Tables for
Volume I
X-ray absorption spectroscopy and related techniques
Edited by C. T. Chantler, F. Boscherini and B. Bunker

International Tables for Crystallography (2023). Vol. I. Early view chapter

The use of XAS and related methods in cultural heritage investigations

Koen Janssensa* and Marine Cotteb

aAXES, Department of Chemistry, University of Antwerp, Antwerp, Belgium, and bEuropean Synchrotron Radiation Facility, Grenoble, France
Correspondence e-mail:

The literature on the use of X-ray absorption spectroscopy (XAS) for the characterization of cultural heritage (CH) materials and to gain a deeper insight into the spontaneous degradation phenomena that they are subjected to is reviewed. In the CH context, XAS is mostly employed in combination with related methods such as X-ray fluorescence and X-ray diffraction, which are capable of providing information on the elemental and/or crystalline composition of a material. Since CH materials are usually composed of multiple compounds, often mixed together in a strongly heterogeneous manner, it is mostly the laterally resolved variants of the abovementioned methods that find application in CH studies. To conclude, several methodological developments are outlined that may become relevant for the characterization of CH artefacts and materials in the near future.

Keywords: cultural heritage.

1. Introduction

From prehistoric times onwards, both artists and craftsmen have sought to manipulate natural and/or manmade materials to produce artefacts of either utilitarian or aesthetic value. Initially, such artefacts, for example obsidian fist axes or ivory sewing needles, were relatively simple and (thus) closely related to the original, natural materials from which they were made. These could be wood, bone, clay, various types of stone, different vegetable fibres (cotton, flax …) and animal tissues (leather, hair …), indigenous metals (copper, gold, silver …), naturally formed glass (obsidian), (powdered) minerals with an intense colour etc. As material culture expanded and ancient technologies evolved, artefacts of increasing sophistication were made, for example by combining several materials in one artefact (metal-inlaid wooden tools, painted earthen­ware bowls …). Another important evolution was that, next to natural materials, more manmade materials such as silicate glass, refined metals/metal alloys, ceramics and other products of proto-chemical workshops gradually began to be used. While the materials that could be employed for the manufacture of artefacts were originally limited to those that were locally available, an increase in trade between early human communities also expanded the variety of available materials, allowing new or more expensive equivalents of local starting materials to be used. In turn this stimulated the imagination of artists and artisans, leading to cultural innovations both on the material level as well as the artistic level. The technological advances realized during past historical periods such as the Ancient Kingdom in Egypt, Mediaeval Europe, 18–19th century China and Japan and post-colonial America can be reconstructed by careful material study of the artefacts that have survived from these periods. Such artefacts are usually (relatively) rare and require appropriate conditions to guarantee their long-term preservation and the possibility for scholars and the general public alike to appreciate them, either for their techno-historical or their culturo-aesthetic value. These valuable, often irreplaceable, objects `out of the past' (such as paintings/drawings, tapestries, garments, photographs, objects in metal, wood, clay, stone, glass …) are generally denoted cultural heritage (CH) artefacts.

Depending on the (complexity of the combination of) materials that were employed to manufacture these CH artefacts, the degree to which the individual materials may have survived the passage of time since their creation may vary widely. This broadly depends on the one hand on the characteristics of the material itself (for example, artefacts made of gold will corrode far less than those made of bronze) and on the other hand on the environmental circumstances in which the artefacts have passed important parts of their lifetime. For example, stained window glass may resist significant corrosion when kept intact inside the window frames of a well ventilated cathedral, while the same glass, buried for 400 years in moist soil, may become severely weakened in mechanical strength and develop brown staining. While there is a general belief that oil paintings are complex but essentially static assemblages of widely different (in)organic materials, at or just below the seemingly placid surface of these works of art chemical reactions are taking place that slowly alter the chemical make-up of the paint layers. While some of these reactions are the result of intimate contact between the different materials, most are driven forward by external physicochemical factors. A prime stimulus for reduction–oxidation (redox) reactions is light absorption by coloured substances (molecules) in the ultraviolet (UV) and visible (Vis) range. Such reactions can lead to the spontaneous in situ formation of secondary chemicals that will often differ from the original materials in their macroscopic properties (such as colour, volume and porosity). Both the organic components of paint (the protein-, saccharide- or lipid/oil-based binding media, organic dyes etc.) and/or the inorganic components (mostly pigments based on metal ions) may be affected. In a similar manner, statues and related CH artefacts composed of different metals may develop significant corrosion at locations where different materials meet or where other sources of mechanical stress were applied to the material. In the degradation of glass, metal and paint alike, another important factor is the often cyclic variation in relative humidity in museums, warehouses or archaeological depots, which causes the condensation and re-evaporation of minute moisture droplets within the microporous material that may have formed on their surface. The latter can act as miniature galvanic cells in which redox reactions can occur at the interface between the original material, the material that is covering or touching it and water. In addition, phenomena such as the crystallization of salts, the leaching of metal cations from the original materials and their in situ recombination with short-chain organic acids such as formates, acetates, oxalates or longer carboxylic acids may lead to insoluble metal soaps that can either protect or undermine the mechanical integrity of a CH artefact. Cycles of condensation/evaporation may also transport secondary alteration compounds towards the surface, leading to the formation of weathering crusts. These crusts can be partly crystalline; almost all have a colour and texture that is quite different from those of the original material.

In order to obtain insights into the chemical (and in particular redox) transformations (i) that were used to manufacture the objects/materials, (ii) that slowly (or more rapidly) can change the outlook and/or threaten the long-term integrity of CH artefacts and (iii) that were introduced during conservation treatments, X-ray absorption spectroscopy (and methods related to it) has proven to be particularly valuable in the last few decades.

Since XAS experiments are almost exclusively conducted at synchrotron facilities, most XAS studies are performed on small samples that are taken from CH artefacts. Only in a few rare cases have XAS or related measurements been performed directly and in a non-invasive manner on the artefacts as a whole. For this purpose, the latter were transported to the appropriate synchrotron beamline. The displacement of unique, irreplaceable or very valuable artefacts to synchrotron-radiation (SR) facilities is hampered by the fact that they are difficult to organize and/or fund (insurance costs). Moreover, most XAS beamlines are designed to accommodate relatively small samples and have difficulty in accepting large-scale CH artefacts such as entire statues or paintings.

The experience of the last 20 years has shown that XAS is most often employed to characterize (the degradation of) inorganic materials such as glass, ceramics, minerals, pigments and paints (see Fig. 1[link]). On the other hand, in the case of wood, paper, textiles etc., where an inorganic (minor) component may be responsible for the degradation of the organic matrix, XAS can provide very valuable clues about the chemical transformations that have caused the unwanted damage.

[Figure 1]

Figure 1

(a) Number of papers published annually describing the use of XAS and related methods for the characterization of various types of CH materials. (b) Distribution of published papers over the chemical elements.

2. X-ray microprobes, X-ray microscopes and XAS in CH studies

The use of XAS and related methods in cultural heritage has been reviewed by several authors (Cotte et al., 2010[link]; Bertrand et al., 2012[link]; Janssens et al., 2010[link]; Farges & Cotte, 2016[link]). Fig. 1[link](a) shows the number of published studies in the period 1995–2016. The first applications of XAS generally start appearing from 1995 onwards, with a regular number of papers appearing annually since 2004. Among these, K-edge XAS of the elements sulfur, manganese, iron and copper is frequently employed to study predominantly ceramic, pigmented and glassy materials. Iron- and copper-rich metallic artefacts and related problems are also well studied by means of XAS.

The change in publication pace in 2004 is related to the fact that SR-based X-ray microprobes (hard X-ray region, E > 5 keV) and X-ray microscopes (soft X-ray region, E < 5 keV) started routine operation at second- and third-generation synchrotron facilities around this period. Since CH materials are usually multi-component and often also strongly heterogeneous in nature, while degradation phenomena tend to change the material properties predominantly at the very surface, i.e. in the topmost few micrometres, only those forms of X-ray spectroscopy that can extract localized information are relevant in this context. This can take essentially two forms: either as a form of full-field microscopy in which spectroscopic information is obtained from all pixels of the sample area under study in a parallel manner or via a scanning X-ray microspectroscopy approach in which only a very tiny spot on the sample surface is irradiated, yielding spectroscopic information. Full-field forms of XAS-based microanalysis include scanning transmission X-ray microscopy (STXM), a method relaying on the absorption of monochromatic X-rays that traditionally operates in the 0.1–1 keV range and that `interrogates' the K absorption edges of elements such as carbon, nitrogen and oxygen (Chen, 1997[link]; de Smit et al., 2008[link]; Solomon et al., 2005[link]; Urquhart & Ade, 2002[link]). It is therefore suitable for extracting information on the organic fraction of CH materials. In recent years, the possibility of performing spectroscopic measurements in full-field imaging mode in transmission geometry has also been realized (see Section 4[link]; Pouyet et al., 2015[link]; Meirer et al., 2013[link]). (Hard) X-ray microprobes, generally operating in the energy range from 1–2 to 23 keV, can address a much larger series of K, L (and occasionally M) edges of relevant elements. Since these devices frequently employ rhodium-coated mirrors, the absorption-edge energy of this element (23.229 keV) in many cases defines the upper working energy of X-ray microprobes. Next to silicon, accessible elements include alkaline and alkaline-earth elements such as sodium, magnesium, potassium and calcium (the major constituents of glass, ceramics …) and all first-row transition elements (Ti–Zn, the major constituents of most metallic CH artefacts and of most inorganic pigments, inks …; Cabaret et al., 2010[link]), which may all be studied via their K edges. XAS of heavier elements (with K edges above 23 keV, i.e. Pd–Ba), which are occasionally present in metal alloys and glass/ceramics, can be performed using their L edges (situated in the 3–6 keV energy range). The same applies to the heavy elements mercury, lead and bismuth, elements that are frequently encountered in paints, with L-edge energies from 12 to 16 keV; in rare cases the M edges of these elements are also used (2–3 keV range). The X-ray microprobes very often work in X-ray fluorescence (XRF) mode and only occasionally employ transmission mode for recording XAS data. XRF-mode XAS data acquisition allows information to be obtained over a wider concentration range and is also more compatible with strongly absorbing sample matrices, the thickness of which is less critical/limiting. Since reproducible energy scanning without measureable changes of the position, orientation or size of the primary X-ray microbeam is not possible in practice at many experimental stations, in many CH studies data acquisition is limited to micro-XANES (X-ray absorption near-edge spectroscopy) measurements. XANES measurements involve recording X-ray absorption in a region of around 100 eV around the edge of interest. Only when the X-ray microprobe endstation is specifically optimized for it or when fairly homogeneous materials/samples (such as glass and some types of metal alloys) are examined does it become possible to record XAS spectra over a larger energy range (>500 eV) in order to record laterally resolved extended X-ray absorption fine-structure (EXAFS) data. Such studies are much rarer than those relying on micro-XANES data. Another limiting factor in this respect is that due to the complex and heterogeneous character of the samples analyzed, leading to complex speciation, the X-ray absorption signal is averaged and almost no information can usually be deduced beyond the first coordination sphere. In these situations, XANES analysis may/must be considered as sufficient and has often been preferred to full EXAFS data collection, interpretation and modelling.

Since the extraction of micro-XAS data from CH materials is frequently realized by means of X-ray microprobes, the same (CH) material is often examined by means of a combination of X-ray-based microprobe modalities: next to information on valence state (micro-XANES), nearest-neighbour types, number and orientation (micro-EXAFS), microscopic X-ray powder diffraction (micro-XRPD) is very frequently employed to allow a more specific identification of the crystalline compounds that are present and to visualize their distribution throughout the examined area. A mode of operation that is frequently combined with the recording of micro-XANES spectra from individual sample locations is the recording of micro-XRF maps (yielding distribution maps of one or more chemical elements) at a few relevant energies close to an absorption edge of an element of interest (for example iron) to obtain semi-quantitative distribution maps of this element in various valence states (for example Fe2+ and Fe3+). This modus operandi is gradually being replaced by full-field (FF) or full-scale (FS) XANES imaging.

3. Representative XAS-based studies of different classes of CH materials

3.1. Glass and ceramics

Both XANES and EXAFS have extensively been used to study the structure of silicate glasses (Greaves, 1985[link]), including the valence state and coordination of its major, minor and trace components or elements responsible for defining/altering the colour of the glass. The oven redox conditions during the production of naturally coloured glass have strong implications for its final hue because they affect the Fe3+/ΣFe ratio. In Roman archaeological glass, samples and equivalent soda–lime–silica calibration Fe3+/ΣFe values were determined in parallel with Fe K-edge XANES (by using the pre-edge peak position) and with optical absorbance spectrophotometry at 1100 nm (Ceglia et al., 2014[link], 2015[link]). Potash and soda–lime stained glasses from the 12th and 13th centuries, coloured blue by cobalt, were investigated by Mn, Fe and Cu K-edge X-ray and optical absorption spectroscopies in order to determine the oxidation states of these elements and their impact on the blue colour (Hunault et al., 2016[link]). Normally, Co2+ is present with tetrahedral coordination; replacing the alkali metal from K+ to Na+ increases the local disorder around the cobalt ion (Hunault et al., 2014[link]). XANES and EXAFS at the Co K edge were combined to examine the influence of the alteration on the local cobalt environment (Robinet et al., 2011[link], 2013[link]).

In a number of historical periods, including the Antique period, opaque glass was made by the presence of small crystalline particles dispersed in the translucent vitreous matrix. XAS and other methods have been used to characterize a number of very rare, highly decorated/coloured intact Italian glass vessels and beads from the seventh to fourth century BC (Arletti et al., 2008[link]; see Fig. 2[link]). No sampling of these objects was possible, making it necessary to transport them to a synchrotron facility. Iron was mostly present in reduced form in the bulk glass of the vessels and in the oxidized form in the decorations, indicating that these glass artefacts were produced in at least two distinct processing steps under different furnace conditions. Roman mosaic tesserae, opacified by means of calcium antimonate, were also studied (Lahlil et al., 2010[link]), revealing that they were prepared via in situ crystallization, probably by using roasted stibnite (Sb2O4) and by heat-treating the glass–stibnite mixture for one or two days. However, to prepare the opacified white, blue and turquoise glasses of the 18th Egyptian dynasty, early Egyptian glassmakers first synthesized calcium antimonate opacifiers such as nanocrystalline CaSb2O7 (which does not occur in nature) to add them to glass.

[Figure 2]

Figure 2

(a) Bronze-age glass artefact, (b) glass shard from the 18th Egyptian dynasty. Adapted from (a) Arletti et al. (2008[link]) and (b) Lahlil et al. (2011[link]).

Mediaeval and renaissance pottery was sometimes decorated with lustre surfaces, a glassy material featuring highly valued optical effects such as metallic reflection and iridescence (Colomban, 2009[link]). The earliest lustre pottery was made in Iraq in the ninth century (Pradell et al., 2008[link]), later spreading via Spain (Smith et al., 2006[link]) to central Italy during the 15th and 16th centuries (Padeletti & Fermo, 2003[link]; Guglieri Rodriguez et al., 2015[link]). Lustre can be considered to be the first intentionally made and reproducible nanostructured thin metallic film (Pérez-Arantegui et al., 2001[link]). EXAFS was used (Padovani et al., 2003[link], 2004[link]) to characterize the Italian production: copper and silver nanoparticles were responsible for the red and gold colours, respectively.

Historical glass, especially nondurable mediaeval glass, can undergo corrosion. This sometimes results in the formation of dark-coloured manganese-rich inclusions that reduce the transparency of the glass (Mn-browning or Mn-staining). While unaltered bulk glass contains manganese mainly present in the +2 valence state, inside the inclusions manganese is present in higher valence states (+3 to +4; Schalm et al., 2011[link]; Janssens et al., 2000[link]; Ferrand et al., 2015[link]). XANES imaging has been be used to monitor or evaluate conservation treatments aiming to reduce the manganese (Cagno et al., 2011[link]) as well as quantitative mapping of the manganese speciation (Nuyts et al., 2015[link]).

3.2. Mineral pigments and paints

Traditionally, artists' oil paints are prepared by mixing a finely ground (inorganic) pigment with a lipid- or protein-based binding medium. Upon `drying', the latter polymerizes into a three-dimensional network that immobilizes and shields the inorganic pigment grains from outside chemicals, humidity and light. However, given sufficient time, many inorganic pigments form undesired secondary products that usually have quite a different visual outlook to the original pigment. Usually, the chemical changes are limited to the outmost superficial layer of the objects. This makes the characterization of such phenomena challenging. Analyses with sub­micrometre resolution are particularly well suited for the study of transversal paint cross sections, since they allow discrimination between original and altered regions.

Micro-XANES, either in scanning or full-field mode, is increasingly used to study the chemical reactions involved in pigment-alteration processes. The sulfur-based pigments HgS (cinnabar when natural, vermilion red when synthetic), CdS (cadmium yellow) and As2S3/As4S4 (orpiment/realgar) have all been found to suffer from discolorations. While red HgS tends towards shades of grey or black (Cotte et al., 2006[link]; Radepont et al., 2011[link], 2015[link]), bright yellow CdS may evolve into a transparent to grey/white material (Van der Snickt et al., 2009[link], 2012[link]; Mass et al., 2013[link]; Pouyet et al., 2015[link]). The sulfides of arsenic lose their vivid yellow/red-orange hues, resulting in whitening or transparency of the paint surface (Keune et al., 2015[link], 2016[link]; Vermeulen et al., 2016[link]).

To elucidate the reasons for the darkening of the originally bright chrome yellow paint in works by Van Gogh, a combination of micro-XRF and S and Cr K-edge micro-XANES has been particularly helpful. This pigment alteration proved to be caused by the reduction of chromium(VI) to chromium(III) (Monico et al., 2011[link]). This is illustrated in Fig. 3[link] (Monico et al., 2015[link]; Monico, Janssens, Miliani, Brunetti et al., 2013[link]; Monico, Janssens, Miliani, Van der Snickt et al., 2013[link]). The darkening of zinc yellow (K2O·4ZnCrO4·0.3H2O) has also been studied by XAS and other methods (Zanella et al., 2011[link]).

[Figure 3]

Figure 3

(a) Photograph of Sunflowers by Van Gogh (Arles, 1889; Van Gogh Museum, Amsterdam) including sampling locations. (b) RGB (red–green–blue) composite SR micro-XRF image of sample F458/4 (124 × 51.2 µm; 6.090 keV). (c) Chromium(VI)/chromium(III) chemical state map of area 4-II. (d) XANES spectra collected from the areas indicated in (b) and (c). Adapted from Monico et al. (2015[link]).

The fading of Prussian blue {MFeIII[FeII(CN)6xH2O, with M = K+, [{\rm NH}_{4}^+] or Na+} in the presence of various white pigments has been investigated (Samain et al., 2011[link]; Samain, Gilbert et al., 2013[link]; Samain, Grandjean et al., 2013[link]; Gervais et al., 2015[link]; Gervais, Languille, Réguer, Gillet, Pelletier et al., 2013[link]) using Fe K-edge XAS, 57Fe Mössbauer spectroscopy and other methods. XAS revealed an effective decrease in the iron coordination number in the aged samples, which, when combined with the Mössbauer data, suggest a reduction of the surface iron ions in Prussian blue upon exposure to light.

3.3. Biomaterials

The 17th century Swedish warship Vasa was recovered in good condition after 333 years in Stockholm harbour. S K-edge micro-XANES demonstrated the presence of elemental sulfur within the wooden beams; at the surface, mostly sulfates were present (Sandström et al., 2002[link]). A similar situation was encountered with the Mary Rose, Henry VIII's warship that sank close to the Isle of Wight in 1536 (Sandström et al., 2005[link]). Here, micro-XANES was used to reveal an environmentally significant accumulation of organosulfur compounds in the waterlogged wood. The total concentration of sulfur in reduced forms was around one mass percent throughout the timbers, whereas the iron concentration may be as high as several percent.

Iron gall inks were largely used for writing in western European countries from the Middle Ages to the 20th century. These inks can damage the paper via two major mechanisms: (i) acid hydrolysis, which is enhanced by humidity, and (ii) oxidative depolymerization provoked by the presence of oxygen and free Fe2+ ions, the latter measured via Fe K-edge XANES (Rouchon, Duranton et al., 2011[link]). To investigate the ink penetration on the scale of a paper fibre, SR-based STXM was used (Rouchon & Bernard, 2015[link]), allowing in situ mapping of the iron redox state and carbon speciation down to the submicrometre scale. Fe K-edge XANES was also used to evaluate the effects of various antioxidizing treatments based on either the chelation of iron ions (Rouchon, Pellizzi et al., 2011[link]) or on radical scavenging (Rouchon et al., 2013[link]). In these materials extensive beam-induced reduction of iron can be observed (Gervais, Languille, Réguer, Gillet, Vicenzi et al., 2013[link]).

XAS techniques were also exploited to track possible heat-induced colour transformations in bone-like materials. Investigations on blue-coloured odontolite, i.e. palaeontological ivory used as a semi-precious stone in mediaeval art objects, using Mn K-edge XANES and EXAFS showed that this material obtained its colour from the presence of manganese(V) that, in the form of [{\rm MnO}_{4}^{3-}] ions, can substitute [{\rm PO}_{4}^{3-}] ions in the hydroxyapatite matrix of the bone. The blue coloration can generally be ascribed to the presence of manganese(V) species (Reiche et al., 2001[link], 2002[link]; Reiche & Chalmin, 2008[link]). In grey bones the colour can have different origins, but is generally caused by the presence of manganese oxides or oxyhydroxides; by means of XANES, it could be shown that Mn4+ ions in octahedral coordination, as in pyrolusite (MnO2), are present (Chadefaux et al., 2009[link]).

3.4. Metals

XAS allows the direct observation of the corrosion of metals, which is a major concern in art conservation (Adriaens & Dowsett, 2010[link]). Such measurements have mostly been performed on iron (Dillmann et al., 2007[link]) and bronze (Northover et al., 2008[link]; Lozzi et al., 2011[link]) artefacts. Usually, a multimodal approach is adopted involving SEM-EDX, XRF, XRD, Raman and XAS (De Ryck et al., 2003[link]). The XRF/XAS combination is advantageous since all of the XRF emission lines below the XANES edge being investigated are recorded simultaneously.

The corrosion of iron archaeological artefacts in soils has been studied by means of a combination of X-ray absorption speciation techniques at the Fe, Cl, S and P K edges (around 7.1, 2.8, 2.5 and 2.1 keV, respectively) with other synchrotron or laboratory methods. This led in particular to a better understanding of the structure and reactivity of the chlorinated iron compounds that are known to play a major role in iron corrosion, such as the iron oxyhydroxide compound akaganeite (β-FeOOH), and to a better understanding and distinguishing of the patterns of corrosion products formed in various environments (Mirambet et al., 2010[link]; Monnier et al., 2011a[link],b[link], 2014[link]; Réguer et al., 2015[link]; Monnier, Neff et al., 2010[link]; Monnier, Réguer et al., 2010[link]; Saheb et al., 2011[link]). X-ray-excited optical luminescence (XEOL) signals can be used to study superficial corrosion layers of both copper-based (Adriaens et al., 2013[link]; Sabbe et al., 2014[link]) and silver-based (Wiesinger et al., 2015[link]) metals.

4. Recent developments

Since in a number of cases X-ray emission spectroscopy (XES) and resonant inelastic X-ray spectroscopy (RIXS) can offer a higher spectral resolution than `regular' XAS and thus may allow more species-specific information to be obtained, in the near future they might become very useful for CH investigations, provided that it will become possible to employ them in microprobe mode (van Bokhoven & Lamberti, 2016[link]).

While most current CH studies make use of `hard' (E > 3 keV) X-rays, in the soft X-ray range a number of analytical possibilities could be better exploited. Scanning transmission X-ray microscopy (STXM) is a method that provides speciation information on carbon, nitrogen and oxygen that is often complementary to that obtained at transition-metal K edges (Rouchon & Bernard, 2015[link]; Ferrand et al., 2014[link]). The equivalent of STXM in the hard-energy regime (sometimes called full-field XANES) is also proving itself to be useful for CH investigations (Cotte et al., 2017[link]).

Note: This chapter was originally written in 2016.


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