Research Article

Received: 25 October 2009 Revised: 28 February 2010 Accepted: 1 March 2010 Published online in Wiley Interscience: 7 May 2010

(www.interscience.com) DOI 10.1002/xrs.1257

SANDRA: a portable XRF system for the study of Mexican cultural heritage
J. L. Ruvalcaba Sil, D. Ramrez Miranda, V. Aguilar Melo and F. Picazo
This work presents the portable X-ray system SANDRA (Sistema de Analisis No Destructivo por RAyos X or System for Non Destructive Analysis using X-rays) developed at the Physics Institute of the UNAM, Mexico, for the study of Mexican cultural heritage collections. The X-ray uorescence (XRF) SANDRA device can use 75 W Mo, Rh and W X-ray tubes and Amptek Si-PIN and Cd-Te detectors that are selected and combined depending on the elemental range detection requirements and the specic problem to be studied. In this paper, a full description and characterization of this system, sensitivities for the X-ray tubes and detectors as well as the detection limits are discussed. Examples of applications to technological studies on pre-Columbian metallic artifacts and analysis of color materials of ancient Mexican codex are shown. Copyright c 2010 John Wiley & Sons, Ltd.

Introduction
X-ray uorescence (XRF) is a fast and high sensitivity multielemental technique; it can be applied directly for non-destructive and non-invasive studies.[1,2] This technique is well established as a basic analytical tool for cultural heritage applications for more than 30 years.[3 13] Although there are many museums and conservation laboratories equipped with static or portable XRF equipments in developed countries, nowadays, the use of portable devices for the characterization of objects and collections of museums, libraries, or in general, materials from the archaeological record or art history is fortunately increasing in countries of Latin America. Since the early works using portable XRF systems[1,3,5,7,11] , many improvements have been achieved.[1,2,14 16] With the development of Si-PIN and silicon drift detectors,[17 19] the systems became lighter and the portability was signicantly improved for in situ measurements. Thus, several systems have been developed in many countries, mainly in Europe. Currently, different types of X-ray sources including radioactive sources and X-ray tubes and detectors are used.[20 25] XRF apparatus are extensively applied for the characterization of all kind of cultural heritages materials.[26 33] Often, XRF analyses are complemented by other portable spectrometers, such as the Raman ones,[13 34] and also using other X-ray based techniques such as particle induced X-ray emission spectroscopy (PIXE).[35,36] The last improvements on XRF systems consider the development of devices combining X-ray diffraction (XRD) and XRF in situ.[37 39] Despite the rich cultural heritage of the Latin American area and the improvements in the experimental devices, very few portable XRF equipments have been developed in the last years in this region.[40 42] This paper presents the portable X-ray system SANDRA (Sistema de Analisis No Destructivo por RAyos X or System for Non Destructive Analysis using X-rays) developed at the Physics Institute of the UNAM, Mexico, for the study of outstanding Mexican cultural heritage collections. The main applications of the SANDRA system are related to pre-Columbian and colonial manuscript analyses, paintings for palettes studies and painters techniques from colonial to modern periods, 16th17th centuries polychrome colonial sculpture, pre-Columbian metallic artifacts (gold, bronzes), pre-Hispanic turquoises and green stone objects,

as well as ancient photographs. Some examples of applications are also discussed in this paper.

The SANDRA System

Our actual SANDRA system is the result of a previous prototype with a Rover system with Si-PIN and CZT X-ray detectors from Amptek.[41,42] In the past years, it has been renovated and new detectors may be used. To improve our system, several comparisons with PIXE and RBS measurements have been carried out on books decorations from 17th to 19th centuries,[43] Maya pottery and pre-Hispanic copper artifacts.[44] SANDRA system has a typical geometric conguration; the detector is set at 45 from the direction of the excitation X-rays (Fig. 1). The available X-ray tubes have Mo, Rh and W anodes with 125 m beryllium window. The maximum power of the X-ray tubes is 75 W (50 kV, 1.5 mA). They correspond to the XTF5011 model from Oxford Instruments. The X-ray tube is powered by a high voltage power supply XLG50P100 from Spellman. The X-ray tube is mounted on an XYZ support, so it can be manually moved 3 cm in each direction in front of the studied object to smoothly reach the selected region of analysis. Three small fans and a main fan at the bottom of the X-ray tube provide the necessary cooling for the X-ray tube. A thermocouple is provided in the X-ray tube for temperature monitoring. The maximum X-ray tube operation temperature is 50 C. The SANDRA system is mounted on an articulating arm boom stand that ensures high mobility and exibility in the movement (Fig. 2). With this setup, it is possible to reach corners and difcult locations on the studied object. The system can be used for analysis on the vertical and horizontal planes or it can be tilted as necessary.

Correspondence to: J. L. Ruvalcaba Sil, Instituto de Fsica, Universidad Nacional Autonoma de Mexico (UNAM), Apdo. Postal 20-364, Mexico DF 01000, Mexico. E-mail: sil@sica.unam.mx Instituto de Fsica, Universidad Nacional Autonoma de Mexico (UNAM), Apdo. Postal 20-364, Mexico DF 01000, Mexico

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Article published as part of the special issue on Portable X-ray Spectrometers.

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SANDRA portable XRF system cable. The performance of this Si-PIN detector is similar to the one described above. For the SANDRA operation a LED security light turns on when X-ray tube is working. The X-rays from the tube can be stopped by a shutter. To determine the region of analysis, two focusable laser pointers intercept at 8 mm from the X-ray tube exit collimator. An X-ray screen may be used to set properly the working distance and the laser pointers. The total distance from the X-ray tube exit window to the sample surface is 9 cm while the X-rays emitted from the sample have to travel 1.5 cm in air before reaching the detector. The incident X-ray beam spot at the sample surface was measured for 1.0, 1.5 and 2 mm diameter using 250 m diameter Au wire and mounted on a XY translation stage with 10-m resolution. We determined that there is no signicant scattering and the increase in the beam diameter is lower to 15% of the collimator diameter. Considering the previous parameters, Rh and Mo K peaks from the X-ray tube loss only 1% of their intensities in the air path while L lines from Mo and Rh have a signicant absorption and only 3.6 and 12.6% may reach the sample, respectively. For this reason, the corresponding X-ray scattering is very weak and it is not often detected. The Mo-L peak may overlap S-K and Pb-M peaks, whereas the Cl-K peak may be overlapped by Rh-L peak. On the contrary, W L and L lines show a lower absorption in air (about 10%), then the scattering peaks are frequently observed in the spectra using the W X-ray tube. Nevertheless, the Mo, Rh and W L peaks may be easily removed using lters in the incident X-ray path, such as a foil of 12 m of Cr or Zn. On the other hand, only the X-rays emitted from sample by the lighter elements are absorbed signicantly in the 1.5 cm air path. For Al, Si, S, Cl, K, Ca, Ti, Fe and Cu K the transmitted X-rays are 5, 24, 36, 51, 61, 76, 85, 92, 97 and 99%, respectively. This fact means that if low energy X-rays detection is required for the analysis with our equipment, it will be necessary to use a He jet at the X-ray detector and at the path of the X-ray incident beam as well. Finally, to improve the data record during the analysis and to observe the irradiated region at the object surface simultaneously to the X-ray spectra acquisitions, a webcam with medium resolution is used. In this way, both an image and the corresponding spectra are stored in the computer.

X-ray tube

fans

X-Y-Z support

beam shutter focusable lasers

region of analysis

webcam

Si-PIN detector

Figure 1. The SANDRA XRF system during the study of a collection of Mexican historic photography. Main components are pointed out.

Figure 2. The SANDRA XRF system supported on its articulating arm boom stand. Analysis of the Colombino codice.

The X-ray beam diameter is determined by a lead collimator. The beam diameters may be 0.5, 1.0, 1.5 and 2.0 mm. Two X-ray detectors can be used: a Si-PIN detector (XR-100-CR model) and a Cd-Te detector (XR-100T-Cd-Te model) from Amptek. The Si-PIN detector has a 6 mm2 active area, a 500 m thickness and a 0.5 m Be window while the Cd-Te detector dimensions are 5 5 1 mm (25 mm2 active area) and 4 m Be window. The energy resolution at 5.9 keV (Mn-K line) of the Si-PIN and Cd-Te detectors are 180 and 360 eV, respectively. A conic piece in aluminum covers the detector head for its protection and it could be used to set a He jet for light elements detection improvement. The cone has a cylindrical aperture of 4 mm of diameter. Under this conguration, this cone is working as a collimator only for the Cd-Te detector, as the exposed area is then 12.5 mm2 , a half of the total detector active area. The X-ray detector signal is processed by a PX4 digital pulse processor from Amptek before reaching the laptop computer. Recently, the complete X123 Si-PIN spectrometer system from Amptek has been tested as well. This system provides together the X-ray detector, the amplier and the power supply in a small packing and it is directly connected to the computer by a USB

Characterization of the XRF System

The full characterization of the SANDRA system was required to determine their advantages and limitations, as well as the most suitable congurations. Measurements on a full set of standard reference materials from Micromatter Co. were carried out for the Mo, Rh and W X-ray tubes and the Si-PIN and Cd-Te detectors. The elemental range covered from Si to Sn for K and L lines and Pb and Au L lines. From the X-ray uorescence spectra, the sensitivity was calculated[1] from the ratio of the peak area (counts) and the product of the concentration (g/cm2 ) and the time (s). For calculation of sensitivities, peak areas were measured using AXIL program. Figures 3 and 4 show the sensitivity curves as a function of the X-ray energy for the Si-PIN and the Cd-Te for the Mo, Rh and W under the same voltage and current conditions (45 kV and 0.3 mA). Filters were not used. From the sensitivity curves, it is clear that the W X-ray tube gives rise to higher sensitivities for both detectors from 3 to 8 keV (K to Cu) mainly due to the WL lines excitation while for the higher

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Sensitivity (counts/ g/cm2 * s)

100

Sensitivity normalized by Fe sensitivity

Mo Rh W

100

Si-Pin K lines Si-Pin L lines Cd-Te K lines Cd-Te L lines

Ag

Zn

10

-1

Fe V Ca

Zn As

Br Sr

Sn

10-1
Ca

Fe V Au Pb

Br Sr

10-2

Cl Si

10-2

Cl

Ag Sn

Si

Si-Pin detector 10-3 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 X-ray energy (keV)

10-3 0 2 4 6 8

Mo X-ray tube
10 12 14 16 18 20 22 24 26 28 X-ray energy (keV)

Figure 3. Sensitivity curves as a function of the X-ray energy using the Si-PIN detector and the Mo, Rh and W X-ray tubes under similar conditions (0.3 mA, 45 kV). A set of Micromatter Co. thin reference materials was used.

Figure 5. Comparison between the sensitivities normalized by Fe sensitivity for the Si-PIN and Cd-Te detectors for the Mo X-ray tube under the same power conditions (0.3 mA, 45 kV).

101

Sensitivity (counts/ g/cm2 * s)

Mo Rh W
100
Zn Fe V As Br Sr

Si

101

Sn

Detection limit (g/cm2)

Ag

100
Sn Ag Cl

10-1

Ca

Cl

10-1
Ca Ti Fe Zn Br Sr

Cd-Te detector
10-2 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 X-ray energy (keV) 10

Mo X-ray tube
15 20 25 30 35 40 45

Si-Pin Cd-Te
50 55

Atomic number Z

Figure 4. Sensitivity curves as a function of the X-ray energy using the Cd-Te detector and the Mo, Rh and W X-ray tubes under similar conditions (0.3 mA, 45 kV). A set of Micromatter Co. thin reference materials was used.

Figure 6. Detection limits comparison for the Si-PIN and Cd-Te detectors for the Mo X-ray tube under the same excitation conditions (0.3 mA, 45 kV). A set of Micromatter Co. thin reference materials was used.

energy range (1026 keV) the sensitivies are similar by comparison to the Mo and Rh X-ray tubes. On the other hand, despite a rapid decrease in the sensitivity for the Si-PIN detector and the Rh tube for X-ray energies higher than 18 keV, the sensitivies are very similar for the Mo and Rh X-ray tubes from Si to Sr. For energies lower than 14 keV, the Mo-K lines are energetically closer to the K-edge of the elements in this range than the Rh-K lines (and therefore the respective photoelectric cross sections are higher). However, the Rh anode source offers more intense bremsstrahlung radiation in the same range which is actually the most signicant contribution in the ionization process of the corresponding elements. For these reasons the sensitivities are comparable. A comparison between the sensitivities normalized by Fe sensitivity for the Si-PIN and the Cd-Te detectors using the Mo X-ray tube is shown in Fig. 5. It is observed that the normalized sensitivities for the Si-PIN detector are higher in the light elements range (the factor decreases from 3 for Cl when the X-ray energy

increases). In the medium X-ray energy range (from V to As), the normalized sensitivities are very similar and they are slightly higher for the Cd-Te detector from 11 keV. Nevertheless, for X-ray energies higher than 18 keV the normalized sensitivities for Cd-Te are higher than the Si-PIN normalized sensitivities from a factor of 3.5 up to 7 as X-ray energy increases. The Cd-Te detection starts from Cl because of the low energy X-ray absorption in its thick window (4 m), but the Cd-Te efciency increases rapidly for higher energies improving its sensitivity. The detection limits[2] calculated as the ratio between the product of the concentration by three times the square root of the background and the peak area, for the Mo X-ray tube and for both detectors, show that the lower detection limits are reached in all the cases for the Si-PIN detector (Fig. 6). Peak to background ratios are in general higher for the Si-PIN detector than for the Cd-Te detector. For Fe, these ratios are 0.97 and 0.7 for the Si-PIN and the Cd-Te detector, respectively, while for Ag the same ratios are 0.92 and 0.57. Despite the higher sensitivity for the Cd-Te in

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SANDRA portable XRF system complemented by Raman spectroscopy, Mid-Fourier-transform infrared (FTIR) in situ and VIS-NIR light spectrometry. Our SANDRA system has been extensively used for the study of Mexican cultural heritage collections since the construction of our rst prototype several years ago. Due to the success of this device, other apparatus have been constructed. Actually, three devices are operational and they are used in collaboration with the most relevant Mexican museums. The main applications are related to studies of pre-Columbian and Colonial manuscripts, paintings for palette and painters techniques from Colonial to modern painting, polychrome colonial sculptures, pre-Columbian metallic artifacts (gold, bronzes), pre-Hispanic turquoises and green stone pieces, as well as historic photographs. Recent applications include metallic threads and textiles. In this work, two examples of our researches using the SANDRA system are presented.
26

Si

104
Cl Au Cu

Sediment (SRM 2711, 2704) Tomato leaves (SRM 1573a) Gold alloy (588/340)

Detection limit (g/g)

103

Ag

Pb

102
Ca

Sr Br

101 0 2 4

Fe

Mo X-ray tube Si-pin detector

8 10 12 14 16 18 20 22 24

X-ray energy (keV)

Pre-Columbian gold and silver artifacts In Mexico, few pre-Columbian artifacts and collections of precious metals are preserved. Most important items are kept in national museums and due to their importance it is very difcult to transport them to laboratories for analytical studies, and sampling is not allowed or it is very limited. In some cases, non-destructive and non-invasive studies were carried out by PIXE on a reduced amount of gold items[45] and previously only few artifacts were irradiated in situ using portable XRF.[46] For this reason, scarce information on Mesoamerican gold work exists and there were insufcient data concerning the silver artifacts before our research. Certainly, the richest and most important collection with an archaeological context from Mesoamerica is the Tomb 7 from Monte Alban, central Oaxaca in the South of Mexico, corresponding to the Mixtec Culture of the late postclassic period (12001521 A.D.). In the case of this collection, few electron microscope analyses (SEM-EDS) were carried out on a small number of samples from selected items.[47] Recently, a set of portable equipments were transported to the Museo de las Culturas de Oaxaca in Oaxaca City to perform a non-destructive and non-invasive characterization. The state of conservation of the collection is very good. Then, for the gold artifacts and most of the silver items there were unexpected important patina effects on the analytical results. Considering the sensitivity data, the Cd-Te detector and the Mo X-ray tube combination was chosen for this study as the metallic alloys are composed by medium and heavy elements. In particular, the detection of Ag K lines is important for this study as they provide more representative information of the bulk composition than Ag-L lines. In this way, more than 600 XRF analyses were performed on 49 artifacts within 5 days in the museum during the usual opening hours. X-ray tube conditions were 45 kV and 0.15 mA using a 1.5 mm beam spot. A spectrum required 60 s per region of analysis. The number of measurements on each object varied depending on the complexity of the artifact and its heterogeneity. Most complex artifacts such as necklaces required many analyses, and then the X-ray tube lament current was increased to 0.3 mA to reduce the acquisition time to 30 s and to obtain suitable spectra. A Degussa gold alloys set (including the Au/Ag contents 585/340, 750/120, 750/40, 585/140 and 900/40) as well as silver alloys (0.925, 0.720 sterling Ag) were irradiated under the same conditions to get a suitable system calibration.[48] AXIL program was used for X-ray peak area calculations. The elemental concentrations were obtained following a procedure described by Karydas.[26]

Figure 7. Detection limits for the Si-PIN and Cd-Te detectors for the Mo X-ray tube (0.3 mA, 45 kV) from solid reference materials NIST SRM 2704, 2711, 1573a and a Degussa gold alloy (Au 585/Ag 340).

the high energy range, the background in the spectrum is much higher and the corresponding detection limits are larger. On the other hand, several reference standard materials from NIST were used to evaluate the detection limits for solid samples analysis: SRM 2704 Buffalo river sediment, SRM 2711 Montana sediment unpuried, SRM 1573a Tomato leaves and a homogeneous gold alloy reference 585/340 from Degussa were irradiated by 5 min using the Mo X-ray tube and the SiPIN detector. The X-ray tube power parameters are 45 kV and 0.3 mA. Considering the same detection limit criteria as above, the graph shown in Fig. 7 was obtained. For sediments and the plant reference, the detection limits may reach 40 g/g for Cu and 25 g/g for other heavier elements, like Sr. Detection limit for Fe increases to 100 g/g while for Ca and Cl, the detection limits are 400 and 1000 g/g, respectively. We may expect similar results for other materials with a matrix similar to sediments (stone, glass). For the gold matrix, Cu has a detection limit of 450 g/g and Ag may reach 2400 g/g while the Au may attain 1340 g/g. From the previous measurements, we can conclude that a Mo or Rh X-ray tube with a Si-PIN detector represent the best combination for a rst general analysis including light elements. Cd-Te detector may be useful for the detection of higher X-ray energies or heavier elements. The combined use of these X-ray detectors may also be considered.

Some Applications to Cultural Heritage Studies

For research in cultural heritage and a rst characterization of a collection or specic objects, XRF in situ is a powerful analytical tool. XRF analysis provides enough information in short time to establish the nature of the materials (inorganic or organic) and the use of complementary techniques. After a collection study by XRF, it is possible to select representative objects for further studies in the laboratory or, if necessary, to determine a strategy of sampling with minimum damage to the objects. This analytical approach has been adopted for the study of Mexican collections by our interdisciplinary group. After the application of imaging techniques and microscopical examination, XRF is applied and

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211

213

212

358 357 356 359

210 209

215

211

355 354 360 353

207 208

350 350 348 352

Figure 8. Gold pendant of Xochipilli god, piece A. Other four similar pieces complete the original set. Mixtec culture, Oaxaca, Mexico. ca 15th century.

351

Two of the artifacts, including the regions of analysis, are shown in Figs 8 and 9: a gold pedant and a silver nger ornament. The corresponding results are plotted in the graphs of Figs 10 and 11, respectively. The high homogeneity of the alloys composition is not surprising.[45,49] These artifacts were casted by false ligree lost wax procedure. For the gold pendant, the X-ray incident angle was modied until a grazing geometry of irradiation in at areas was achieved; nevertheless, gold enrichment at the surface of the gold pendant was not observed.[50] The mean composition of this artifact is Au 46.9%, Ag 32.8%, Cu 20.3%, similar to other three identical pendants of the collection. They may be produced in the same workshop with the same gold alloy. Their composition is quite different if we compare it with other pieces of the collection (mean Au 77%, Ag 15%, Cu 8%). Concerning the silver ring elemental composition, this is similar to the rest of the silver items of the collection, with Cu average contents of 2% and very low amounts of Au. The same alloy was used for all the parts of the nger ornament, except for one of the bells (region 356), attached by a plastic wire. We can assert that after the discovery of the tomb, this bell was added to the ornament but this modication to complete the artifact is not right, as it does not match the expected composition of the artifact. These are just few results[49] ; a detailed paper with the full set of artifacts and data of the collection is in progress. Studies of early colonial codices In the pre-Hispanic and early colonial codices an important amount of knowledge is preserved including religion and traditions of the ancient Mexican people. Most of these manuscripts were destroyed during the catholic evangelization in the 16th and 17th centuries. Some of these documents survived, and nowadays they are kept in European collections. In the Mexican collections, only one pre-Hispanic codice, the Colombino, is preserved in the

Figure 9. Silver nger ornament of eagle. Other three similar pieces complete the original set. Mixtec culture, Oaxaca, Mexico. ca 15th century.

65 60 55 50 Concentration (%) 45 40 35 30 25 20 15 10
6 7 8 9 0 1 2 3 4 5 6 7 8 9 0 1 22 20 20 20 20 21 21 21 21 21 21 21 21 21 21 22 22 2

Cu Ag Au

Figure 10. Elemental contents of Cu, Ag and Au determined by XRF for the Xochipilli god pendant, piece A.

Biblioteca Nacional de Antropologia e Historia (INAH) with about other 40 colonial codices written after the Spanish conquest. A research project on this kind of manuscripts has been developed to determine the materials used in these documents, to understand how they were written and to propose preventive conservation strategies. In fact, there are scarce analyses on codice materials.[42,51] The SANDRA system and other portable equipments were transported to the security areas of the library to carry out the analysis of the most important codices of the Mexican collection. In

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SANDRA portable XRF system (conrmed by our XRF analysis[52] ), has colored drawings of local plants, with their names written in red ink in ancient Mexican language Nahuatl and the description of the recipes written in Latin (Fig. 12). Special attention was focused on the color materials. The rst XRF analyses were carried out using the Cd-Te detector and the Mo X-ray tube (45 kV and 0.3 mA using 1-mm beam spot) as mineral pigments could be found. After a rst general analysis of several pages at the beginning, middle and end of the document, only arsenic in one kind of yellow color, probably due to orpiment, and high iron contents (earth pigments) in brown color were detected. Then, green, blue, red and other kinds of yellow color may be organic as their spectra are similar to the paper one.[52] A second round of analysis and new measurements were carried out using the Si-PIN detector and similar X-ray tube conditions. As an example, Fig. 12 shows the pages 9 and 12 recto of the de al Cruz Badiano codex with the analyzed regions. The main results are plotted in the graph of Fig. 13. The identication of two yellow was conrmed, one organic and the other one (B191) tting the orpiment composition (As, S). The white color (B137, B195) is related to Ca and S signals, i.e. gypsum. Brown and ochre are clearly correlated to high amounts of Fe, and in some cases Mn, typical of earth pigments (B139, B194). Sometimes they can be mixed with orpiment. Despite the variability observed for the green, blue and red colors, mainly due to the overlapping of the color layers and color combinations with gypsum and orpiment, the intensities of the main detected elements for these colors are very similar to the paper signals. Considering the previous data collected with the Cd-Te detector, we conclude that these colors must be organic (dyes) and the presence of Si, K and Ca indicate that clays could be used to x the dye, such as in the Maya blue manufacture with indigo and palisgorskite.[53] This preparation of colors is related to pre-Hispanic origin and it does not correspond to European
188 141 189 194 142 193

100 95 90 Concentration (%) 85 80 Cu Ag Au

10

0.1
34 8 34 9 35 0 35 1 35 2 35 3 35 4 35 5 35 6 35 7 35 8 35 9 36 0

Figure 11. Elemental contents of Cu, Ag and Au determined by XRF for the silver nger ornament of eagle.

the rst stage of research, the Colombino codice and two colonial codices (de la Cruz Badiano, Azoyu) were studied.[51] In this case, we discuss the analysis of one colonial codice. Among the most important early colonial manuscripts, the de la Cruz Badiano codice was written in 1552 in the Franciscans school for noble Indians (Santa Cruz de Tlatelolco) in Mexico City just 31 years after the conquest of the Aztec capital, Tenochtitlan. This European book style codice was discovered in the Vatican Library and it was given as a present to Mexico by the Pope in 1990. The main subject of this document is the pre-Hispanic traditions of use of plants and minerals for medical purposes.[36] The manuscript, written with iron-gallic inks within minium margins

143

190 191 192

136 139 137 138 131 133 134 132 196 197 198 140 195

135 199

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Figure 12. Nine and 12 recto pages of the de la Cruz Badiano codice (1552). XRF analyzed regions are shown.

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folio 9r

white

brown yellow

folio 12r

brown white

104 X-ray intensity (counts)

green blue red paper green Si S K Ca Fe As Pb

103

102

101
BD 13 1 BD 13 6 BD 13 8 BD 14 0 BD 13 7 BD 14 2 BD 13 9 BD 19 1 BD 18 9 BD 19 0 BD 19 2 BD 19 3 BD 19 4 BD 19 5

Figure 13. X-ray intensities from the XRF spectra of the analyzed regions of Fig. 12, de la Cruz Badiano codice.

lacquers.[54] It is clear that the use of dyes and pigments for coloring followed a specic pattern, like in the case of the red color; minium (lead tetraoxide) never appears in the gures and it was exclusively used in the red margins and mixed in the red inks probably with a red dye. The de la Cruz Badiano codice shows the syncretism of the preColumbian and European traditions of writing at the beginning of the colonial period in Mexico. The European document format and book style, written with iron-gallic inks, integrates representations of plants with pre-Hispanic iconographical elements and a selective use of dyes and pigments following the pre-Columbian codice traditions. Only in the late colonial codices, dyes are replaced by European pigments.[42,51] Further analyses on the codices collection using XRF and other complementary techniques, such as Raman and Mid-FTIR in situ are in progress.

Acknowledgements This research is part of the interdisciplinary Mexican project MOVIL: Non-destructive methodologies for the In situ Study of the Cultural Heritage supported by CONACYT Mexico grant U49839-R. The authors thank K. Lopez, J. Beristain, J. G. Morales and J. C. Pineda for their technical support as well as E. Hernandez Vazquez for the de la Cruz Badiano codex and the gold and silver artifacts photographs. The study of gold and silver pre-Columbian items was carried out in the Museo Regional de Oaxaca, Oaxaca, Mexico with the collaboration of the INAH Center Oaxaca and the Conservation Metals y Workshop of Escuela Nacional de Restauracion, Conservacion Museograa (INAH), as well as the Instituto de Investigaciones Antropologicas and Instituto de Investigaciones Esteticas, UNAM. The studies of Mexican codexes were carried out in collaboration with the Biblioteca Nacional de Antropologia e Historia, INAH and Laboratorio de Diagnostico de Obras de Arte of Instituto de Investigaciones Est eticas, UNAM.

Conclusions
This paper showed the main analytical features of the portable XRF spectrometer SANDRA, developed in the Instituto the Fisica, UNAM, Mexico. It has been used for various applications including technical studies of metallic artifacts (gold, bronzes), analyses of pre-Columbian and colonial manuscripts, studies of painting for palette and painters techniques, conservation studies of historic photographs as well as characterization of pre-Hispanic turquoises and green stone objects. The SANDRA system provides outstanding information for materials identication and use of materials, technological studies and for conservation and restoration purposes. Under the actual conguration of the SANDRA system, the Mo and/or Rh X-ray tubes combined with the Si-PIN detector is the most appropriate setup for a rst general study. The combination of detectors and X-ray tubes provides complementary information for cultural heritage with a convenient set of detected elements and X-ray energy ranges. This device represents a suitable choice using low cost semiconductor X-ray detectors and standard X-ray tubes. This fact has to be considered for limited budgets like in the case of Latin American countries.

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