Raman scattering features of lead pyroantimonate compounds: implication for the non‐invasive identification of yellow pigments on ancient ceramics. Part II. In situ characterisation of Renaissance plates by portable micro‐Raman and XRF studies

The effectiveness of Raman spectroscopy (using a bench‐top system on standard pigments) for the characterisation of modified lead antimonate yellows was demonstrated in the already published Part I. The knowledge gained is employed here for the study of yellow glazes on genuine Renaissance plates with the aim of identifying non‐invasively lead pyroantimonate compounds by portable micro‐Raman equipment. The investigation was carried out directly on site, at the Victoria and Albert Museum (London, UK) and at the Museo Statale d'Arte Medievale di Arezzo (Arezzo, Italy), combining Raman and X‐ray fluorescence analyses. In addition to the spectral features of both unmodified Naples yellow and Sn‐ and Zn‐modified lead antimonate compounds, the Raman patterns related to partially modified pyrochlore structures were observed. For this reason, the possible Sn‐induced modification of Naples yellow by cassiterite (SnO₂), present within the glaze as opacifier was explored on lead antimonate yellow glaze mock‐ups fired at different temperatures. Copyright © 2010 John Wiley & Sons, Ltd.     

Characterization of chromium‐containing ceramic pigments by XRF and XRD

As no methodology was found in the literature for characterizing ceramic pigments chemically and mineralogically, the present study was undertaken to establish a methodology for the chemical and phase characterization of ceramic pigments by x‐ray fluorescence (XRF) spectrometry and x‐ray diffraction (XRD). In view of the large number of pigments described in the literature (around 44), the present study was limited to characterizing pigments that contained chromium, which is the most versatile chromophore used in ceramics. Copyright © 2004 John Wiley & Sons, Ltd.     

Iron speciation in ancient Attic pottery pigments: a non‐destructive SR‐XAS investigation

The present work reports a detailed investigation on the speciation of iron in the pigments of decorated pottery fragments of cultural heritage relevance. The fragments come from the Gioiosa Guardia archaeological site in the area of the `Strait of Messina' (Sicily, Southern Italy), and date back to VI–V century BC. The purpose of this study is to characterize the main pigmenting agents responsible for the dark‐red coloration of the specimens using non‐destructive analytical techniques such as synchrotron radiation X‐ray absorption spectroscopy (SR‐XAS), a well established technique for cultural heritage and environmental subjects. Absorption spectra were collected at the Fe K‐edge on the Italian beamline for absorption and diffraction (BM8‐GILDA) at the European Synchrotron Radiation Facility in Grenoble (France). In order to determine the speciation of Fe in the samples, principal component analysis and least‐squares fitting procedures were applied to the near‐edge part of the absorption spectra (XANES). Details on the local structure around the Fe sites were obtained by analyzing the extended part of the spectra (EXAFS). Furthermore, an accurate determination of the average Fe oxidation state was carried out through analysis of the pre‐edge peaks of the absorption spectra. Samples resulted composed of an admixture of Fe₂O₃ (hematite or maghemite) and magnetite (Fe₃O₄), occurring in different relative abundance in the dark‐ and light‐colored areas of the specimens. The results obtained are complementary to information previously obtained by means of instrumental neutron activation analysis, Fourier transform infrared absorbance and time‐of‐flight neutron diffraction.     

Precious coral non‐destructive characterization by Raman and XRF spectroscopy

Precious corals are some of the most valuable living marine resources, growing and commercially exploited only in limited areas of the world, namely the Mediterranean Sea and the Northern Pacific Ocean. Their skeleton is formed by calcium carbonate crystallized in the form of calcite whereas their color is because of the presence of partially demethylated polyene pigments. Recently, Pacific corals have been included in the appendix II of CITES list, while Mediterranean corals are still excluded. Different Corallium species of Corallidae family (e.g. Corallium rubrum, Corallium elatius and Corallium secundum) collected from different locations of the Mediterranean Sea and the Pacific Ocean were analyzed by Raman spectroscopy for the characterization of the reddish pigment and by X‐ray fluorescence (XRF) for the determination of the chemical composition of their skeletons, in order to obtain molecular and elemental data with two relatively easy and non‐destructive techniques, which can be used quite steadily for authentication purposes. Raman analysis demonstrated the presence of specific vibrational bands useful to identify the colored pigments as a mixture involving methylated and demethylated polyenes such as carotenoids and parrodienes, characterized by the presence of ―CH₃ groups along the polyene chain. The ratio between the Raman signal and fluorescence background was found to vary as a function of the macroscopic color of the coral, but Raman analyses resulted inadequate for distinguishing between corals having similar color but different origins. On the other side, XRF data provided reliable information for an appropriate separation between Pacific and Mediterranean corals at the elemental level. The results of this study will be of great relevance for the authentication and identification of the origin of corals in trade market by means of completely non‐destructive techniques. Copyright © 2016 John Wiley & Sons, Ltd.     

Analysis of mural paintings using in situ non‐invasive XRF,FTIR spectroscopy and optical microscopy

An analytical protocol consisting of X‐ray fluorescence spectroscopy, optical microscopy and Fourier transform infrared spectroscopy was used to study the origin and the nature of the materials (pigments, binders and coating preparation) of the Fundenii Doamnei church mural paint from Bucharest. The main interest of the present study consisted in the original votive paint from narthex, painted in 1757 in a secco technique. During analysis, an unexpected pigment in the votive paint could be detected by the combined analytical techniques: ultramarine blue. Along with this pigment, the presence of gypsum binder based on egg and flax seed oil could also be evidenced. These results demonstrated a secco execution technique of the votive paint and also the presence of a restoration treatment. Moreover, during the present study, the components of the preparation layer and the constitutive pigments from both 1699 and 1757 years mural paints have been analyzed. Hence, the following pigments could be identified: vermilion, azurite, cinnabar, lead white, ochre, natural umber and gold, by using the combination of the analytical techniques. The novelty of our results consists in detecting the composition of the materials used in this church painting (fresco and a secco) during these 254 years since its first restoration. The results of these investigations pointed to the suitability of the non‐destructive and semi‐destructive analytical techniques in the complex characterization of the paints realized in different techniques, at different periods. Copyright © 2013 John Wiley & Sons, Ltd.     

Testing of Raman spectroscopy as a non‐invasive tool for the investigation of glass‐protected pastels

Five French pastels and a sanguine drawing dating from the 17th to the 20th century were studied by Raman spectroscopy. Different operative conditions were used: the pastels were investigated through their protective glass, and the results obtained were compared with those obtained after removing the glass and after sampling a micrometric particle of pigment. Different parameters (wavelengths, powers of excitation and objectives) were tested in order to assess the optimal procedure of analysis for this fragile work of art. The results obtained for black (carbons), yellow (chrome/cobalt yellow), red (lead oxide, vermillion, orpiment), brown (red lead and chrome yellow), blue (Prussian blue, lapis lazuli/ultramarine), green (mixture of above blue and yellow pigments) and white (calcite, lead white, anatase) pigments are presented and the consistency of the pigments' period of use with the dating proposed for each pastel is evaluated. In one of the pastels, the blackening of the carnation colour made of an unstable mixture of lead white, red lead and vermilion was studied. Copyright © 2010 John Wiley & Sons, Ltd.     

MA‐XRF investigation of the Altenberg Retable from 1330

The Altenberg Retable is one of the most important works of German art from the early 14th century. Composed of a shrine, a Madonna figure, and painted wings, it once adorned the high altar of the convent church in Altenberg/Lahn. The side and rear walls of the shrine were overpainted in 1609. Although conventional methods such as infrared reflectography and X‐ray radiography could not reveal the underlying medieval paint layer, we succeeded by conducting μ‐X‐Ray fluorescent studies. The latter measurements included a handheld spectrometer as well as μ‐X‐Ray fluorescent large area scanner. Nine sections of the side and rear walls were examined as well as a field on one of the wings (as a reference). In each section, spectra were recorded that comprised about 20 elements ranging from K to Bi. Maps of Ca, Fe, Co, Cu, Zn, As, Hg, and Pb were evaluated and interpreted on the basis of the results of prior color sampling analysis. By superposing several element maps, the original medieval iconographic program with its rows of standing saints could be revealed. With the help of iconographic comparison, these saints could be identified: St. Christopher in the central part of the rear wall, flanked by the 4 female saints Clare, Agnes, Dorothy, and Barbara. On the side walls, the apostles Peter and Paul, as well as the deacons Stephen and Lawrence were depicted. Discussed are not only different scenarios of usage for these images behind the altar but also the limits and possibilities of the measurement technology in this specific application.     

Testing of Raman spectroscopy as a non‐invasive tool for the investigation of glass‐protected miniature portraits

Six French miniature portraits on ivory and paper dating back to the 18th to 19th centuries have been studied by Raman spectroscopy. The miniatures have been investigated through their protective glass cover using different operating conditions: various laser wavelengths (1064, 785 and 532 nm), spectrometers (fixed and mobile) and objectives (10× to 200×). The results obtained for black (carbon), grey (carbon + chalk), red (lead oxide, vermillion), blue (Prussian or phthalocyanine blue), green (emerald or Paris green) and white (lead white) pigments are presented. The consistency of the period of use of the pigments with the proposed dating for each artwork is evaluated. Attention is paid to the analysis of the ivory substrates (assigned to Asian elephant ivory) and to the protective glass. Copyright © 2011 John Wiley & Sons, Ltd.     

Determination of gold,platinum and uranium in South African ores by high‐energy XRF spectrometry

An automated energy‐dispersive x‐ray fluorescence spectrometer, called the AZTEC, was developed for the non‐destructive determination of gold, platinum and uranium in Witwatersrand ores, by utilizing the high‐energy spectral regions of the K x‐ray lines of these elements. It provides a viable alternative to fire assay, and measures gold concentrations down to <1 ppm. About 100 g of pulverized sample are presented for analysis in a 20 mm diameter tube, and the fluorescent x‐rays are detected by an array of up to 12 high‐purity germanium detectors. Count‐rates of up to 10⁶ counts per second per detector can be processed by the signal processing electronics. The AZTEC technique is a variant of the scattered radiation technique. Concentration is related to peak intensities corrected for background, matrix variations, density and line overlaps. Provided that the samples are finely pulverised, the AZTEC analyses compare well with those obtained by fire assay. Production instruments are being used mainly in the gold mining industry, where they have analysed over 10⁷ samples to date. Copyright © 2004 John Wiley & Sons, Ltd.     

Potentiality of non‐destructive XRF analysis for the determination of Corinthian B amphorae provenance

Numerous samples of archaic transport Corinthian B type amphorae coming from the archaeological excavations of Gela (Sicily, South Italy) were analysed using non‐destructive X‐ray fluorescence (portable InnovX‐Systems ‘Alpha 4000’). Between the 6th and the 5th century BC the Corinthian B amphorae were diffused throughout the Western Mediterranean regions and Greece. Some researchers assigned these amphorae to different production areas, both in Southern Italy and in Greece, although, up to now, the exact attribution to the production centres is still under discussion. In this paper, with the aim to characterise the production sites of this important typology of amphorae, common ceramics, undoubtedly produced in Corinth, Corfù and Sybaris, were also analysed as these important Greek and Magna Graecia cities are considered by the archaeologists as the production centres of ‘Corinthian B’ amphorae. The multivariate analysis, performed on selected elements, clearly distinguished two groups of amphorae which, on the basis of archeological considerations, and by the comparison with reference ceramics, were assigned to Magnae Grecia (Sybaris and surroundings) and Greek productions. Copyright © 2011 John Wiley & Sons, Ltd.     

A risk assessment study of heavy metals in ambient air by WD‐XRF spectrometry using aerosol‐generated filter standards

A risk assessment study of the air quality in the surrounding of roads covered with slags coming from the non‐ferrous metal industry was performed. A monitoring campaign was carried out at three locations in Flanders by collecting the PM10 fraction and the total suspended particulates (TSP) of the airborne dust particles, entrapping heavy metals, on membrane filters. The heavy metal concentration on the dust filters was determined by wavelength‐dispersive x‐ray fluorescence (WD‐XRF) spectrometry. The XRF calibration curves were set up with filter standards prepared in the laboratory using an aerosol‐generated loading system. The acquired WD‐XRF results were confirmed by inductively coupled plasma atomic emission spectrometric (ICP‐AES) measurements after acid digestion on a selected number of filters. Electron probe microanalysis (EPMA) confirmed that aerosol‐loaded filter standards and dust filters with a concentration level of the analyzed element below 3300 ng cm^?2 were homogeneously distributed. Dust filters with higher concentrations, and especially filters loaded with the TSP fraction, reflected an inhomogeneous distribution of the analyzed element on the filter. The WD‐XRF analytical results acquired in the monitoring campaign revealed that the concentration of Pb on the dust filters never exceeded the immission standard (yearly average) of 2000 ng m^?3. It can be stated that the impact on human health is limited and can still be reduced by covering the polluted roads with a layer of asphalt. Further evaluation of soil and water samples from the nearby surroundings reveals that the heavy metal content in the slags makes an important contribution to environmental pollution, especially the contamination of groundwater. Copyright © 2003 John Wiley & Sons, Ltd.     

Quantitative non‐destructive determination of trace elements in archaeological pottery using a portable beam stability‐controlled XRF spectrometer

A portable beam stability‐controlled XRF spectrometer developed at the LNS/INFN laboratories at Catania (Italy) was used for the non‐destructive determination of some trace elements (Rb, Sr, Y, Zr and Nb) in fine pottery artefacts. The XRF system and the method developed to control the energy and intensity stability of the excitation beam are briefly discussed. Concentrations of Rb, Sr, Y, Zr and Nb were determined in 50 fine potsherds from the votive deposit of San Francesco in Catania by using a multi‐linear regression method. Additionally, in order to test the homogeneity of the material composing the fine pottery samples, a small portion of a few potsherds was powdered and analysed using the XRF system and the multilinear regression method. A comparison between non‐destructive and destructive approaches is presented and discussed. Finally, quantitative XRF data were compared with those obtained by chemical analysis of the powdered samples. The results allowed the testing of a non‐destructive methodology to be used for the identification and grouping of the different typological classes of fine pottery mainly represented in the San Francesco sanctuary. Copyright © 2005 John Wiley & Sons, Ltd.     

Real‐time non‐invasive detection of inhalable particulates delivered into live mouse airways

Fine non‐biological particles small enough to be suspended in the air are continually inhaled as we breathe. These particles deposit on airway surfaces where they are either cleared by airway defences or can remain and affect lung health. Pollutant particles from vehicles, building processes and mineral and industrial dusts have the potential to cause both immediate and delayed health problems. Because of their small size, it has not been possible to non‐invasively examine how individual particles deposit on live airways, or to consider how they behave on the airway surface after deposition. In this study, synchrotron phase‐contrast X‐ray imaging (PCXI) has been utilized to detect and monitor individual particle deposition. The in vitro detectability of a range of potentially respirable particulates was first determined. Of the particulates tested, only asbestos, quarry dust, fibreglass and galena (lead sulfate) were visible in vitro. These particulates were then examined after delivery into the nasal airway of live anaesthetized mice; all were detectable in vivo but each exhibited different surface appearances and behaviour along the airway surface. The two fibrous particulates appeared as agglomerations enveloped by fluid, while the non‐fibrous particulates were present as individual particles. Synchrotron PCXI provides the unique ability to non‐invasively detect and track deposition of individual particulates in live mouse airways. With further refinement of particulate sizing and delivery techniques, PCXI should provide a novel approach for live animal monitoring of airway particulates relevant to lung health.     

Distribution of selected elements in atherosclerotic plaques of apoE/LDLR‐double knockout mice assessed by synchrotron radiation‐induced micro‐XRF spectrometry

Apolipoprotein E and LDL receptor double‐knockout (apoE/LDLR^?/?) mice represent a reliable experimental model of atherosclerosis. The aim of the present study was to examine the elemental content of atherosclerotic plaques using synchrotron radiation‐induced micro x‐ray fluorescence (XRF) spectrometry. Numerous essential and trace elements were detected in cross‐sections of aortic roots collected from 6‐month‐old apoE/LDLR^?/? mice fed with chow diet. Two‐dimensional maps of the elemental distribution and point recordings were compared with images of consecutive sections stained histologically, allowing precise localization of the analyzed elements in morphologically defined areas of aortic lesion. The sulphur was detected in areas occupied by macrophages and smooth muscle cells. Iron was observed in high concentrations in cardiac and smooth muscle, blood clots and in adjacent coronary vessels. Lower concentrations of iron were seen in the regions of plaques rich in macrophages and lipids. Copper was detected in higher amounts only in cardiac muscle and its concentration in plaques was very low. There was a quite high content of calcium in aortic plaque areas containing lipids and macrophages. Much higher concentrations of calcium were observed in mineral deposits, mostly located in the aortic media. Similar distribution was also characteristic for phosphorus. Zinc was observed in moderately low concentrations in atheromas. Higher content of zinc was seen in smooth musculature, in cardiac muscle and in mineral concretions. The presented results provide a substantial morphological and physicochemical background for further investigations aiming to evaluate pharmacological and dietary treatment of atherosclerosis in an apoE/LDLR^?/? mouse model. Copyright © 2008 John Wiley & Sons, Ltd.     

Quantitative analysis of sulphides and sulphates by WD‐XRF: Capability and constraints

In the course of geochemical characterisations, total sulphur analyses are common practice although a differentiated quantification of sulphur species could provide valuable additional information, particularly when samples from unclear or changing redox environments are investigated. Unfortunately, a likewise simple distinct determination of just sulphide and sulphate already requires considerable efforts as sample dissolution or extra equipment. Two comparatively convenient strategies based on extended routine wavelength dispersive X‐ray fluorescence spectrometry measurements were adapted and optimised for a reliable quantitative sulphur speciation whereupon the matrix influence can be neglected. About 100 synthetic samples with different concentration ratios of sulphides and sulphates have been prepared and analysed using a WD‐XRF spectrometer. The first approach to differentiate between oxidation states and their quantification takes advantage of the Kα_1,2 doublet shift. Sulphide lines are located at 2309 eV, sulphate lines at 2310 eV, and mixtures can be quantified by a regression curve of fluorescence energy versus sulphide amount. Secondly, the amount of sulphide can be calculated by a regression curve based on the quotient Kβ′/Kβ of the sulphur peak heights or areas. In contrast to sulphides, sulphates show sulphur Kβ′ satellite peaks, and the intensity of S Kβ′ increases with the increasing sulphate content. However, the applicability of this second method is limited by the lower detection limit of sulphide (10 g kg^?1 sulphide in the sample) and interferences with lead (Pb Mβ line). Both approaches are validated by an independent method, Electrothermal Vaporisation Inductively Coupled Plasma Optical Emission Spectrometry, and already employed in investigations of ore‐containing mining dumps in Saxony/Germany. Copyright © 2016 John Wiley & Sons, Ltd.     

X‐ray‐induced alteration of specimens as crucial obstacle in XRF spectrometry of fluorine in rocks and soils

Occasionally suggested yet rarely performed X‐ray fluorescence (XRF) spectrometry of fluorine seems to fail systematically in yielding reliable quantitative results for rocks and soils. Repeated analyses reveal continuously drifting fluorescence intensities for fluorine, boron and chlorine. Typically, an increase, but in few cases also a decrease, over X‐ray exposure time is observed. For instance, fluorine concentrations in a soil standard appear to increase steadily from below the detection limit in the first run to nearly 850 mg/kg F more than 10 h later in the last. In contrast, cryolite is characterised by drastically decreasing intensities for fluorine. Although fluorescence intensities may be affected by preparation methods, specimen surface conditions and dynamic contamination, it is shown that none of these influencing factors is responsible for the observed trends. In fact, there is evidence that X‐radiation impact mobilises fluorine, boron and chlorine. Diffusion of radiolysis products towards the specimen's surface as well as the kinetics of adsorption and desorption or chemical reactions are believed to control the analyte concentration in the analysed layer decisively. Furthermore, during analysis, the latter is altered by considerable losses of binder or flux – if applicable – thus enhancing XRF intensities of boron and fluorine because of reduced absorption. In any case, signal stability appears to be limited by insufficient sample and specimen stability. It is concluded that for many soil and rock samples, XRF spectrometry is inappropriate to quantify fluorine, although the crucial obstacle is neither the analytical method nor the spectrometer sensu strictu. Copyright © 2012 John Wiley & Sons, Ltd.     

Semiempirical approach for standardless calibration in µ‐XRF spectrometry using capillary lenses

Quantitative µ‐XRF analysis based on standardless calibration is limited by the lack of information on the shape of the excitation spectrum resulting from using capillary lenses. The measurement of radiation scattered from a sample was used in combination with Monte Carlo simulation of radiation transport to estimate the energy spectral distribution of the excitation radiation. Further, a standardless calibration based on the fundamental parameter method implemented in the IAEA‐QXAS software package was carried out and verified for glass and fused ore certified reference materials. The accuracy and repeatability achieved are reported. Copyright © 2004 John Wiley & Sons, Ltd.     

Characterization of Indian Ayurvedic herbal medicines for their metal concentrations using WD‐XRF spectrometry

This article describes the details of metal concentrations evaluated using wavelength dispersive X‐ray fluorescence (WD‐XRF) spectrometry. A total of 22 elements, Na, Mg, Al, Si, P, S, K, Ti, Ca, Cr, Mn, Fe, Ni, Cu, Zn, As, Cd, Hg, Pb, Ba, Au, and Sn from 16 Ayurvedic medicines were characterized. The method was validated by analyzing the six certified reference materials of soil standards [NIST SRM‐2710, CRM 027‐050 (US‐EPA certified), PS‐1, TILL‐1 and TILL‐4 (Canadian certified reference material, CCRMP) and JSO‐1 (Japanese certified reference material)]. The elemental concentrations in all the standards are found to be within ± 10% of the reported values. Crystalline phases in the individual drug samples were explained by powder X‐ray diffraction (XRD) technique. Qualitative phase identification was done using the ICDD database. Copyright © 2010 John Wiley & Sons, Ltd.     

Direct chemical characterisation of clay suspensions by WD‐XRF

This study was performed to develop a method for directly controlling the chemical composition of clay slurries used in preparing ceramic floor and wall tile bodies by wavelength‐dispersive X‐ray fluorescence (WD‐XRF) spectrometry, without the prior need to dry and prepare the samples as fused beads or pellets for WD‐XRF measurement, owing to the importance of knowing the suspension chemical composition in real time for appropriate control of the industrial process. The study was conducted on a wide range of ceramic floor and wall tile bodies, which are used to prepare different suspensions. The influence of suspension viscosity (from 300 to 7000 cp), of suspension solids content (between 66 and 69%), and of the type of body composition (floor or wall tile) on the WD‐XRF measurement was determined. In these viscosity and solid content ranges, no appreciable differences were observed in the WD‐XRF measurement results, indicating that the possibly arising variations in viscosity and solids content in such clay suspensions in industrial practice do not influence the WD‐XRF measurement. In contrast, the type of body composition did influence the WD‐XRF measurement. The developed method is rapid, reproducible, and accurate, which was verified by analysis of the materials using the customary method of WD‐XRF measurement on fused beads. In addition, this method is cheaper and more harmless to the environment; it minimises waste generation, since no sample preparation is required and the plastic sample holders can be reused, thanks to the reusable sample holder system designed at the Instituto de Tecnología Cerámica laboratories. Copyright © 2011 John Wiley & Sons, Ltd.     

Chemical characterisation by WD‐XRF and XRD of silicon carbide‐based grinding tools

This paper addresses the chemical characterisation of silicon carbide‐based grinding tools. These are among the most widely used grinding tools in the ceramic sector, and instruments are required that enable the grinding tool quality to be controlled, despite the considerable complexity involved in determining grinding tool chemical composition. They contain components of quite different nature, ranging from the silicon carbide abrasive to the resin binder. To develop the analysis method, grinding tools containing silicon carbide with different grain sizes were selected from different tile polishing stages. To develop the grinding tool characterisation method, the different measurement process steps were studied, from sample preparation, in which different milling methods (each appropriate for the relevant type of test) were used, to the optimisation of the determination of grinding tool components by spectroscopic and elemental analyses. For each technique, different particle sizes were used according to their needs. For elemental analysis, a sample below 150 µm was used, while for the rest of the determinations a sample below 60 µm was used. After milling, the crystalline phases were characterised by X‐ray powder diffraction and quantified using the Rietvel method. The different forms of carbon (organic carbon from the resin, inorganic carbon from the carbonates and carbon from the silicon carbide) were analysed using a series of elemental analyses. The other elements (Si, Al, Fe, Ca, Mg, Na, K, Ti, Mn, P and Cl) were determined by wavelength‐dispersive X‐ray fluorescence spectrometry, preparing the sample in the form of pressed pellets and fused beads. The chemical characterisation method developed was validated with mixtures of reference materials, as there are no reference materials of grinding tools available. This method can be used for quality control of silicon carbide‐based grinding tools. Copyright © 2010 John Wiley & Sons, Ltd.