The application of LIBS for the analysis of archaeological
ceramic and metal artifacts
Kristalia Melessanaki a,* , Maripaz Mateo a,1 , Susan C. Ferrence b , Philip P. Betancourt b , Demetrios Anglos a a Foundation for Research and Technology-Hellas (FORTH), Institute of Electronic Structure and Laser, P.O. Box 1527, 71110 Heraklion, Crete, Greece b Department of Art History, Temple University, Philadelphia, PA 19122, USA Abstract A bench-top laser-induced breakdown spectroscopy (LIBS) system has been used in the examination of pottery, jewelry and metal artifacts found in archaeological excavations in central and eastern Crete, Greece. The objects date from the Middle and Late Minoan periods (ca. 20th13th century B.C.) through Byzantine and Venetian to Ottoman times (ca. 5th19th century A.D.). The spectral data indicates the qualitative and often the semi-quantitative elemental composition of the examined materials. In the case of colored glazed ceramics, the identity of pigments was established while in the case of metal and jewelry analysis, the type of metal or metal alloy used was determined. The analyses demonstrate the potential of the LIBS technique for performing routine, rapid, on-site analysis of archaeological objects, which leads to the quick characterization or screening of different types of objects. # 2002 Elsevier Science B.V. All rights reserved. Keywords: Laser-induced breakdown spectroscopy (LIBS); Archaeological artifacts; Minoan; Pottery analysis; Metal analysis 1. Introduction The analysis of ancient artifacts provides archaeol- ogists and historians with meaningful information about the use and origin of archaeological objects as well as the materials that were used. For example, identication of compositional materials in pottery found on a particular site could determine whether it was originally created in a different location, allowing researchers to draw conclusions relative to commu- nication, trade and partnerships. Also, important tech- nological insight is provided by means of systematic chemical and structural analysis, which reveals infor- mation about the techniques available for processing materials in order to obtain the nal product. Various analytical techniques have been used exten- sively in the study of archaeological and art objects providing important physical and chemical insight to the structure of objects and materials. For example, polarized light optical microscopy and scanning elec- tron microscopy (SEM), X-ray uorescence (XRF), proton induced X-ray emission (PIXE), X-ray diffrac- tion (XRD), inductively coupled plasma coupled to optical emission or mass spectrometry (ICPOES, ICPMS) and Raman microscopy [114] are among the most widely used techniques in archaeological analysis and art conservation. However, one concern with most laboratory techniques relates to the require- ment for special sample preparation and handling procedures and to limitations imposed by instrumen- Applied Surface Science 197198 (2002) 156163 * Corresponding author. 1 Present address: Department of Analytical Chemistry, Uni- versity of Malaga, 29071 Malaga, Spain. 0169-4332/02/$ see front matter # 2002 Elsevier Science B.V. All rights reserved. PII: S0 1 6 9 - 4 3 3 2 ( 0 2 ) 0 0 4 5 9 - 2 tation factors. In addition, transportation of archae- ological samples and works of art to specialized analytical laboratories is often subject to strict regula- tions and as a result requires lengthy procedures. In this context, laser-induced breakdown spectro- scopy (LIBS) is a potential alternative to other spectro- scopic, mass spectrometric, or X-ray techniques used in art conservationandarchaeologyrelatedapplications. It is a practically non-destructive as well as rapid elemen- tal analysis technique with the critical advantage of being applicable in situ, thereby avoiding sampling and sample preparation. Indeed, LIBS has been used for the analysis of pigments in easel paintings, icons, polychromes and pottery [1520] and demonstrates the prospects of the technique to become a useful analytical tool in art and archaeology. Furthermore, quantitative LIBS analysis leading to absolute concentration values for each element is ideal for the accurate compositional characterization of the materials analyzed, and several papers have addressed this problem in the literature proposing different methodologies [1820]. In this paper, we present results from studies per- formed on different pottery and metal samples in excavations in the central and eastern parts of the island of Crete (Greece) from ve different time periods: Middle Bronze age (ca. 20th18th century B.C.), Late Bronze age (ca. 17th13th century B.C.), Byzantine (ca. 5th14th century A.D.), Venetian (ca. 14th16th century A.D.) and Ottoman (ca. 16th19th century A.D.) and ve different locations: Knossos, Chrysokamino, Hagia Photia, and the islands of Pseira and Mochlos. Analytical information from the LIBS measurements was used in order to characterize painted pottery (pigment identication), metal objects, and jewelry. This work is part of a broader project whose main goal has been to develop, optimize, and test a compact and transportable prototype LIBS work- station. This integrated, user-friendly system will pro- vide on-site, rapid, analytical information about the qualitative and quantitative elemental composition of a wide variety of materials aiding the quick character- ization of archaeological objects and/or samples. Table 1 Analytical emission lines used for identifying elements in LIBS spectra Element Wavelength (nm) Ag 272.177 (I), 328.068 (I), 338.289 (I) Al 257.510 (I), 265.248 (I), 266.039 (I), 308.215 (I), 309.271 (I), 394.400 (I), 396.152 (I) As 274.50 (I), 278.022 (I), As 286.044 (I), As 289.87 (I) Au 264.148 (I), 267.595 (I), 274.825 (I), 288.345 (I) (290.704291.352) (II), 293.219, 302.920 (I), 312.278 (I), 320.472 (I), 323.063 (I) Ca 315.887 (II), (317.933318.128) (II), 393.366 (II), 396.847 (II), 422.673 (I) Cr 357.869 (I), 359.349 (I), 360.533 (I), 375.766 (I), 427.480 (I), 428.972 (I) Cu 261.837 (I), 276.637 (I), 282.437 (I), 296.116 (I), 301.084 (I), 303.610 (I), 306.341 (I), 309.993 (I), 310.860 (I), 312.611 (I), 324.754 (I), 327.396 (I), 329.054 (I), 330.795 (I) Fe 258.454 (II), (259.837259.940) (II), (260.651 (II)260.683 (I)260.709 (II)), 261.187 (II), 261.382 (II), (261.762 (II)261.802 (I)), 262.567 (II), 262.829 (II), (263.105263.132) (II), (271.903272.090) (I), (274.948 (II)275.014 (I)), 296.689 (I), 298.357 (I), 299.443 (I), 302.064 (I) Mg 279.553 (II), 280.270 (II), 285.213 (I) Mn 370.608 (I), 371.893 (I), 380.672 (I), 382.351 (I), 383.436 (I), 384.108 (I), (403.076403.307403.449) (I), 404.136 (I), (407.924407.942408.294408.363) (I), (413.112413.504) (I), (423.514423.529) (I), 446.202 (I) Pb 257.726 (I), (261.365261.417) (I), 266.315 (I), 280.199 (I), 282.319 (I), 283.305 (I), 287.331 (I), 357.273 (I), 363.957 (I), 368.346 (I), 373.993 (I), 401.963 (I), 405.781 (I) Si 263.128 (I), 288.158 (I), 390.552 (I) Sn 266.124 (I), 270.651 (I), 277.981 (I), 281.358 (I), 283.999 (I), 286.332 (I), 291.354 (I), 300.914 (I), 303.412 (I), 317.505 (I), 326.234 (I), 333.062 (I) Ti 323.452 (II), 334.188 (I), 334.941 (II), 336.121 (II), (337.044 (I), 337.145 (I), 337.280 (II)), 338.376 (II) Wavelengths in parentheses indicate two or more lines not adequately resolved in low-resolution spectra. The wavelengths refer to emission from neutral atoms when followed by (I) and to emission from singly charged ions when followed by (II). K. Melessanaki et al. / Applied Surface Science 197198 (2002) 156163 157 2. Experimental In the present study, the output of a nanosecond Q- switched Nd:YAG laser operating at its fundamental wavelength (1064 nm, 15 ns, 25 mJ per pulse) was focused with a planoconvex lens (f 100 mm) on the sample surface inducing the formation of a transient plasma plume. The focused beam intensity was in the range of 0.54 GW/cm 2 . The plume emission was collected with a quartz optical ber and analyzed in a 0.32 m imaging spectrograph (TRIAX-320, Jobin Yvon/Spex) with gratings of 600 and 2400 grooves/ mm (spectral resolution 0.04 and 0.01 nm, respec- tively) and the LIBS spectrum was recorded on an intensied charge coupled device (ICCD) detector (DH520-18F, Andor Technology). The detector was gated by means of a digital delay/pulse generator (DG535, Stanford Research Systems) in order to discriminate the atomic emission from the continuum background present. Delay time of 100500 ns and gate time of 500 ns were used in the measurements reported herein. For the analysis, each sample was placed on a translation stage and positioned within 2 mm from the focal point of the lens. This way, high spatial resolution was achieved which allowed analy- sis of minor features, such as inclusions in pottery, with sizes as low as 100 mm. The analysis can be characterized as practically non-destructive because the laser beam is focused on a tiny spot of typical diameter in the range of 100150 mm. In a few cases, depending on the material probed, more extended effects (up to 500 mm) were observed resulting either from thermal discoloration of the paint or from ejec- tion of poorly adhered material induced by the laser shock wave which accompanies the ablation process. Emission spectra were recorded for a single laser pulse and were subsequently analyzed. In cases a depth proling study was required, spectra were col- lected separately for each one of several successive laser pulses. Elements were identied on the basis of the comparison between the emission lines in the obtained spectra and the distinctive lines of metals listed in Table 1. In general, the spectra were clear enough to allow an immediate identication despite the use of the low-resolution grating for light disper- sion. In certain cases, the use of the high-resolution grating claried or simply conrmed the results obtained at low-resolution. 3. Results and discussion A broad variety of archaeological ndings were examined including painted and glazed pottery, dif- ferent types of metal objects, and jewelry. Some of the objects examined are shown in Fig. 1. LIBS analyses were carried out in order to identify pigments or characterize metal alloys, and selected spectral data are presented to show the type of analytical questions addressed and the information extracted. 3.1. Pottery analysis Ceramic objects are ubiquitous in antiquity and have been employed as storage containers, serving dishes, and votive gurines, among other uses. They are often made from local clay sources, although it is known that Minoan towns often traded goods includ- ing pottery. In the analysis of ceramic sherds, ques- tions are related to the characterization of pigments, the determination of elemental composition of clay, and the characterization of surface encrustation. For example, systematic PIXE analysis of the white paint on pottery sherds from various locations in central and eastern Crete has shown large but non-random varia- tions in the elemental content of Mg, Ca, Si, and Al which appear to correlate quite well with the location of ceramic production [8,21]. Several types of ceramic objects were analyzed by LIBS. One of the objects was a polychromed pottery sherd (Fig. 1a) from an offering table dating to the Middle Minoan IIB period (ca. 18th century B.C.), found at Knossos (Minoan palace outside Heraklion, Crete). White, black and red paint has been used in decorating the surface of the object. Selected spectra from the black pigment are shown in Fig. 2a. As seen by the characteristic emission lines marked in the spectrum, the paint contains substantial amounts of Mg, Si and Al with a relatively high content of Fe, but low content of Ca. Ti is also detected in this paint. In order to further clarify the presence and identify the emission lines of Fe, a high-resolution spectrum, shown in Fig. 2a (inset), was taken. Iron-rich minerals, with the iron primarily in the form of hematite (Fe 2 O 3 ), goethite (FeOOH) and other oxides, have been extensively used as pigments in antiquity. Upon ring, they undergo transformations to different dark minerals, such as magnetite, a mixed iron oxide 158 K. Melessanaki et al. / Applied Surface Science 197198 (2002) 156163 (Fe 3 O 4 ) [7]. The rest of the elements originate from the clay co-existing with the pigment, which is a mixture of aluminosilicate minerals. Other ceramic sherds analyzed date from the Byzantine, Venetian, and Ottoman periods on Crete and were found at two locations, the small island of Pseira and the metallurgy site at Chrysokamino. These were differently painted glazed ceramics most likely from household items (Fig. 1b and c). Glaze is a silica- based mixture often containing pigment applied on the surface of a ceramic vessel and then red over 1200 8C producing a decorative, impermeable, glassy coating. The black paint, used for decorating a white dish (Fig. 1b) was analyzed, and the LIBS spectrum showed the presence of manganese suggesting that MnO has been employed (Fig. 2b). The intense lead signal indicates the presence of lead white, which was also detected in other areas of the object and was the primary white pigment used throughout the Byzantine era. Calcium, aluminum and silicon detected originate from the glaze. In another case, the bright yellow glaze used to decorate the interior and exterior rim of a Turkish bowl was analyzed on a sherd from the site of Chrysokamino. The yellow glaze was found to con- tain Pb, Ca and Cr (Fig. 3a). A high-resolution spectrum of the yellow pigment was also recorded (Fig. 3a, inset), conrming the presence of chromium on the basis of characteristic emission lines. The combined presence of lead and chromium suggests that chromium yellow (lead chromate, PbCrO 4 ) has been used. Chromium yellow, a synthetic pigment, was introduced as a coloring agent approximately 1818. This implies that the pottery analyzed dates not before the early 19th century, which is in fact in agreement with the excavation data as the sherd was found close to the surface of the area excavated. Furthermore, this type of information suggests that LIBS can be employed to determine/conrm the date of certain types of pottery. In several sherds examined, the green paint was found to be rich in Cu suggesting the extended use of Fig. 1. Pictures of selected archaeological objects analyzed. (a) Minoan polychromed ceramic sherd from Knossos (T907); (b) Byzantine glazed ceramic sherd from Pseira (PS3048); (c) Late Byzantine/Venetian glazed ceramic sherd from Pseira (PS1079); (d) Minoan metal rivet from Pseira (PS1004); (e) Byzantine metal ring from Pseira (PS438); (f) Minoan metal chisel from Hagia Photia (AN4666). K. Melessanaki et al. / Applied Surface Science 197198 (2002) 156163 159 Cu based pigments. Several green as well as blue pigments, which are copper compounds, have been used in painting from antiquity through to the modern era [12,13]. In a few cases, for example, in the pottery sample shown in Fig. 1c (interior glaze decoration on Late Byzantine/Venetian open vessel from Pseira), the presence of tin along with copper in the green pigment was obvious (Fig. 3b). Identifying the source of tin in the green pigment is an important question in under- standing the type of pigment used. One possible case is that a bronze (coppertin alloy) object may have been used for preparing the green pigment. It is known that green pigments are produced from copper through a chemical oxidation procedure. However, the presence of large quantities of bronze from archaeological remains may have led to the use of bronze instead of copper in the production of pigments. Alternatively, the presence of Sn can be due to the mixture of a lead tin yellow pigment (Pb 2 SnO 4 or PbSn 1x Si x O 3 ) with a copper based green or blue pigment. Further studies are under way for resolving the identity of this type of pigments. 3.2. Metal analysis Another large class of objects in archaeological excavations are metal artifacts ranging from tools and weapons to home utensils and jewelry. The main materials used in the Bronze age have been copper and coppertin alloys (bronze). Addition of tin to copper at the level of 510% by weight was found to produce a slightly harder alloy, which was easier to cast. Other metals used include lead and tin. Silver or gold alloys have been used in jewelry and as decoration for different objects. The rst analytical question con- cerning a metal object is to identify the type of metal or metal alloy. Furthermore, determination of the quantitative content of the various metals and of the trace elements can lead to a more complete character- ization of the objects. A rivet from the island of Pseira (Fig. 1d), dated to Late Minoan IB (ca. 16th century B.C.), used to hold the blade within the wooden handle of a dagger, was examined. It was found to be composed of copper by probing representative points around the cylindrical Fig. 2. LIBS spectra of black pigments on: (a) Minoan poly- chromed sherd (inset: high-resolution spectrum); (b) Byzantine glazed ceramic sherd. Fig. 3. LIBS spectra from glazed ceramic sherds. (a) Yellow glaze (inset: high-resolution spectrum); (b) green glaze ( * mark Sn emission lines). 160 K. Melessanaki et al. / Applied Surface Science 197198 (2002) 156163 surface. While taking additional spectra on the at sides of the rivet, a surprising result was found. Intense emission from silver was recorded in the LIBS spec- trum (Fig. 4a). This indicates the presence of silver on the exposed at sides of the rivet, possibly from a silver coating. This rivet is the rst of its type found on the site of Pseira. Other parallels for this type of object come from the Mycenaean shaft graves in mainland Greece. LIBS spectra from a metal pin analyzed are shown in Fig. 4b and c. While emission lines due to copper are observed when the outside part of the pin is examined, additional emission from tin is clearly detected when the core of the object is probed by the laser beam. This nding is quite dramatic and indicates two possible situations. The rst is that the pin is actually constructed from an inner part made of bronze and an outer part made of pure copper. The other (and more likely) possibility is that extended metal corrosion has resulted in total loss of tin from the heavily corroded outside layer while part of it has been preserved in the core of the material. In another case, a Byzantine bronze ring fromPseira (Fig. 1e) was examined and was found to contain copper and tin with signicant amounts of lead as seen in the corresponding spectrum (Fig. 5a). Also, an Early Minoan IB (ca. 27th century B.C.) metal chisel from the cemetery at Hagia Photia (Fig. 1f) was examined and was found to contain both lead and arsenic in addition to copper (Fig. 5b). The presence of arsenic in copper objects of this time period has a long history in the literature [2225]. Finally, a spectrum from Late Minoan IIIA (ca. 14th13th century B.C.) jewelry (golden bead) from the island of Mochlos is shown in Fig. 5c indicating the use of a AuAgCu alloy. Other similar objects were analyzed showing different relative intensities of emission lines suggesting variable proportions of Au, Ag and Cu in the alloy used. These results indicate that LIBS analysis can quickly provide infor- Fig. 4. LIBS spectra of Minoan metal samples obtained: (a) on the at face of copper rivet; (b) on the outside of metal pin; (c) in the core of the same metal pin. Fig. 5. LIBS spectra from: (a) Byzantine metal ring; (b) Minoan metal chisel; (c) Minoan golden bead. K. Melessanaki et al. / Applied Surface Science 197198 (2002) 156163 161 mation on the qualitative and semi-quantitative ele- mental content of different metal objects and aid their characterization and classication. Quantitative ana- lysis by LIBS is also possible using proper reference samples or alternative approaches, such as the one recently used for the quantitative analysis of precious metal alloys [26]. At this point, it is important to stress two factors that might affect the reliability of the analysis in the identication of the chemical composition of metal artifacts. The rst is the corrosion of metals, which leads to material alteration and possible loss of certain metals in the form of soluble salts. This effect was shown in the LIBS analysis of the bronze pin as indicated in the LIBS spectra in Fig. 4b and c. One, therefore, has to be aware that surface examination probes mainly the corrosion products. Conclusions regarding the elemental composition of the original object should be drawn with care as certain corrosion products are known to leach out of the object, and therefore, their lowcontent does not necessarily reect the composition of the metal at the time of object manufacture. For example, surface analysis techni- ques (sensitive only to a layer depth of 10100 mm) can give misleading results in cases where extended metal corrosion is present. The other concern when dealing with metals analysis is the heterogeneous character of a metal alloy object that often results from poor mixing of the different metal alloy compo- nents at the time of production. These two factors can affect both the qualitative and, more signicantly, the quantitative analysis of metal objects. In this respect, great care must be taken in performing the analysis and reporting the results. 4. Conclusions The results presented in this paper demonstrate the advantages of LIBS analysis in obtaining elemental analysis information about the materials used for making and decorating ancient pottery or metal arti- facts. An important aspect of LIBS is the speed of analysis, which can allow the quick examination of a large number of samples in the eld, at a museum, or at an excavation site. Compact and user-friendly instrumentation could make a powerful tool for the analysis of a large variety of materials leading to quick characterization and classication of archaeological ndings. Acknowledgements The authors wish to thank the Institute for Aegean Prehistory (INSTAP) and the Foundation of Research and Technology-Hellas (FORTH) for funding and collaboration on this project. They also owe many thanks to N. Papadakis and A. Nikakis of the 24th Ephoria of East Crete and S. Chlouveraki and T. Brogan of the INSTAP Study Center of East Crete. The authors would also like to thank J. 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