr (1-gg) LREEL (1-gg) LREEH (1-gg) ~REE l ~REEH EuEu
Carrara 352plusmn009 283plusmn008 073+001 401plusmn009 030plusmn004 Hymetto 51+03 41plusmn02 102+001 40plusmn02 037plusmn006 Naxos 84 + 04 78 plusmn 04 060 plusmn 002 131 + 04 045plusmn008 Paros 60 plusmn 02 54 plusmn 02 064 + 002 84 plusmn 02 046plusmn005 Pentelico 51 + 04 44 + 04 068 + 001 65 plusmn 04 UogravetgtplusmnUU~
Thassos 588 plusmn 001 4764 + 0005 1113 plusmn 0008 428 + 003 032plusmn004 Afyon 333 plusmn 007 261 + 005 072 + 002 235 plusmn 009 055+007 Aphrodisias 106 + 06 95 + 02 110plusmn003 859 + 004 066plusmn005 Denizli 52 + 01 47+01 055 plusmn 001 92 + 01 044plusmn003 Marmara 75 + 02 63 + 03 11 plusmn 01 56 + 02 512plusmn009 U~ak 150 plusmn 007 064 plusmn 004 087 plusmn 004 074 + 009 032plusmn004
3 Results and discussion
REE contents of the investigated marbles are reported in Table 2 Samples have been grouped according to the quarry and reported values are the averages and the standard deviations often or more independent determinations for all samples ofthe same site Analytical precision is usually below 8 An evaluation ofthe accuracy ofthe method can be obtained by looking at the data on NIST Standard Reference Materia 1633a Coal Fly Ash reported in Table 3 and comparing them with existing values in the literature2829
The data being the average of20 independent runs agree very well and validate the reliability ofthe method More information is obtained if some parameters based on REE concentration for all samples are considered the sum ofmeasured REE concentrations (IREEr) the sum ofthe concentrations oflight REE (IREEL) the sum ofthe concentrations of heavy REE (IHREEH) the ratio of REEL to REEH All samples showing a light REE (La-Eu) enrichment compared to the heavy ones (Gd-Lu)
426
Sessi an 82 - Evaluation of damage restoration and conservati an of monuments buildings and historical garden s
Discriminant power of REEs to distinguish the source origin of white marble in the Mediterranean basin had been evidentiated to compute Hotellings (T2 test) for matched group designs using the RELIABILITY routine of SPSS30
Differences in the values of LREEr a statistica meaningful differences were obtained in 95 confidence leve of cases in the values of L REE L a statistica meaningful differences were obtained in 93 l confidence leve of cases the values of REEH a statistica meaningful differences were obtained in 89 confidence leve of cases and the values of LREEdLREEH a statistica meaningful differences w ere obtained in 90 confidence leve of cases Ali of them show also the so-called Eu negative anomaly the intensity of this anomaly is evaluated in terms of depth expressed as the ratio EuEu of the normalized Eu content to the one Eu obtained as the geometrica mean of the normalized content of the adjacent elements Sm and Gd as shown in Table 4 Not is a good discriminate parameter for quarries because depend the redox conditions This result therefore aimed to apply experience in marble provenancing by RNAA acquired to study the marble provenance of veiled Aphrodite statue of the Palazzo Ducale in Mantua (Italy) one of the few pieces not sold to Charles I of England (1627-1628) and one of the few to escape the dispersion following the sack of the Lanzichenecchi in 1630 and 1631 31
The samples were provided inthe form of small fragments from two areas of a sculpture (C1 and C2) and about 800 mg of powdered marble was obtained from them usually by drilling using a standard 5 mm masonry (tungsten carbide) bit The initial drillings were discarded to avoid materia that may have been modified by weathering processes Marble samples were ground (SI 00 mesh) and homogeneised and 05 g w ere submitted to RNAA REE content are given in table 5 A close examination of the REE data allows the identification of some parameters that can be used t o discriminate the white marble quarries ofthe Mediterranean basin (Table 6) The values ofthis quantity for the marble samples from the veiled Aphrodite are very similar to the one ofthe Paros quarrying
Table 5- Average and standard deviation REE conteni (pglg) ofthe veiled Aphrodite
ttemem 1(1 IC2
La 147plusmn009 146plusmn006 Ce 25plusmn01 24plusmn01 Pr 026plusmn001 027plusmn001 N d 095plusmn001 096plusmn002 Sm 017plusmn001 017plusmn002 Eu 0056plusmn0006 0061plusmn0002 Gd 015plusmn001 015plusmn001 Tb 0025plusmn0002 0025plusmn0001 Dy 019plusmn001 019plusmn001 Ho 0033plusmn0002 0033plusmn0002 Er 0098plusmn0003 0099plusmn0003 T m 0016plusmn0002 0016plusmn0002 Yb 0063plusmn0002 0065plusmn0004 Lu 0013plusmn0002 0014plusmn0001
Table 6-Statue EuEu
C1 076plusmn003 C2 066plusmn008
4 Conclusions
The routine neutron activation analysis of marble standard samples within a given irradiation batch has demonstrated the stability of the counting system and the reproducibility of the neutron activation technique The severa batch es of samples were analysed over the course of about 25 years The replicate analysis of the quarries samples some ten years apart also confirms the reproducibility of the technique In conclusion some basic provenancing procedures by the evaluation ofthe distribution ofthe REE especially may be confidently used
427
Session B2 - Evaluation of damage restoration and conservation ofmonuments buildings and historical gardens
5 References l Manfra L Masi U Turi B (1975) Archaeometry 17215-221 2 Herz N Dean NE (1986) Applied Geochemistry l 139-151 3 Herz N(l987) Archaeometry 2935-43 4 HerzN(l992)Archaeometry 34185-194 5 Dean NE (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 315-323 p 6 Germann K Gruben G Knoll H Valis V Winkler FJ (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 251-262 p 7 Lazzarini L Mariottini M Pecorara M Pensabene P (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 399-410 p
8 Lazzarini L Masi U Tucci P (1995) in The Study of Marble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd Londonl61-169 p
9 Moens L Roos P De Rudder J De Paepe P Van Hende J Waelkens M (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 243-250 p
10 Roos P Moens L De Rudder J De Paepe P Van Hende J Waelkens M(l988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 263-272 p
llMeloni S Oddone M Zezza U (1995) in The Study of Marble and other Stones used in Antiquity (Y Maniatis N Heamp Y Basiakos eds) Archetype Publications Ltd Londonl81-186 p
12Asgari N Matthews KJ in The Study ofMarble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd Londonl23-129 p
13 Jongste PFB Jansen JB Moens L De Paepe P(l995) in The Study of Marble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd London 143-150 p
14 Lapuente P Turi B (1995) Science and Technology for Cultura Heritage 4 33-42 15 Castorina F Preite Martinez M Turi B (1997) Science and Technology for Cultura Heritage 6145-150 16 Barbin V Zezza U Pardo E S (1995) in The Study ofMarble and other Stones used in Antiquity (Y Maniatis
N Herz Y Basiakos eds) Archetype Publications Ltd London 131-135p 17 Blanc P (1995) in The Study ofMarble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos
eds) Archetype Publications Ltd London137-14lp 18 Attanasio D Brilli M Bruno M (2008) Archaeometry 50 747-774 19 Biricotti F Severi M Valeri C (2000) Abstract from ASMOSIA 2000 Venice 15-18 June 2000 20 Van der Merwe N Herrmann J Newman R Tykot R and Herz N (1995) in The Study of Marble and
Other Stones Used in Antiquity Asmosia 3 Athens (Y Maniatis N Herz and Y Basiakos eds) Archetype Publications Ltd London 187-198p
21 Capedri S Venturelli G Photiades A (2004) Joumal ofCultural Heritage 5 27-47 22Barbin V Bums S Decrouez D Oddone M Zezza U (1991) in the 2nd Intemational Symposium for the
Conservation of Monuments in the Mediterranean Basin (D Decrouez J Chamay and F Zezza eds) Gegraveneva Ville de Gegraveneve 47-62 p
23 Meloni S Oddone M Zezza 0(1995) in The Study ofMarble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd London 181-186 pp
24 Rollinson HR(l993)Using geochemical data Evaluation presentation interpretation Longman Harlow (UK) 51 O 25 Oddone M Meloni S Genova N (1984) Inorganica Chimica Acta 94 283-290 26 Monna D Pensabene P Sodini JP (1985) Studi Miscellanei26 28-29 27 Jaffrezic H (1976) Talanta 23 497-501 28 National Bureau of Standard Certificate of analysis SRM 1633a Trace Elements in Coal Fly Ash
Gaithersburg MD (USA) 1985 29 Korotev RL (1987) J Radioanal Nucl Chem 110 179-189 30 SPSS 17 for Windows SPSS Inc 2009 31 Gorrini ME (2008) Flos Italiae 8 333-358
428
Finito di stampare prima edizione giugno 20 l O dalla laquoGrafica Elettronicaraquo srl Napoli te +390815595114 middotfax +390815597681 infoautorineditiit middot wwwautorineditiit
Publishing coordinati an and realization Angelo Ferrari - CNR Inst of Chemical Methodologies Italy
Digitai Editing and Data Processing Stefano Tardiola Secretariat Enza Sirugo - CNR Inst of Chemical Methodologies Italy Elvira Possagno Manuela Manfredi AIC Secretariat Italy
Session B2 - Evaluation of damage restoration and conservati an ojmonuments buildings and historical gardens
REES TO DISTINGUISH SOURCE ORIGIN OF MAIN WHITE MARBLE IN THE MEDITERRANEAN BASIN
ODDONE MASSIMO National Research Council (CNR) Institute for Energetics and Interphases (IENI) Department ofPavia Generai Chemistry
Department University ofPavia viale T Taramelli 12 27100 Pavia (Italy) Fax -39-382- 528544 -mai oddonealunipvit
Abstract Many investigations ha ve been reported in the literature on the provenance of a number of stone materials used to manufacture artifacts of archaeological or historical interest with special reference to marble Some of these investigations dea with geologica (ie geochemical mineropetrographic) parameters or have a physical approach (Cathodoluminescence ESR-EPR spectrometry etc) In other cases a chemical approach is followed involving the determination of the elemental composition with different techniques X-ray fluorescence Spectrophotometry Plasma Spectrometry Atomic Absorption Spectrometry or Neutron Activation Analysis (NAA) as in the present case Attention was then addressed to the rare-earth elements (REEs) which usually are useful in a number of geochemical studies such as those conceming the formation evolution and classification ofa number ofrocks and soils as well as in archaeometric studies REEs were determined by neutron activation analysis in the 250 Kw Triga Mark II reactor of the University of Pavia and radiochemical separations based on the precipitation and purification ofREEs fluorides For ali samples showing a light REE (La-Eu) enrichment compared to the heavy ones (Gd-Lu) ali of them show also the soshycalled Eu negative anomaly The intensity ofthis anomaly is evaluated in terms ofdepth expressed as the ratio EuEu ofthe normalized Eu content to the one Eu obtained as the geometrica mean of the normalized content of the adjacent elements Sm and Gd Discriminant power of REEs to distinguish the source origin of white marble in the Mediterranean basin had been evidentiated The results are presented discussed and compared
Keywords White marbles Neutron Activation Analysis Rare Earth Element Provenance
l Introduction Many papers have been devoted to the characterization of marbles in generai (in particular white marbles) from important ancient quarries using mainly petrographic and geochemical parameters 1 15 but a Iso other techniques including cathodoluminescence16bull17 electron spin resonance (ESR) 18 and light diffusion 19 The same parameters have been applied to the provenancing of archaeological marbles0 Marbles were derived from the metamorphic recrystallisation of carbonate-dominant protoliths (mainly limestones magnesian or dolomitic limestones) containing also minor silicate minerals as accessory The accessory minerals have recently been shown21 to be important in the discrimination of Mediterranean marble quarries and so they may a iso be used in the provenancing ofarchaeological marbles alone or in combination with the routinely applied parameters From a compositional point or view the distribution ofthe rare earth elements (REE) was found to be significant 2223
In order to verify these hypotheses attention has been addressed to rare-earth elements (REE) Usually in geochemical studies REE are useful to elucidate rock forming processes and to classify rocks and soils of different origin As it is well known carbonate rocks have a poorer REE content than silicate rocks 24 Radiochemical Neutron Activation Analysis (RNAA) is at the moment the most used analytical technique for the determination poor REE abundance in geologica samples on account of its high sensitivity ofthe possibility of determining all the elements and ofthe undisputed accuracy and reliability ofits results 25
2 Experimental
21 Analysed materials The investigated middotmarble samples were ali relative to quarry materials sampling by Manna et al26 Italian marble from Carrara Greek marbles from Hymettus Naxos Paros Penteli and Thasos and Turkish marbles from Afyon Aphrodisias Denizli Marmara and U~ak (Fig 1) Their choice has been made as for marble specimens in relation to the common varieties employed in monuments and considering mostly the facies of larger diffusion in the quarrying districts and with common contents of accessory minerals (silicates sulphides oxides etc) were here considered for investigation of REE Marble samples (10-20 g) were ground (l 00 mesh) and homogeneised Randomly collected subsamples in the range 01-1 g were then submitted to homogeneity tests according to Jaffrezic27 The variance analysis taken as an evaluation of the sample variability due to sampling provides evidence that aliquots of 400 mg or greater are homogeneous and representative of the investigated marble sample Usually 05 g of marble sample were inserted into polyethylene vials for irradiation
424
Sessi an B2 - Evauation of damage restoration and conservation of monuments buildings and historical gardens
Fig 1- Map ofthe marble quarries
Table l- REEs Nuclear data Statue LREET (jgg) LREEL (lgg) LREEH (jgg) L RE EL l EuEu
L RE EH C1 60plusmn007 535plusmn009 063plusmn002 85plusmn04 076plusmn003
C2 59plusmn03 53plusmn03 064plusmn004 82plusmn01 066plusmn008
22 Reference standards A synthetic reference standard was prepared by adding known amounts of the REE to pure CaC03bull In addition NIST SRM1633a Coal Fly Ash 2 was used in marble analysis
23 Irradiations and cooling Marble samples and reference standards were irradiated in the 250 Kw TRIGA MARK II reactor of the University ofPavia at a thermal neutron flux of about lxl0 12 n cm-2smiddot Irradiation time was 20 hours a second irradiation of 15 minutes was carried out at a thermal flux ofabout 2xl0 12 n cm-2s1 after the radiochemical separation step for the determination of short-lived radionuclides and the evaluation ofthe chemical yield After the flrst irradiation samples and reference standard were left to decay for 3 days before being processed after the second irradiation samples were left to decay for l hour before being submitted to y-spectrometry
24 Radioactivity measurement Induced radioactivity was measured by y-ray spectrometry using a HP-Ge detector coupled to a computer assisted OR TEC spectral analysis system The y-rays utilized in this work are reported in Table l
25 Radiochemical procedure After the decay period the irradiated samples were transferred to a beaker and known amounts (lO mg) of Se and REE (except La Nd Pr Dy and Er) added as carriers The mixture was then submitted to an acid attack with 4M CH3COOH solution The precipitation of REE-fluorides was carried out by adding a mixture of 50 HF and 10 NH4F solutions together with La+3 carrier solution The fluorides were separated dissolved with a HN03 solution and borie acid saturated solution and again precipitated as described above without La+3 carrier addition The
425
Session B2 - Evaluation of darnage restoration and conservation ojrnonurnents buildings and historical gardens
fluorides were then dissolved as described and brought to a 1 O cm3 volume a 9 cm3 aliquot was used for radioactivity measurement and the remaining 1 cm3 was re-irradiated together with REE reference standard for the determination of N d Pr Dy Er and the evaluation of the chemical yield The latter resulted to be throughout the present investigation equa to 98plusmn225
Table 2- Average and standard deviation REE content (pg1) ofthe investigated samplesfrom different quarries ltalian Greek Turkish
Element
Carrara (80) Hymetto(10) Naxos (10) Paros (25) Pentelico (30) Thassos (10) Afyon(10) Aphrodisias (25) Denizli (20) Maramara (30) U~ak (10)
La 089plusmn008 132plusmn007 209plusmn005 154plusmn008 149plusmn007 1239plusmn0002 0701plusmn0002 244plusmn005 147plusmn009 169plusmn009 0140plusmn0009
Ce 106plusmn004 170plusmn005 414plusmn009 246plusmn006 1413plusmn0006 2033plusmn0001 108plusmn004 299plusmn003 167plusmn009 205plusmn007 0214plusmn0005
Pr 016plusmn006 051plusmn003 0376plusmn0007 026plusmn001 0222plusmn0007 0222plusmn0002 0111plusmn0004 087plusmn002 0381 plusmn0009 0425plusmn0007 0018plusmn0006
N d 056plusmn007 0334plusmn0008 110plusmn007 0956plusmn0007 106plusmn008 0992plusmn0001 0563plusmn0005 289plusmn006 0964plusmn0006 197plusmn004 0086plusmn0001
Sm 0171plusmn0008 0271plusmn0004 0096plusmn0003 0170plusmn0006 017plusmn003 0278plusmn0001 0157plusmn0003 0265plusmn0007 0178plusmn0005 0211plusmn0006 0184plusmn0002
Eu 0026plusmn0005 0041plusmn0005 0025plusmn0002 0052plusmn0003 0047plusmn0003 0043plusmn0003 0049plusmn0001 0071plusmn0004 0038plusmn0009 0487plusmn0004 0031plusmn0005
Gd 0163plusmn0003 0266plusmn0002 0146plusmn0005 0145plusmn0005 0150plusmn0005 0345plusmn0003 020plusmn001 0261plusmn0005 0161plusmn0003 0195plusmn0009 0240plusmn0005
Tb 0030plusmn0008 0043plusmn0003 0030plusmn0003 0026plusmn0002 0021plusmn0002 0042plusmn0008 0030plusmn0004 0052plusmn0003 0025plusmn0004 0035plusmn0004 0038plusmn0001
Dy 0169plusmn0009 0294plusmn0004 0199plusmn0009 0119plusmn0004 021 0plusmn0003 0250plusmn0005 0179plusmn0009 0324plusmn0003 0141plusmn0005 0217plusmn0014 0229plusmn0002
Ho 0045plusmn0005 0052plusmn0001 0030plusmn0003 0033plusmn0002 0033plusmn0004 0063plusmn0001 0039plusmn0006 0247plusmn0004 0035plusmn0003 0035plusmn0003 0049plusmn0001
Er 0117plusmn0004 0145plusmn0003 0079plusmn0011 0110plusmn0007 01 00plusmn0005 0156plusmn0002 0095plusmn0001 0202plusmn0007 0069plusmn0004 0087plusmn0005 0121plusmn0002
T m 0021plusmn0008 0022plusmn0001 0014plusmn0002 0017plusmn0002 0018plusmn0004 0025plusmn0001 0015plusmn0003 0024plusmn0001 0012plusmn0004 0009plusmn0002 0019plusmn0008
Yb 0115plusmn0041 0133plusmn0004 0072plusmn0008 0064plusmn0004 0073plusmn0006 0164plusmn0002 0097plusmn0001 027plusmn004 0053plusmn0005 0035plusmn0005 0122plusmn0007
Lu 0017plusmn0005 0021plusmn0001 0011 plusmn0001 0014plusmn0002 0021plusmn0004 0025plusmn0002 0015plusmn0002 001 0plusmn0001 0008plusmn0001 0004plusmn0001 0017plusmn0004
Table 3- REE abundances Lgg) ofthe investigated NIS T SRMJ633 C l Fl A h a o a ty s
NBS SRM 1633a This work Found
Element Rif 28 Rif 29 La 82plusmn02 791plusmn01 Ce 1755plusmn04 180 1683plusmn16 Pr 201plusmn09 - -N d 767plusmn03 - 757plusmn20 Sm 176plusmn02 - 1683plusmn020 Eu 367plusmn004 4 358plusmn007 Gd 169plusmn03 - -Tb 240plusmn004 - 238plusmn007 Dy 156plusmn06 - -Ho 381plusmn004 - -Er 83plusmn04 - -T m 123plusmn004 -Yb 768plusmn005 - 750+013 Lu 1190plusmn0006 - 1075plusmn0013
Table 4- Some useful parameters based on REEfor the different w h bl h u d b zte mar e quarnes in t e e iterranean asin
Quarries LREEr (1-gg) LREEL (1-gg) LREEH (1-gg) ~REE l ~REEH EuEu
Carrara 352plusmn009 283plusmn008 073+001 401plusmn009 030plusmn004 Hymetto 51+03 41plusmn02 102+001 40plusmn02 037plusmn006 Naxos 84 + 04 78 plusmn 04 060 plusmn 002 131 + 04 045plusmn008 Paros 60 plusmn 02 54 plusmn 02 064 + 002 84 plusmn 02 046plusmn005 Pentelico 51 + 04 44 + 04 068 + 001 65 plusmn 04 UogravetgtplusmnUU~
Thassos 588 plusmn 001 4764 + 0005 1113 plusmn 0008 428 + 003 032plusmn004 Afyon 333 plusmn 007 261 + 005 072 + 002 235 plusmn 009 055+007 Aphrodisias 106 + 06 95 + 02 110plusmn003 859 + 004 066plusmn005 Denizli 52 + 01 47+01 055 plusmn 001 92 + 01 044plusmn003 Marmara 75 + 02 63 + 03 11 plusmn 01 56 + 02 512plusmn009 U~ak 150 plusmn 007 064 plusmn 004 087 plusmn 004 074 + 009 032plusmn004
3 Results and discussion
REE contents of the investigated marbles are reported in Table 2 Samples have been grouped according to the quarry and reported values are the averages and the standard deviations often or more independent determinations for all samples ofthe same site Analytical precision is usually below 8 An evaluation ofthe accuracy ofthe method can be obtained by looking at the data on NIST Standard Reference Materia 1633a Coal Fly Ash reported in Table 3 and comparing them with existing values in the literature2829
The data being the average of20 independent runs agree very well and validate the reliability ofthe method More information is obtained if some parameters based on REE concentration for all samples are considered the sum ofmeasured REE concentrations (IREEr) the sum ofthe concentrations oflight REE (IREEL) the sum ofthe concentrations of heavy REE (IHREEH) the ratio of REEL to REEH All samples showing a light REE (La-Eu) enrichment compared to the heavy ones (Gd-Lu)
426
Sessi an 82 - Evaluation of damage restoration and conservati an of monuments buildings and historical garden s
Discriminant power of REEs to distinguish the source origin of white marble in the Mediterranean basin had been evidentiated to compute Hotellings (T2 test) for matched group designs using the RELIABILITY routine of SPSS30
Differences in the values of LREEr a statistica meaningful differences were obtained in 95 confidence leve of cases in the values of L REE L a statistica meaningful differences were obtained in 93 l confidence leve of cases the values of REEH a statistica meaningful differences were obtained in 89 confidence leve of cases and the values of LREEdLREEH a statistica meaningful differences w ere obtained in 90 confidence leve of cases Ali of them show also the so-called Eu negative anomaly the intensity of this anomaly is evaluated in terms of depth expressed as the ratio EuEu of the normalized Eu content to the one Eu obtained as the geometrica mean of the normalized content of the adjacent elements Sm and Gd as shown in Table 4 Not is a good discriminate parameter for quarries because depend the redox conditions This result therefore aimed to apply experience in marble provenancing by RNAA acquired to study the marble provenance of veiled Aphrodite statue of the Palazzo Ducale in Mantua (Italy) one of the few pieces not sold to Charles I of England (1627-1628) and one of the few to escape the dispersion following the sack of the Lanzichenecchi in 1630 and 1631 31
The samples were provided inthe form of small fragments from two areas of a sculpture (C1 and C2) and about 800 mg of powdered marble was obtained from them usually by drilling using a standard 5 mm masonry (tungsten carbide) bit The initial drillings were discarded to avoid materia that may have been modified by weathering processes Marble samples were ground (SI 00 mesh) and homogeneised and 05 g w ere submitted to RNAA REE content are given in table 5 A close examination of the REE data allows the identification of some parameters that can be used t o discriminate the white marble quarries ofthe Mediterranean basin (Table 6) The values ofthis quantity for the marble samples from the veiled Aphrodite are very similar to the one ofthe Paros quarrying
Table 5- Average and standard deviation REE conteni (pglg) ofthe veiled Aphrodite
ttemem 1(1 IC2
La 147plusmn009 146plusmn006 Ce 25plusmn01 24plusmn01 Pr 026plusmn001 027plusmn001 N d 095plusmn001 096plusmn002 Sm 017plusmn001 017plusmn002 Eu 0056plusmn0006 0061plusmn0002 Gd 015plusmn001 015plusmn001 Tb 0025plusmn0002 0025plusmn0001 Dy 019plusmn001 019plusmn001 Ho 0033plusmn0002 0033plusmn0002 Er 0098plusmn0003 0099plusmn0003 T m 0016plusmn0002 0016plusmn0002 Yb 0063plusmn0002 0065plusmn0004 Lu 0013plusmn0002 0014plusmn0001
Table 6-Statue EuEu
C1 076plusmn003 C2 066plusmn008
4 Conclusions
The routine neutron activation analysis of marble standard samples within a given irradiation batch has demonstrated the stability of the counting system and the reproducibility of the neutron activation technique The severa batch es of samples were analysed over the course of about 25 years The replicate analysis of the quarries samples some ten years apart also confirms the reproducibility of the technique In conclusion some basic provenancing procedures by the evaluation ofthe distribution ofthe REE especially may be confidently used
427
Session B2 - Evaluation of damage restoration and conservation ofmonuments buildings and historical gardens
5 References l Manfra L Masi U Turi B (1975) Archaeometry 17215-221 2 Herz N Dean NE (1986) Applied Geochemistry l 139-151 3 Herz N(l987) Archaeometry 2935-43 4 HerzN(l992)Archaeometry 34185-194 5 Dean NE (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 315-323 p 6 Germann K Gruben G Knoll H Valis V Winkler FJ (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 251-262 p 7 Lazzarini L Mariottini M Pecorara M Pensabene P (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 399-410 p
8 Lazzarini L Masi U Tucci P (1995) in The Study of Marble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd Londonl61-169 p
9 Moens L Roos P De Rudder J De Paepe P Van Hende J Waelkens M (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 243-250 p
10 Roos P Moens L De Rudder J De Paepe P Van Hende J Waelkens M(l988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 263-272 p
llMeloni S Oddone M Zezza U (1995) in The Study of Marble and other Stones used in Antiquity (Y Maniatis N Heamp Y Basiakos eds) Archetype Publications Ltd Londonl81-186 p
12Asgari N Matthews KJ in The Study ofMarble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd Londonl23-129 p
13 Jongste PFB Jansen JB Moens L De Paepe P(l995) in The Study of Marble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd London 143-150 p
14 Lapuente P Turi B (1995) Science and Technology for Cultura Heritage 4 33-42 15 Castorina F Preite Martinez M Turi B (1997) Science and Technology for Cultura Heritage 6145-150 16 Barbin V Zezza U Pardo E S (1995) in The Study ofMarble and other Stones used in Antiquity (Y Maniatis
N Herz Y Basiakos eds) Archetype Publications Ltd London 131-135p 17 Blanc P (1995) in The Study ofMarble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos
eds) Archetype Publications Ltd London137-14lp 18 Attanasio D Brilli M Bruno M (2008) Archaeometry 50 747-774 19 Biricotti F Severi M Valeri C (2000) Abstract from ASMOSIA 2000 Venice 15-18 June 2000 20 Van der Merwe N Herrmann J Newman R Tykot R and Herz N (1995) in The Study of Marble and
Other Stones Used in Antiquity Asmosia 3 Athens (Y Maniatis N Herz and Y Basiakos eds) Archetype Publications Ltd London 187-198p
21 Capedri S Venturelli G Photiades A (2004) Joumal ofCultural Heritage 5 27-47 22Barbin V Bums S Decrouez D Oddone M Zezza U (1991) in the 2nd Intemational Symposium for the
Conservation of Monuments in the Mediterranean Basin (D Decrouez J Chamay and F Zezza eds) Gegraveneva Ville de Gegraveneve 47-62 p
23 Meloni S Oddone M Zezza 0(1995) in The Study ofMarble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd London 181-186 pp
24 Rollinson HR(l993)Using geochemical data Evaluation presentation interpretation Longman Harlow (UK) 51 O 25 Oddone M Meloni S Genova N (1984) Inorganica Chimica Acta 94 283-290 26 Monna D Pensabene P Sodini JP (1985) Studi Miscellanei26 28-29 27 Jaffrezic H (1976) Talanta 23 497-501 28 National Bureau of Standard Certificate of analysis SRM 1633a Trace Elements in Coal Fly Ash
Gaithersburg MD (USA) 1985 29 Korotev RL (1987) J Radioanal Nucl Chem 110 179-189 30 SPSS 17 for Windows SPSS Inc 2009 31 Gorrini ME (2008) Flos Italiae 8 333-358
428
Session B2 - Evaluation of damage restoration and conservati an ojmonuments buildings and historical gardens
REES TO DISTINGUISH SOURCE ORIGIN OF MAIN WHITE MARBLE IN THE MEDITERRANEAN BASIN
ODDONE MASSIMO National Research Council (CNR) Institute for Energetics and Interphases (IENI) Department ofPavia Generai Chemistry
Department University ofPavia viale T Taramelli 12 27100 Pavia (Italy) Fax -39-382- 528544 -mai oddonealunipvit
Abstract Many investigations ha ve been reported in the literature on the provenance of a number of stone materials used to manufacture artifacts of archaeological or historical interest with special reference to marble Some of these investigations dea with geologica (ie geochemical mineropetrographic) parameters or have a physical approach (Cathodoluminescence ESR-EPR spectrometry etc) In other cases a chemical approach is followed involving the determination of the elemental composition with different techniques X-ray fluorescence Spectrophotometry Plasma Spectrometry Atomic Absorption Spectrometry or Neutron Activation Analysis (NAA) as in the present case Attention was then addressed to the rare-earth elements (REEs) which usually are useful in a number of geochemical studies such as those conceming the formation evolution and classification ofa number ofrocks and soils as well as in archaeometric studies REEs were determined by neutron activation analysis in the 250 Kw Triga Mark II reactor of the University of Pavia and radiochemical separations based on the precipitation and purification ofREEs fluorides For ali samples showing a light REE (La-Eu) enrichment compared to the heavy ones (Gd-Lu) ali of them show also the soshycalled Eu negative anomaly The intensity ofthis anomaly is evaluated in terms ofdepth expressed as the ratio EuEu ofthe normalized Eu content to the one Eu obtained as the geometrica mean of the normalized content of the adjacent elements Sm and Gd Discriminant power of REEs to distinguish the source origin of white marble in the Mediterranean basin had been evidentiated The results are presented discussed and compared
Keywords White marbles Neutron Activation Analysis Rare Earth Element Provenance
l Introduction Many papers have been devoted to the characterization of marbles in generai (in particular white marbles) from important ancient quarries using mainly petrographic and geochemical parameters 1 15 but a Iso other techniques including cathodoluminescence16bull17 electron spin resonance (ESR) 18 and light diffusion 19 The same parameters have been applied to the provenancing of archaeological marbles0 Marbles were derived from the metamorphic recrystallisation of carbonate-dominant protoliths (mainly limestones magnesian or dolomitic limestones) containing also minor silicate minerals as accessory The accessory minerals have recently been shown21 to be important in the discrimination of Mediterranean marble quarries and so they may a iso be used in the provenancing ofarchaeological marbles alone or in combination with the routinely applied parameters From a compositional point or view the distribution ofthe rare earth elements (REE) was found to be significant 2223
In order to verify these hypotheses attention has been addressed to rare-earth elements (REE) Usually in geochemical studies REE are useful to elucidate rock forming processes and to classify rocks and soils of different origin As it is well known carbonate rocks have a poorer REE content than silicate rocks 24 Radiochemical Neutron Activation Analysis (RNAA) is at the moment the most used analytical technique for the determination poor REE abundance in geologica samples on account of its high sensitivity ofthe possibility of determining all the elements and ofthe undisputed accuracy and reliability ofits results 25
2 Experimental
21 Analysed materials The investigated middotmarble samples were ali relative to quarry materials sampling by Manna et al26 Italian marble from Carrara Greek marbles from Hymettus Naxos Paros Penteli and Thasos and Turkish marbles from Afyon Aphrodisias Denizli Marmara and U~ak (Fig 1) Their choice has been made as for marble specimens in relation to the common varieties employed in monuments and considering mostly the facies of larger diffusion in the quarrying districts and with common contents of accessory minerals (silicates sulphides oxides etc) were here considered for investigation of REE Marble samples (10-20 g) were ground (l 00 mesh) and homogeneised Randomly collected subsamples in the range 01-1 g were then submitted to homogeneity tests according to Jaffrezic27 The variance analysis taken as an evaluation of the sample variability due to sampling provides evidence that aliquots of 400 mg or greater are homogeneous and representative of the investigated marble sample Usually 05 g of marble sample were inserted into polyethylene vials for irradiation
424
Sessi an B2 - Evauation of damage restoration and conservation of monuments buildings and historical gardens
Fig 1- Map ofthe marble quarries
Table l- REEs Nuclear data Statue LREET (jgg) LREEL (lgg) LREEH (jgg) L RE EL l EuEu
L RE EH C1 60plusmn007 535plusmn009 063plusmn002 85plusmn04 076plusmn003
C2 59plusmn03 53plusmn03 064plusmn004 82plusmn01 066plusmn008
22 Reference standards A synthetic reference standard was prepared by adding known amounts of the REE to pure CaC03bull In addition NIST SRM1633a Coal Fly Ash 2 was used in marble analysis
23 Irradiations and cooling Marble samples and reference standards were irradiated in the 250 Kw TRIGA MARK II reactor of the University ofPavia at a thermal neutron flux of about lxl0 12 n cm-2smiddot Irradiation time was 20 hours a second irradiation of 15 minutes was carried out at a thermal flux ofabout 2xl0 12 n cm-2s1 after the radiochemical separation step for the determination of short-lived radionuclides and the evaluation ofthe chemical yield After the flrst irradiation samples and reference standard were left to decay for 3 days before being processed after the second irradiation samples were left to decay for l hour before being submitted to y-spectrometry
24 Radioactivity measurement Induced radioactivity was measured by y-ray spectrometry using a HP-Ge detector coupled to a computer assisted OR TEC spectral analysis system The y-rays utilized in this work are reported in Table l
25 Radiochemical procedure After the decay period the irradiated samples were transferred to a beaker and known amounts (lO mg) of Se and REE (except La Nd Pr Dy and Er) added as carriers The mixture was then submitted to an acid attack with 4M CH3COOH solution The precipitation of REE-fluorides was carried out by adding a mixture of 50 HF and 10 NH4F solutions together with La+3 carrier solution The fluorides were separated dissolved with a HN03 solution and borie acid saturated solution and again precipitated as described above without La+3 carrier addition The
425
Session B2 - Evaluation of darnage restoration and conservation ojrnonurnents buildings and historical gardens
fluorides were then dissolved as described and brought to a 1 O cm3 volume a 9 cm3 aliquot was used for radioactivity measurement and the remaining 1 cm3 was re-irradiated together with REE reference standard for the determination of N d Pr Dy Er and the evaluation of the chemical yield The latter resulted to be throughout the present investigation equa to 98plusmn225
Table 2- Average and standard deviation REE content (pg1) ofthe investigated samplesfrom different quarries ltalian Greek Turkish
Element
Carrara (80) Hymetto(10) Naxos (10) Paros (25) Pentelico (30) Thassos (10) Afyon(10) Aphrodisias (25) Denizli (20) Maramara (30) U~ak (10)
La 089plusmn008 132plusmn007 209plusmn005 154plusmn008 149plusmn007 1239plusmn0002 0701plusmn0002 244plusmn005 147plusmn009 169plusmn009 0140plusmn0009
Ce 106plusmn004 170plusmn005 414plusmn009 246plusmn006 1413plusmn0006 2033plusmn0001 108plusmn004 299plusmn003 167plusmn009 205plusmn007 0214plusmn0005
Pr 016plusmn006 051plusmn003 0376plusmn0007 026plusmn001 0222plusmn0007 0222plusmn0002 0111plusmn0004 087plusmn002 0381 plusmn0009 0425plusmn0007 0018plusmn0006
N d 056plusmn007 0334plusmn0008 110plusmn007 0956plusmn0007 106plusmn008 0992plusmn0001 0563plusmn0005 289plusmn006 0964plusmn0006 197plusmn004 0086plusmn0001
Sm 0171plusmn0008 0271plusmn0004 0096plusmn0003 0170plusmn0006 017plusmn003 0278plusmn0001 0157plusmn0003 0265plusmn0007 0178plusmn0005 0211plusmn0006 0184plusmn0002
Eu 0026plusmn0005 0041plusmn0005 0025plusmn0002 0052plusmn0003 0047plusmn0003 0043plusmn0003 0049plusmn0001 0071plusmn0004 0038plusmn0009 0487plusmn0004 0031plusmn0005
Gd 0163plusmn0003 0266plusmn0002 0146plusmn0005 0145plusmn0005 0150plusmn0005 0345plusmn0003 020plusmn001 0261plusmn0005 0161plusmn0003 0195plusmn0009 0240plusmn0005
Tb 0030plusmn0008 0043plusmn0003 0030plusmn0003 0026plusmn0002 0021plusmn0002 0042plusmn0008 0030plusmn0004 0052plusmn0003 0025plusmn0004 0035plusmn0004 0038plusmn0001
Dy 0169plusmn0009 0294plusmn0004 0199plusmn0009 0119plusmn0004 021 0plusmn0003 0250plusmn0005 0179plusmn0009 0324plusmn0003 0141plusmn0005 0217plusmn0014 0229plusmn0002
Ho 0045plusmn0005 0052plusmn0001 0030plusmn0003 0033plusmn0002 0033plusmn0004 0063plusmn0001 0039plusmn0006 0247plusmn0004 0035plusmn0003 0035plusmn0003 0049plusmn0001
Er 0117plusmn0004 0145plusmn0003 0079plusmn0011 0110plusmn0007 01 00plusmn0005 0156plusmn0002 0095plusmn0001 0202plusmn0007 0069plusmn0004 0087plusmn0005 0121plusmn0002
T m 0021plusmn0008 0022plusmn0001 0014plusmn0002 0017plusmn0002 0018plusmn0004 0025plusmn0001 0015plusmn0003 0024plusmn0001 0012plusmn0004 0009plusmn0002 0019plusmn0008
Yb 0115plusmn0041 0133plusmn0004 0072plusmn0008 0064plusmn0004 0073plusmn0006 0164plusmn0002 0097plusmn0001 027plusmn004 0053plusmn0005 0035plusmn0005 0122plusmn0007
Lu 0017plusmn0005 0021plusmn0001 0011 plusmn0001 0014plusmn0002 0021plusmn0004 0025plusmn0002 0015plusmn0002 001 0plusmn0001 0008plusmn0001 0004plusmn0001 0017plusmn0004
Table 3- REE abundances Lgg) ofthe investigated NIS T SRMJ633 C l Fl A h a o a ty s
NBS SRM 1633a This work Found
Element Rif 28 Rif 29 La 82plusmn02 791plusmn01 Ce 1755plusmn04 180 1683plusmn16 Pr 201plusmn09 - -N d 767plusmn03 - 757plusmn20 Sm 176plusmn02 - 1683plusmn020 Eu 367plusmn004 4 358plusmn007 Gd 169plusmn03 - -Tb 240plusmn004 - 238plusmn007 Dy 156plusmn06 - -Ho 381plusmn004 - -Er 83plusmn04 - -T m 123plusmn004 -Yb 768plusmn005 - 750+013 Lu 1190plusmn0006 - 1075plusmn0013
Table 4- Some useful parameters based on REEfor the different w h bl h u d b zte mar e quarnes in t e e iterranean asin
Quarries LREEr (1-gg) LREEL (1-gg) LREEH (1-gg) ~REE l ~REEH EuEu
Carrara 352plusmn009 283plusmn008 073+001 401plusmn009 030plusmn004 Hymetto 51+03 41plusmn02 102+001 40plusmn02 037plusmn006 Naxos 84 + 04 78 plusmn 04 060 plusmn 002 131 + 04 045plusmn008 Paros 60 plusmn 02 54 plusmn 02 064 + 002 84 plusmn 02 046plusmn005 Pentelico 51 + 04 44 + 04 068 + 001 65 plusmn 04 UogravetgtplusmnUU~
Thassos 588 plusmn 001 4764 + 0005 1113 plusmn 0008 428 + 003 032plusmn004 Afyon 333 plusmn 007 261 + 005 072 + 002 235 plusmn 009 055+007 Aphrodisias 106 + 06 95 + 02 110plusmn003 859 + 004 066plusmn005 Denizli 52 + 01 47+01 055 plusmn 001 92 + 01 044plusmn003 Marmara 75 + 02 63 + 03 11 plusmn 01 56 + 02 512plusmn009 U~ak 150 plusmn 007 064 plusmn 004 087 plusmn 004 074 + 009 032plusmn004
3 Results and discussion
REE contents of the investigated marbles are reported in Table 2 Samples have been grouped according to the quarry and reported values are the averages and the standard deviations often or more independent determinations for all samples ofthe same site Analytical precision is usually below 8 An evaluation ofthe accuracy ofthe method can be obtained by looking at the data on NIST Standard Reference Materia 1633a Coal Fly Ash reported in Table 3 and comparing them with existing values in the literature2829
The data being the average of20 independent runs agree very well and validate the reliability ofthe method More information is obtained if some parameters based on REE concentration for all samples are considered the sum ofmeasured REE concentrations (IREEr) the sum ofthe concentrations oflight REE (IREEL) the sum ofthe concentrations of heavy REE (IHREEH) the ratio of REEL to REEH All samples showing a light REE (La-Eu) enrichment compared to the heavy ones (Gd-Lu)
426
Sessi an 82 - Evaluation of damage restoration and conservati an of monuments buildings and historical garden s
Discriminant power of REEs to distinguish the source origin of white marble in the Mediterranean basin had been evidentiated to compute Hotellings (T2 test) for matched group designs using the RELIABILITY routine of SPSS30
Differences in the values of LREEr a statistica meaningful differences were obtained in 95 confidence leve of cases in the values of L REE L a statistica meaningful differences were obtained in 93 l confidence leve of cases the values of REEH a statistica meaningful differences were obtained in 89 confidence leve of cases and the values of LREEdLREEH a statistica meaningful differences w ere obtained in 90 confidence leve of cases Ali of them show also the so-called Eu negative anomaly the intensity of this anomaly is evaluated in terms of depth expressed as the ratio EuEu of the normalized Eu content to the one Eu obtained as the geometrica mean of the normalized content of the adjacent elements Sm and Gd as shown in Table 4 Not is a good discriminate parameter for quarries because depend the redox conditions This result therefore aimed to apply experience in marble provenancing by RNAA acquired to study the marble provenance of veiled Aphrodite statue of the Palazzo Ducale in Mantua (Italy) one of the few pieces not sold to Charles I of England (1627-1628) and one of the few to escape the dispersion following the sack of the Lanzichenecchi in 1630 and 1631 31
The samples were provided inthe form of small fragments from two areas of a sculpture (C1 and C2) and about 800 mg of powdered marble was obtained from them usually by drilling using a standard 5 mm masonry (tungsten carbide) bit The initial drillings were discarded to avoid materia that may have been modified by weathering processes Marble samples were ground (SI 00 mesh) and homogeneised and 05 g w ere submitted to RNAA REE content are given in table 5 A close examination of the REE data allows the identification of some parameters that can be used t o discriminate the white marble quarries ofthe Mediterranean basin (Table 6) The values ofthis quantity for the marble samples from the veiled Aphrodite are very similar to the one ofthe Paros quarrying
Table 5- Average and standard deviation REE conteni (pglg) ofthe veiled Aphrodite
ttemem 1(1 IC2
La 147plusmn009 146plusmn006 Ce 25plusmn01 24plusmn01 Pr 026plusmn001 027plusmn001 N d 095plusmn001 096plusmn002 Sm 017plusmn001 017plusmn002 Eu 0056plusmn0006 0061plusmn0002 Gd 015plusmn001 015plusmn001 Tb 0025plusmn0002 0025plusmn0001 Dy 019plusmn001 019plusmn001 Ho 0033plusmn0002 0033plusmn0002 Er 0098plusmn0003 0099plusmn0003 T m 0016plusmn0002 0016plusmn0002 Yb 0063plusmn0002 0065plusmn0004 Lu 0013plusmn0002 0014plusmn0001
Table 6-Statue EuEu
C1 076plusmn003 C2 066plusmn008
4 Conclusions
The routine neutron activation analysis of marble standard samples within a given irradiation batch has demonstrated the stability of the counting system and the reproducibility of the neutron activation technique The severa batch es of samples were analysed over the course of about 25 years The replicate analysis of the quarries samples some ten years apart also confirms the reproducibility of the technique In conclusion some basic provenancing procedures by the evaluation ofthe distribution ofthe REE especially may be confidently used
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Session B2 - Evaluation of damage restoration and conservation ofmonuments buildings and historical gardens
5 References l Manfra L Masi U Turi B (1975) Archaeometry 17215-221 2 Herz N Dean NE (1986) Applied Geochemistry l 139-151 3 Herz N(l987) Archaeometry 2935-43 4 HerzN(l992)Archaeometry 34185-194 5 Dean NE (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 315-323 p 6 Germann K Gruben G Knoll H Valis V Winkler FJ (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 251-262 p 7 Lazzarini L Mariottini M Pecorara M Pensabene P (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 399-410 p
8 Lazzarini L Masi U Tucci P (1995) in The Study of Marble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd Londonl61-169 p
9 Moens L Roos P De Rudder J De Paepe P Van Hende J Waelkens M (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 243-250 p
10 Roos P Moens L De Rudder J De Paepe P Van Hende J Waelkens M(l988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 263-272 p
llMeloni S Oddone M Zezza U (1995) in The Study of Marble and other Stones used in Antiquity (Y Maniatis N Heamp Y Basiakos eds) Archetype Publications Ltd Londonl81-186 p
12Asgari N Matthews KJ in The Study ofMarble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd Londonl23-129 p
13 Jongste PFB Jansen JB Moens L De Paepe P(l995) in The Study of Marble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd London 143-150 p
14 Lapuente P Turi B (1995) Science and Technology for Cultura Heritage 4 33-42 15 Castorina F Preite Martinez M Turi B (1997) Science and Technology for Cultura Heritage 6145-150 16 Barbin V Zezza U Pardo E S (1995) in The Study ofMarble and other Stones used in Antiquity (Y Maniatis
N Herz Y Basiakos eds) Archetype Publications Ltd London 131-135p 17 Blanc P (1995) in The Study ofMarble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos
eds) Archetype Publications Ltd London137-14lp 18 Attanasio D Brilli M Bruno M (2008) Archaeometry 50 747-774 19 Biricotti F Severi M Valeri C (2000) Abstract from ASMOSIA 2000 Venice 15-18 June 2000 20 Van der Merwe N Herrmann J Newman R Tykot R and Herz N (1995) in The Study of Marble and
Other Stones Used in Antiquity Asmosia 3 Athens (Y Maniatis N Herz and Y Basiakos eds) Archetype Publications Ltd London 187-198p
21 Capedri S Venturelli G Photiades A (2004) Joumal ofCultural Heritage 5 27-47 22Barbin V Bums S Decrouez D Oddone M Zezza U (1991) in the 2nd Intemational Symposium for the
Conservation of Monuments in the Mediterranean Basin (D Decrouez J Chamay and F Zezza eds) Gegraveneva Ville de Gegraveneve 47-62 p
23 Meloni S Oddone M Zezza 0(1995) in The Study ofMarble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd London 181-186 pp
24 Rollinson HR(l993)Using geochemical data Evaluation presentation interpretation Longman Harlow (UK) 51 O 25 Oddone M Meloni S Genova N (1984) Inorganica Chimica Acta 94 283-290 26 Monna D Pensabene P Sodini JP (1985) Studi Miscellanei26 28-29 27 Jaffrezic H (1976) Talanta 23 497-501 28 National Bureau of Standard Certificate of analysis SRM 1633a Trace Elements in Coal Fly Ash
Gaithersburg MD (USA) 1985 29 Korotev RL (1987) J Radioanal Nucl Chem 110 179-189 30 SPSS 17 for Windows SPSS Inc 2009 31 Gorrini ME (2008) Flos Italiae 8 333-358
428
Sessi an B2 - Evauation of damage restoration and conservation of monuments buildings and historical gardens
Fig 1- Map ofthe marble quarries
Table l- REEs Nuclear data Statue LREET (jgg) LREEL (lgg) LREEH (jgg) L RE EL l EuEu
L RE EH C1 60plusmn007 535plusmn009 063plusmn002 85plusmn04 076plusmn003
C2 59plusmn03 53plusmn03 064plusmn004 82plusmn01 066plusmn008
22 Reference standards A synthetic reference standard was prepared by adding known amounts of the REE to pure CaC03bull In addition NIST SRM1633a Coal Fly Ash 2 was used in marble analysis
23 Irradiations and cooling Marble samples and reference standards were irradiated in the 250 Kw TRIGA MARK II reactor of the University ofPavia at a thermal neutron flux of about lxl0 12 n cm-2smiddot Irradiation time was 20 hours a second irradiation of 15 minutes was carried out at a thermal flux ofabout 2xl0 12 n cm-2s1 after the radiochemical separation step for the determination of short-lived radionuclides and the evaluation ofthe chemical yield After the flrst irradiation samples and reference standard were left to decay for 3 days before being processed after the second irradiation samples were left to decay for l hour before being submitted to y-spectrometry
24 Radioactivity measurement Induced radioactivity was measured by y-ray spectrometry using a HP-Ge detector coupled to a computer assisted OR TEC spectral analysis system The y-rays utilized in this work are reported in Table l
25 Radiochemical procedure After the decay period the irradiated samples were transferred to a beaker and known amounts (lO mg) of Se and REE (except La Nd Pr Dy and Er) added as carriers The mixture was then submitted to an acid attack with 4M CH3COOH solution The precipitation of REE-fluorides was carried out by adding a mixture of 50 HF and 10 NH4F solutions together with La+3 carrier solution The fluorides were separated dissolved with a HN03 solution and borie acid saturated solution and again precipitated as described above without La+3 carrier addition The
425
Session B2 - Evaluation of darnage restoration and conservation ojrnonurnents buildings and historical gardens
fluorides were then dissolved as described and brought to a 1 O cm3 volume a 9 cm3 aliquot was used for radioactivity measurement and the remaining 1 cm3 was re-irradiated together with REE reference standard for the determination of N d Pr Dy Er and the evaluation of the chemical yield The latter resulted to be throughout the present investigation equa to 98plusmn225
Table 2- Average and standard deviation REE content (pg1) ofthe investigated samplesfrom different quarries ltalian Greek Turkish
Element
Carrara (80) Hymetto(10) Naxos (10) Paros (25) Pentelico (30) Thassos (10) Afyon(10) Aphrodisias (25) Denizli (20) Maramara (30) U~ak (10)
La 089plusmn008 132plusmn007 209plusmn005 154plusmn008 149plusmn007 1239plusmn0002 0701plusmn0002 244plusmn005 147plusmn009 169plusmn009 0140plusmn0009
Ce 106plusmn004 170plusmn005 414plusmn009 246plusmn006 1413plusmn0006 2033plusmn0001 108plusmn004 299plusmn003 167plusmn009 205plusmn007 0214plusmn0005
Pr 016plusmn006 051plusmn003 0376plusmn0007 026plusmn001 0222plusmn0007 0222plusmn0002 0111plusmn0004 087plusmn002 0381 plusmn0009 0425plusmn0007 0018plusmn0006
N d 056plusmn007 0334plusmn0008 110plusmn007 0956plusmn0007 106plusmn008 0992plusmn0001 0563plusmn0005 289plusmn006 0964plusmn0006 197plusmn004 0086plusmn0001
Sm 0171plusmn0008 0271plusmn0004 0096plusmn0003 0170plusmn0006 017plusmn003 0278plusmn0001 0157plusmn0003 0265plusmn0007 0178plusmn0005 0211plusmn0006 0184plusmn0002
Eu 0026plusmn0005 0041plusmn0005 0025plusmn0002 0052plusmn0003 0047plusmn0003 0043plusmn0003 0049plusmn0001 0071plusmn0004 0038plusmn0009 0487plusmn0004 0031plusmn0005
Gd 0163plusmn0003 0266plusmn0002 0146plusmn0005 0145plusmn0005 0150plusmn0005 0345plusmn0003 020plusmn001 0261plusmn0005 0161plusmn0003 0195plusmn0009 0240plusmn0005
Tb 0030plusmn0008 0043plusmn0003 0030plusmn0003 0026plusmn0002 0021plusmn0002 0042plusmn0008 0030plusmn0004 0052plusmn0003 0025plusmn0004 0035plusmn0004 0038plusmn0001
Dy 0169plusmn0009 0294plusmn0004 0199plusmn0009 0119plusmn0004 021 0plusmn0003 0250plusmn0005 0179plusmn0009 0324plusmn0003 0141plusmn0005 0217plusmn0014 0229plusmn0002
Ho 0045plusmn0005 0052plusmn0001 0030plusmn0003 0033plusmn0002 0033plusmn0004 0063plusmn0001 0039plusmn0006 0247plusmn0004 0035plusmn0003 0035plusmn0003 0049plusmn0001
Er 0117plusmn0004 0145plusmn0003 0079plusmn0011 0110plusmn0007 01 00plusmn0005 0156plusmn0002 0095plusmn0001 0202plusmn0007 0069plusmn0004 0087plusmn0005 0121plusmn0002
T m 0021plusmn0008 0022plusmn0001 0014plusmn0002 0017plusmn0002 0018plusmn0004 0025plusmn0001 0015plusmn0003 0024plusmn0001 0012plusmn0004 0009plusmn0002 0019plusmn0008
Yb 0115plusmn0041 0133plusmn0004 0072plusmn0008 0064plusmn0004 0073plusmn0006 0164plusmn0002 0097plusmn0001 027plusmn004 0053plusmn0005 0035plusmn0005 0122plusmn0007
Lu 0017plusmn0005 0021plusmn0001 0011 plusmn0001 0014plusmn0002 0021plusmn0004 0025plusmn0002 0015plusmn0002 001 0plusmn0001 0008plusmn0001 0004plusmn0001 0017plusmn0004
Table 3- REE abundances Lgg) ofthe investigated NIS T SRMJ633 C l Fl A h a o a ty s
NBS SRM 1633a This work Found
Element Rif 28 Rif 29 La 82plusmn02 791plusmn01 Ce 1755plusmn04 180 1683plusmn16 Pr 201plusmn09 - -N d 767plusmn03 - 757plusmn20 Sm 176plusmn02 - 1683plusmn020 Eu 367plusmn004 4 358plusmn007 Gd 169plusmn03 - -Tb 240plusmn004 - 238plusmn007 Dy 156plusmn06 - -Ho 381plusmn004 - -Er 83plusmn04 - -T m 123plusmn004 -Yb 768plusmn005 - 750+013 Lu 1190plusmn0006 - 1075plusmn0013
Table 4- Some useful parameters based on REEfor the different w h bl h u d b zte mar e quarnes in t e e iterranean asin
Quarries LREEr (1-gg) LREEL (1-gg) LREEH (1-gg) ~REE l ~REEH EuEu
Carrara 352plusmn009 283plusmn008 073+001 401plusmn009 030plusmn004 Hymetto 51+03 41plusmn02 102+001 40plusmn02 037plusmn006 Naxos 84 + 04 78 plusmn 04 060 plusmn 002 131 + 04 045plusmn008 Paros 60 plusmn 02 54 plusmn 02 064 + 002 84 plusmn 02 046plusmn005 Pentelico 51 + 04 44 + 04 068 + 001 65 plusmn 04 UogravetgtplusmnUU~
Thassos 588 plusmn 001 4764 + 0005 1113 plusmn 0008 428 + 003 032plusmn004 Afyon 333 plusmn 007 261 + 005 072 + 002 235 plusmn 009 055+007 Aphrodisias 106 + 06 95 + 02 110plusmn003 859 + 004 066plusmn005 Denizli 52 + 01 47+01 055 plusmn 001 92 + 01 044plusmn003 Marmara 75 + 02 63 + 03 11 plusmn 01 56 + 02 512plusmn009 U~ak 150 plusmn 007 064 plusmn 004 087 plusmn 004 074 + 009 032plusmn004
3 Results and discussion
REE contents of the investigated marbles are reported in Table 2 Samples have been grouped according to the quarry and reported values are the averages and the standard deviations often or more independent determinations for all samples ofthe same site Analytical precision is usually below 8 An evaluation ofthe accuracy ofthe method can be obtained by looking at the data on NIST Standard Reference Materia 1633a Coal Fly Ash reported in Table 3 and comparing them with existing values in the literature2829
The data being the average of20 independent runs agree very well and validate the reliability ofthe method More information is obtained if some parameters based on REE concentration for all samples are considered the sum ofmeasured REE concentrations (IREEr) the sum ofthe concentrations oflight REE (IREEL) the sum ofthe concentrations of heavy REE (IHREEH) the ratio of REEL to REEH All samples showing a light REE (La-Eu) enrichment compared to the heavy ones (Gd-Lu)
426
Sessi an 82 - Evaluation of damage restoration and conservati an of monuments buildings and historical garden s
Discriminant power of REEs to distinguish the source origin of white marble in the Mediterranean basin had been evidentiated to compute Hotellings (T2 test) for matched group designs using the RELIABILITY routine of SPSS30
Differences in the values of LREEr a statistica meaningful differences were obtained in 95 confidence leve of cases in the values of L REE L a statistica meaningful differences were obtained in 93 l confidence leve of cases the values of REEH a statistica meaningful differences were obtained in 89 confidence leve of cases and the values of LREEdLREEH a statistica meaningful differences w ere obtained in 90 confidence leve of cases Ali of them show also the so-called Eu negative anomaly the intensity of this anomaly is evaluated in terms of depth expressed as the ratio EuEu of the normalized Eu content to the one Eu obtained as the geometrica mean of the normalized content of the adjacent elements Sm and Gd as shown in Table 4 Not is a good discriminate parameter for quarries because depend the redox conditions This result therefore aimed to apply experience in marble provenancing by RNAA acquired to study the marble provenance of veiled Aphrodite statue of the Palazzo Ducale in Mantua (Italy) one of the few pieces not sold to Charles I of England (1627-1628) and one of the few to escape the dispersion following the sack of the Lanzichenecchi in 1630 and 1631 31
The samples were provided inthe form of small fragments from two areas of a sculpture (C1 and C2) and about 800 mg of powdered marble was obtained from them usually by drilling using a standard 5 mm masonry (tungsten carbide) bit The initial drillings were discarded to avoid materia that may have been modified by weathering processes Marble samples were ground (SI 00 mesh) and homogeneised and 05 g w ere submitted to RNAA REE content are given in table 5 A close examination of the REE data allows the identification of some parameters that can be used t o discriminate the white marble quarries ofthe Mediterranean basin (Table 6) The values ofthis quantity for the marble samples from the veiled Aphrodite are very similar to the one ofthe Paros quarrying
Table 5- Average and standard deviation REE conteni (pglg) ofthe veiled Aphrodite
ttemem 1(1 IC2
La 147plusmn009 146plusmn006 Ce 25plusmn01 24plusmn01 Pr 026plusmn001 027plusmn001 N d 095plusmn001 096plusmn002 Sm 017plusmn001 017plusmn002 Eu 0056plusmn0006 0061plusmn0002 Gd 015plusmn001 015plusmn001 Tb 0025plusmn0002 0025plusmn0001 Dy 019plusmn001 019plusmn001 Ho 0033plusmn0002 0033plusmn0002 Er 0098plusmn0003 0099plusmn0003 T m 0016plusmn0002 0016plusmn0002 Yb 0063plusmn0002 0065plusmn0004 Lu 0013plusmn0002 0014plusmn0001
Table 6-Statue EuEu
C1 076plusmn003 C2 066plusmn008
4 Conclusions
The routine neutron activation analysis of marble standard samples within a given irradiation batch has demonstrated the stability of the counting system and the reproducibility of the neutron activation technique The severa batch es of samples were analysed over the course of about 25 years The replicate analysis of the quarries samples some ten years apart also confirms the reproducibility of the technique In conclusion some basic provenancing procedures by the evaluation ofthe distribution ofthe REE especially may be confidently used
427
Session B2 - Evaluation of damage restoration and conservation ofmonuments buildings and historical gardens
5 References l Manfra L Masi U Turi B (1975) Archaeometry 17215-221 2 Herz N Dean NE (1986) Applied Geochemistry l 139-151 3 Herz N(l987) Archaeometry 2935-43 4 HerzN(l992)Archaeometry 34185-194 5 Dean NE (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 315-323 p 6 Germann K Gruben G Knoll H Valis V Winkler FJ (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 251-262 p 7 Lazzarini L Mariottini M Pecorara M Pensabene P (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 399-410 p
8 Lazzarini L Masi U Tucci P (1995) in The Study of Marble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd Londonl61-169 p
9 Moens L Roos P De Rudder J De Paepe P Van Hende J Waelkens M (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 243-250 p
10 Roos P Moens L De Rudder J De Paepe P Van Hende J Waelkens M(l988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 263-272 p
llMeloni S Oddone M Zezza U (1995) in The Study of Marble and other Stones used in Antiquity (Y Maniatis N Heamp Y Basiakos eds) Archetype Publications Ltd Londonl81-186 p
12Asgari N Matthews KJ in The Study ofMarble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd Londonl23-129 p
13 Jongste PFB Jansen JB Moens L De Paepe P(l995) in The Study of Marble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd London 143-150 p
14 Lapuente P Turi B (1995) Science and Technology for Cultura Heritage 4 33-42 15 Castorina F Preite Martinez M Turi B (1997) Science and Technology for Cultura Heritage 6145-150 16 Barbin V Zezza U Pardo E S (1995) in The Study ofMarble and other Stones used in Antiquity (Y Maniatis
N Herz Y Basiakos eds) Archetype Publications Ltd London 131-135p 17 Blanc P (1995) in The Study ofMarble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos
eds) Archetype Publications Ltd London137-14lp 18 Attanasio D Brilli M Bruno M (2008) Archaeometry 50 747-774 19 Biricotti F Severi M Valeri C (2000) Abstract from ASMOSIA 2000 Venice 15-18 June 2000 20 Van der Merwe N Herrmann J Newman R Tykot R and Herz N (1995) in The Study of Marble and
Other Stones Used in Antiquity Asmosia 3 Athens (Y Maniatis N Herz and Y Basiakos eds) Archetype Publications Ltd London 187-198p
21 Capedri S Venturelli G Photiades A (2004) Joumal ofCultural Heritage 5 27-47 22Barbin V Bums S Decrouez D Oddone M Zezza U (1991) in the 2nd Intemational Symposium for the
Conservation of Monuments in the Mediterranean Basin (D Decrouez J Chamay and F Zezza eds) Gegraveneva Ville de Gegraveneve 47-62 p
23 Meloni S Oddone M Zezza 0(1995) in The Study ofMarble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd London 181-186 pp
24 Rollinson HR(l993)Using geochemical data Evaluation presentation interpretation Longman Harlow (UK) 51 O 25 Oddone M Meloni S Genova N (1984) Inorganica Chimica Acta 94 283-290 26 Monna D Pensabene P Sodini JP (1985) Studi Miscellanei26 28-29 27 Jaffrezic H (1976) Talanta 23 497-501 28 National Bureau of Standard Certificate of analysis SRM 1633a Trace Elements in Coal Fly Ash
Gaithersburg MD (USA) 1985 29 Korotev RL (1987) J Radioanal Nucl Chem 110 179-189 30 SPSS 17 for Windows SPSS Inc 2009 31 Gorrini ME (2008) Flos Italiae 8 333-358
428
Session B2 - Evaluation of darnage restoration and conservation ojrnonurnents buildings and historical gardens
fluorides were then dissolved as described and brought to a 1 O cm3 volume a 9 cm3 aliquot was used for radioactivity measurement and the remaining 1 cm3 was re-irradiated together with REE reference standard for the determination of N d Pr Dy Er and the evaluation of the chemical yield The latter resulted to be throughout the present investigation equa to 98plusmn225
Table 2- Average and standard deviation REE content (pg1) ofthe investigated samplesfrom different quarries ltalian Greek Turkish
Element
Carrara (80) Hymetto(10) Naxos (10) Paros (25) Pentelico (30) Thassos (10) Afyon(10) Aphrodisias (25) Denizli (20) Maramara (30) U~ak (10)
La 089plusmn008 132plusmn007 209plusmn005 154plusmn008 149plusmn007 1239plusmn0002 0701plusmn0002 244plusmn005 147plusmn009 169plusmn009 0140plusmn0009
Ce 106plusmn004 170plusmn005 414plusmn009 246plusmn006 1413plusmn0006 2033plusmn0001 108plusmn004 299plusmn003 167plusmn009 205plusmn007 0214plusmn0005
Pr 016plusmn006 051plusmn003 0376plusmn0007 026plusmn001 0222plusmn0007 0222plusmn0002 0111plusmn0004 087plusmn002 0381 plusmn0009 0425plusmn0007 0018plusmn0006
N d 056plusmn007 0334plusmn0008 110plusmn007 0956plusmn0007 106plusmn008 0992plusmn0001 0563plusmn0005 289plusmn006 0964plusmn0006 197plusmn004 0086plusmn0001
Sm 0171plusmn0008 0271plusmn0004 0096plusmn0003 0170plusmn0006 017plusmn003 0278plusmn0001 0157plusmn0003 0265plusmn0007 0178plusmn0005 0211plusmn0006 0184plusmn0002
Eu 0026plusmn0005 0041plusmn0005 0025plusmn0002 0052plusmn0003 0047plusmn0003 0043plusmn0003 0049plusmn0001 0071plusmn0004 0038plusmn0009 0487plusmn0004 0031plusmn0005
Gd 0163plusmn0003 0266plusmn0002 0146plusmn0005 0145plusmn0005 0150plusmn0005 0345plusmn0003 020plusmn001 0261plusmn0005 0161plusmn0003 0195plusmn0009 0240plusmn0005
Tb 0030plusmn0008 0043plusmn0003 0030plusmn0003 0026plusmn0002 0021plusmn0002 0042plusmn0008 0030plusmn0004 0052plusmn0003 0025plusmn0004 0035plusmn0004 0038plusmn0001
Dy 0169plusmn0009 0294plusmn0004 0199plusmn0009 0119plusmn0004 021 0plusmn0003 0250plusmn0005 0179plusmn0009 0324plusmn0003 0141plusmn0005 0217plusmn0014 0229plusmn0002
Ho 0045plusmn0005 0052plusmn0001 0030plusmn0003 0033plusmn0002 0033plusmn0004 0063plusmn0001 0039plusmn0006 0247plusmn0004 0035plusmn0003 0035plusmn0003 0049plusmn0001
Er 0117plusmn0004 0145plusmn0003 0079plusmn0011 0110plusmn0007 01 00plusmn0005 0156plusmn0002 0095plusmn0001 0202plusmn0007 0069plusmn0004 0087plusmn0005 0121plusmn0002
T m 0021plusmn0008 0022plusmn0001 0014plusmn0002 0017plusmn0002 0018plusmn0004 0025plusmn0001 0015plusmn0003 0024plusmn0001 0012plusmn0004 0009plusmn0002 0019plusmn0008
Yb 0115plusmn0041 0133plusmn0004 0072plusmn0008 0064plusmn0004 0073plusmn0006 0164plusmn0002 0097plusmn0001 027plusmn004 0053plusmn0005 0035plusmn0005 0122plusmn0007
Lu 0017plusmn0005 0021plusmn0001 0011 plusmn0001 0014plusmn0002 0021plusmn0004 0025plusmn0002 0015plusmn0002 001 0plusmn0001 0008plusmn0001 0004plusmn0001 0017plusmn0004
Table 3- REE abundances Lgg) ofthe investigated NIS T SRMJ633 C l Fl A h a o a ty s
NBS SRM 1633a This work Found
Element Rif 28 Rif 29 La 82plusmn02 791plusmn01 Ce 1755plusmn04 180 1683plusmn16 Pr 201plusmn09 - -N d 767plusmn03 - 757plusmn20 Sm 176plusmn02 - 1683plusmn020 Eu 367plusmn004 4 358plusmn007 Gd 169plusmn03 - -Tb 240plusmn004 - 238plusmn007 Dy 156plusmn06 - -Ho 381plusmn004 - -Er 83plusmn04 - -T m 123plusmn004 -Yb 768plusmn005 - 750+013 Lu 1190plusmn0006 - 1075plusmn0013
Table 4- Some useful parameters based on REEfor the different w h bl h u d b zte mar e quarnes in t e e iterranean asin
Quarries LREEr (1-gg) LREEL (1-gg) LREEH (1-gg) ~REE l ~REEH EuEu
Carrara 352plusmn009 283plusmn008 073+001 401plusmn009 030plusmn004 Hymetto 51+03 41plusmn02 102+001 40plusmn02 037plusmn006 Naxos 84 + 04 78 plusmn 04 060 plusmn 002 131 + 04 045plusmn008 Paros 60 plusmn 02 54 plusmn 02 064 + 002 84 plusmn 02 046plusmn005 Pentelico 51 + 04 44 + 04 068 + 001 65 plusmn 04 UogravetgtplusmnUU~
Thassos 588 plusmn 001 4764 + 0005 1113 plusmn 0008 428 + 003 032plusmn004 Afyon 333 plusmn 007 261 + 005 072 + 002 235 plusmn 009 055+007 Aphrodisias 106 + 06 95 + 02 110plusmn003 859 + 004 066plusmn005 Denizli 52 + 01 47+01 055 plusmn 001 92 + 01 044plusmn003 Marmara 75 + 02 63 + 03 11 plusmn 01 56 + 02 512plusmn009 U~ak 150 plusmn 007 064 plusmn 004 087 plusmn 004 074 + 009 032plusmn004
3 Results and discussion
REE contents of the investigated marbles are reported in Table 2 Samples have been grouped according to the quarry and reported values are the averages and the standard deviations often or more independent determinations for all samples ofthe same site Analytical precision is usually below 8 An evaluation ofthe accuracy ofthe method can be obtained by looking at the data on NIST Standard Reference Materia 1633a Coal Fly Ash reported in Table 3 and comparing them with existing values in the literature2829
The data being the average of20 independent runs agree very well and validate the reliability ofthe method More information is obtained if some parameters based on REE concentration for all samples are considered the sum ofmeasured REE concentrations (IREEr) the sum ofthe concentrations oflight REE (IREEL) the sum ofthe concentrations of heavy REE (IHREEH) the ratio of REEL to REEH All samples showing a light REE (La-Eu) enrichment compared to the heavy ones (Gd-Lu)
426
Sessi an 82 - Evaluation of damage restoration and conservati an of monuments buildings and historical garden s
Discriminant power of REEs to distinguish the source origin of white marble in the Mediterranean basin had been evidentiated to compute Hotellings (T2 test) for matched group designs using the RELIABILITY routine of SPSS30
Differences in the values of LREEr a statistica meaningful differences were obtained in 95 confidence leve of cases in the values of L REE L a statistica meaningful differences were obtained in 93 l confidence leve of cases the values of REEH a statistica meaningful differences were obtained in 89 confidence leve of cases and the values of LREEdLREEH a statistica meaningful differences w ere obtained in 90 confidence leve of cases Ali of them show also the so-called Eu negative anomaly the intensity of this anomaly is evaluated in terms of depth expressed as the ratio EuEu of the normalized Eu content to the one Eu obtained as the geometrica mean of the normalized content of the adjacent elements Sm and Gd as shown in Table 4 Not is a good discriminate parameter for quarries because depend the redox conditions This result therefore aimed to apply experience in marble provenancing by RNAA acquired to study the marble provenance of veiled Aphrodite statue of the Palazzo Ducale in Mantua (Italy) one of the few pieces not sold to Charles I of England (1627-1628) and one of the few to escape the dispersion following the sack of the Lanzichenecchi in 1630 and 1631 31
The samples were provided inthe form of small fragments from two areas of a sculpture (C1 and C2) and about 800 mg of powdered marble was obtained from them usually by drilling using a standard 5 mm masonry (tungsten carbide) bit The initial drillings were discarded to avoid materia that may have been modified by weathering processes Marble samples were ground (SI 00 mesh) and homogeneised and 05 g w ere submitted to RNAA REE content are given in table 5 A close examination of the REE data allows the identification of some parameters that can be used t o discriminate the white marble quarries ofthe Mediterranean basin (Table 6) The values ofthis quantity for the marble samples from the veiled Aphrodite are very similar to the one ofthe Paros quarrying
Table 5- Average and standard deviation REE conteni (pglg) ofthe veiled Aphrodite
ttemem 1(1 IC2
La 147plusmn009 146plusmn006 Ce 25plusmn01 24plusmn01 Pr 026plusmn001 027plusmn001 N d 095plusmn001 096plusmn002 Sm 017plusmn001 017plusmn002 Eu 0056plusmn0006 0061plusmn0002 Gd 015plusmn001 015plusmn001 Tb 0025plusmn0002 0025plusmn0001 Dy 019plusmn001 019plusmn001 Ho 0033plusmn0002 0033plusmn0002 Er 0098plusmn0003 0099plusmn0003 T m 0016plusmn0002 0016plusmn0002 Yb 0063plusmn0002 0065plusmn0004 Lu 0013plusmn0002 0014plusmn0001
Table 6-Statue EuEu
C1 076plusmn003 C2 066plusmn008
4 Conclusions
The routine neutron activation analysis of marble standard samples within a given irradiation batch has demonstrated the stability of the counting system and the reproducibility of the neutron activation technique The severa batch es of samples were analysed over the course of about 25 years The replicate analysis of the quarries samples some ten years apart also confirms the reproducibility of the technique In conclusion some basic provenancing procedures by the evaluation ofthe distribution ofthe REE especially may be confidently used
427
Session B2 - Evaluation of damage restoration and conservation ofmonuments buildings and historical gardens
5 References l Manfra L Masi U Turi B (1975) Archaeometry 17215-221 2 Herz N Dean NE (1986) Applied Geochemistry l 139-151 3 Herz N(l987) Archaeometry 2935-43 4 HerzN(l992)Archaeometry 34185-194 5 Dean NE (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 315-323 p 6 Germann K Gruben G Knoll H Valis V Winkler FJ (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 251-262 p 7 Lazzarini L Mariottini M Pecorara M Pensabene P (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 399-410 p
8 Lazzarini L Masi U Tucci P (1995) in The Study of Marble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd Londonl61-169 p
9 Moens L Roos P De Rudder J De Paepe P Van Hende J Waelkens M (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 243-250 p
10 Roos P Moens L De Rudder J De Paepe P Van Hende J Waelkens M(l988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 263-272 p
llMeloni S Oddone M Zezza U (1995) in The Study of Marble and other Stones used in Antiquity (Y Maniatis N Heamp Y Basiakos eds) Archetype Publications Ltd Londonl81-186 p
12Asgari N Matthews KJ in The Study ofMarble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd Londonl23-129 p
13 Jongste PFB Jansen JB Moens L De Paepe P(l995) in The Study of Marble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd London 143-150 p
14 Lapuente P Turi B (1995) Science and Technology for Cultura Heritage 4 33-42 15 Castorina F Preite Martinez M Turi B (1997) Science and Technology for Cultura Heritage 6145-150 16 Barbin V Zezza U Pardo E S (1995) in The Study ofMarble and other Stones used in Antiquity (Y Maniatis
N Herz Y Basiakos eds) Archetype Publications Ltd London 131-135p 17 Blanc P (1995) in The Study ofMarble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos
eds) Archetype Publications Ltd London137-14lp 18 Attanasio D Brilli M Bruno M (2008) Archaeometry 50 747-774 19 Biricotti F Severi M Valeri C (2000) Abstract from ASMOSIA 2000 Venice 15-18 June 2000 20 Van der Merwe N Herrmann J Newman R Tykot R and Herz N (1995) in The Study of Marble and
Other Stones Used in Antiquity Asmosia 3 Athens (Y Maniatis N Herz and Y Basiakos eds) Archetype Publications Ltd London 187-198p
21 Capedri S Venturelli G Photiades A (2004) Joumal ofCultural Heritage 5 27-47 22Barbin V Bums S Decrouez D Oddone M Zezza U (1991) in the 2nd Intemational Symposium for the
Conservation of Monuments in the Mediterranean Basin (D Decrouez J Chamay and F Zezza eds) Gegraveneva Ville de Gegraveneve 47-62 p
23 Meloni S Oddone M Zezza 0(1995) in The Study ofMarble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd London 181-186 pp
24 Rollinson HR(l993)Using geochemical data Evaluation presentation interpretation Longman Harlow (UK) 51 O 25 Oddone M Meloni S Genova N (1984) Inorganica Chimica Acta 94 283-290 26 Monna D Pensabene P Sodini JP (1985) Studi Miscellanei26 28-29 27 Jaffrezic H (1976) Talanta 23 497-501 28 National Bureau of Standard Certificate of analysis SRM 1633a Trace Elements in Coal Fly Ash
Gaithersburg MD (USA) 1985 29 Korotev RL (1987) J Radioanal Nucl Chem 110 179-189 30 SPSS 17 for Windows SPSS Inc 2009 31 Gorrini ME (2008) Flos Italiae 8 333-358
428
Sessi an 82 - Evaluation of damage restoration and conservati an of monuments buildings and historical garden s
Discriminant power of REEs to distinguish the source origin of white marble in the Mediterranean basin had been evidentiated to compute Hotellings (T2 test) for matched group designs using the RELIABILITY routine of SPSS30
Differences in the values of LREEr a statistica meaningful differences were obtained in 95 confidence leve of cases in the values of L REE L a statistica meaningful differences were obtained in 93 l confidence leve of cases the values of REEH a statistica meaningful differences were obtained in 89 confidence leve of cases and the values of LREEdLREEH a statistica meaningful differences w ere obtained in 90 confidence leve of cases Ali of them show also the so-called Eu negative anomaly the intensity of this anomaly is evaluated in terms of depth expressed as the ratio EuEu of the normalized Eu content to the one Eu obtained as the geometrica mean of the normalized content of the adjacent elements Sm and Gd as shown in Table 4 Not is a good discriminate parameter for quarries because depend the redox conditions This result therefore aimed to apply experience in marble provenancing by RNAA acquired to study the marble provenance of veiled Aphrodite statue of the Palazzo Ducale in Mantua (Italy) one of the few pieces not sold to Charles I of England (1627-1628) and one of the few to escape the dispersion following the sack of the Lanzichenecchi in 1630 and 1631 31
The samples were provided inthe form of small fragments from two areas of a sculpture (C1 and C2) and about 800 mg of powdered marble was obtained from them usually by drilling using a standard 5 mm masonry (tungsten carbide) bit The initial drillings were discarded to avoid materia that may have been modified by weathering processes Marble samples were ground (SI 00 mesh) and homogeneised and 05 g w ere submitted to RNAA REE content are given in table 5 A close examination of the REE data allows the identification of some parameters that can be used t o discriminate the white marble quarries ofthe Mediterranean basin (Table 6) The values ofthis quantity for the marble samples from the veiled Aphrodite are very similar to the one ofthe Paros quarrying
Table 5- Average and standard deviation REE conteni (pglg) ofthe veiled Aphrodite
ttemem 1(1 IC2
La 147plusmn009 146plusmn006 Ce 25plusmn01 24plusmn01 Pr 026plusmn001 027plusmn001 N d 095plusmn001 096plusmn002 Sm 017plusmn001 017plusmn002 Eu 0056plusmn0006 0061plusmn0002 Gd 015plusmn001 015plusmn001 Tb 0025plusmn0002 0025plusmn0001 Dy 019plusmn001 019plusmn001 Ho 0033plusmn0002 0033plusmn0002 Er 0098plusmn0003 0099plusmn0003 T m 0016plusmn0002 0016plusmn0002 Yb 0063plusmn0002 0065plusmn0004 Lu 0013plusmn0002 0014plusmn0001
Table 6-Statue EuEu
C1 076plusmn003 C2 066plusmn008
4 Conclusions
The routine neutron activation analysis of marble standard samples within a given irradiation batch has demonstrated the stability of the counting system and the reproducibility of the neutron activation technique The severa batch es of samples were analysed over the course of about 25 years The replicate analysis of the quarries samples some ten years apart also confirms the reproducibility of the technique In conclusion some basic provenancing procedures by the evaluation ofthe distribution ofthe REE especially may be confidently used
427
Session B2 - Evaluation of damage restoration and conservation ofmonuments buildings and historical gardens
5 References l Manfra L Masi U Turi B (1975) Archaeometry 17215-221 2 Herz N Dean NE (1986) Applied Geochemistry l 139-151 3 Herz N(l987) Archaeometry 2935-43 4 HerzN(l992)Archaeometry 34185-194 5 Dean NE (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 315-323 p 6 Germann K Gruben G Knoll H Valis V Winkler FJ (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 251-262 p 7 Lazzarini L Mariottini M Pecorara M Pensabene P (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 399-410 p
8 Lazzarini L Masi U Tucci P (1995) in The Study of Marble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd Londonl61-169 p
9 Moens L Roos P De Rudder J De Paepe P Van Hende J Waelkens M (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 243-250 p
10 Roos P Moens L De Rudder J De Paepe P Van Hende J Waelkens M(l988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 263-272 p
llMeloni S Oddone M Zezza U (1995) in The Study of Marble and other Stones used in Antiquity (Y Maniatis N Heamp Y Basiakos eds) Archetype Publications Ltd Londonl81-186 p
12Asgari N Matthews KJ in The Study ofMarble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd Londonl23-129 p
13 Jongste PFB Jansen JB Moens L De Paepe P(l995) in The Study of Marble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd London 143-150 p
14 Lapuente P Turi B (1995) Science and Technology for Cultura Heritage 4 33-42 15 Castorina F Preite Martinez M Turi B (1997) Science and Technology for Cultura Heritage 6145-150 16 Barbin V Zezza U Pardo E S (1995) in The Study ofMarble and other Stones used in Antiquity (Y Maniatis
N Herz Y Basiakos eds) Archetype Publications Ltd London 131-135p 17 Blanc P (1995) in The Study ofMarble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos
eds) Archetype Publications Ltd London137-14lp 18 Attanasio D Brilli M Bruno M (2008) Archaeometry 50 747-774 19 Biricotti F Severi M Valeri C (2000) Abstract from ASMOSIA 2000 Venice 15-18 June 2000 20 Van der Merwe N Herrmann J Newman R Tykot R and Herz N (1995) in The Study of Marble and
Other Stones Used in Antiquity Asmosia 3 Athens (Y Maniatis N Herz and Y Basiakos eds) Archetype Publications Ltd London 187-198p
21 Capedri S Venturelli G Photiades A (2004) Joumal ofCultural Heritage 5 27-47 22Barbin V Bums S Decrouez D Oddone M Zezza U (1991) in the 2nd Intemational Symposium for the
Conservation of Monuments in the Mediterranean Basin (D Decrouez J Chamay and F Zezza eds) Gegraveneva Ville de Gegraveneve 47-62 p
23 Meloni S Oddone M Zezza 0(1995) in The Study ofMarble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd London 181-186 pp
24 Rollinson HR(l993)Using geochemical data Evaluation presentation interpretation Longman Harlow (UK) 51 O 25 Oddone M Meloni S Genova N (1984) Inorganica Chimica Acta 94 283-290 26 Monna D Pensabene P Sodini JP (1985) Studi Miscellanei26 28-29 27 Jaffrezic H (1976) Talanta 23 497-501 28 National Bureau of Standard Certificate of analysis SRM 1633a Trace Elements in Coal Fly Ash
Gaithersburg MD (USA) 1985 29 Korotev RL (1987) J Radioanal Nucl Chem 110 179-189 30 SPSS 17 for Windows SPSS Inc 2009 31 Gorrini ME (2008) Flos Italiae 8 333-358
428
Session B2 - Evaluation of damage restoration and conservation ofmonuments buildings and historical gardens
5 References l Manfra L Masi U Turi B (1975) Archaeometry 17215-221 2 Herz N Dean NE (1986) Applied Geochemistry l 139-151 3 Herz N(l987) Archaeometry 2935-43 4 HerzN(l992)Archaeometry 34185-194 5 Dean NE (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 315-323 p 6 Germann K Gruben G Knoll H Valis V Winkler FJ (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 251-262 p 7 Lazzarini L Mariottini M Pecorara M Pensabene P (1988) in Classica Marble Geochemistry Technology Trade (N Herz M Waelkens eds) NATO ASI Series Series E Applied Sciences vol 153 Kluwer Academic Publishers Dordrecht 399-410 p
8 Lazzarini L Masi U Tucci P (1995) in The Study of Marble and other Stones used in Antiquity (Y Maniatis N Herz Y Basiakos eds) Archetype Publications Ltd Londonl61-169 p
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