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Portable X‐Ray Fluorescence (XRF) has become increasingly popular where traditional laboratory methods are either impractical, time consuming, and/or too costly. While the Limit of Detection (LOD) is generally poorer for XRF compared to laboratory‐based methods, recent advances have improved XRF LODs and increased its potential for field‐based studies. Portable XRF can be used to screen food products for toxic elements such as lead (Pb), cadmium (Cd), mercury (Hg), arsenic (As), manganese, (Mn), zinc (Zn), and strontium (Sr). In this study, 23 seafood samples were analyzed using portable XRF in a home setting. After XRF measurements were completed in each home, the same samples were transferred to the laboratory for re‐analysis using microwave‐assisted digestion and Inductively Coupled Plasma Tandem Mass Spectrometry (ICP‐MS/MS). Four elements (Mn, Sr, As, and Zn) were quantifiable by XRF in most samples, and those results were compared to those obtained by ICP‐MS/MS. Agreement was judged reasonable for Mn, Sr, and As, but not for Zn. Discrepancies could be due to (1) the limited time available to prepare field samples for XRF, (2) the heterogeneous nature of "real samples" analyzed by XRF, and (3) the small beam spot size (~1 mm) of the XRF analyzer. Portable XRF is a cost‐effective screening tool for public health investigations involving exposure to toxic metals. It is important for practitioners untrained in XRF spectrometry to (1) recognize the limitations of portable instrumentation, (2) include validation data for each specific analyte(s) measured, and (3) ensure personnel have some training in sample preparation techniques for field‐based XRF analyses. [ABSTRACT FROM AUTHOR]

Lead poisoning remains the leading cause of diagnosed death for critically endangered California condors, which are annually monitored for lead exposure via blood tests. Blood tests are generally reflective of acute lead exposure. Since condors are victims to both chronic and acute lead exposure, measuring bone, which in humans is reflective of years to decades worth of exposure, is a valuable biomarker. In this study, we measured bone Pb of the tibiotarsus of 64 condors in vivo using a portable x-ray fluorescence device. The average uncertainty for measurements, typically reflective of how effective the device performed, was found to be 3.8 ± 2.2 µg/g bone mineral. The average bone lead level was found to be 26.7 ± 24.5 µg/g bone mineral. Bone lead correlated significantly with a sum of all blood lead measures over the lifetime of each condor. In the future, bone lead can potentially be used to inform treatment planning and address the chronic health implications of lead in the species. [ABSTRACT FROM AUTHOR]

Humans have occupied the Alps over most of the Holocene. Yet, continuous records on the impact of using montane resources and landscapes are scarce or confined to segregated areas or periods. We present a high-resolution geochemical record of the last 4800 years from the ombrotrophic peatland Piller Moor in the Central Alps (Tyrolean Oberland, western Austria), using inductively coupled mass plasma spectrometry (ICP-MS) and highly efficient inter-calibrated portable X-ray fluorescence analysis (pXRF). Fluctuations of metal enrichment factors (EF) for lead (Pb), copper (Cu), zinc (Zn) and antimony (Sb), accumulation rates of anthropogenic lead (Pb anth AR) and mineral matter (MAR), based on titanium (Ti), are in line with archaeological and pollen evidence for human presence and environmental change. Periods of intensified, erosive land use are indicated by MAR around 4400 cal BP, 3400 cal BP and, very prominently, at 2400 cal BP. After low MAR in the early Middle Ages, soil disturbances reappear around 1200 cal BP (750 AD), after 200 cal BP (1750 AD) and during the 20th century AD. We found evidence that metallurgy was practised in the area as early as 4450 cal BP, again from 3500 to 2900 cal BP and episodically between 2400 and 1400 cal BP. The Central Alps were presumably a source of increased Pb-emissions in the post-Roman period from 1500 to 1400 cal BP (450–550 AD). Generally, our findings suggest that mining predates archaeological and historical evidence. Following a continuous increase since the Middle Ages, atmospheric Pb EF and Pb anth AR peak around 1980 AD. The record of mineral atmospheric input illustrates the notable impact of human activities on soil erosion and dust entrainment in the Central Alps. Furthermore, links between Little Ice Age cold phases and reduced human impact and mining are established. Our high-resolution peat-geochemistry data quantifies atmospheric deposition of mineral matter and Pb, which act as proxies for landscape evolution and metallurgy on a local and regional scale. It provides new insights and a deeper understanding of the interaction of climate, environment and humans in mountainous landscapes like the Central Alps. [ABSTRACT FROM AUTHOR]

Abstract Indoor investigations are commonly used to assess the causes and extent of damage to bronze artwork and cultural heritage items; however, these methods typically involve destructive sampling and outdoor bronze sculptures are typically heavy and large, hindering their transport. In this study, 16 contemporary bronze sculptures exposed to outdoor environments for a period exceeding 20 years were evaluated in-situ to develop a non-destructive prediction model that can identify types of corrosion and quantify the amount of corrosion on bronze sculptures that cannot be easily transported. The sculptures were classified into three groups according to their patina chromaticity, reflectivity, and chemical composition. The corrosion characteristics were found to be copper oxide and sulfide patinas. Chromaticity and reflectivity investigations revealed that the chemical composition changes of the patinas corresponded to the formation of corrosion products, thus showing a high potential for the identification of the type of corrosion. Portable XRF spectroscopy showed that the low error rate of Cu make its compositional behavior a good indicator in identifying the type of corrosion of sulfide and chloride patinas. Portable Raman spectroscopy was able to detect basic sulfides such as brochantite, antlerite, and cuprite. The corrosion types and corrosion products on the bronze sculptures could be identified using chromaticity and reflectivity, portable X-ray fluorescence, and portable Raman spectroscopy. The rapid insitu diagnosis of these corrosion attributes is expected to contribute to establishing conservation treatment plans in the future.

Indoor investigations are commonly used to assess the causes and extent of damage to bronze artwork and cultural heritage items; however, these methods typically involve destructive sampling and outdoor bronze sculptures are typically heavy and large, hindering their transport. In this study, 16 contemporary bronze sculptures exposed to outdoor environments for a period exceeding 20 years were evaluated in-situ to develop a non-destructive prediction model that can identify types of corrosion and quantify the amount of corrosion on bronze sculptures that cannot be easily transported. The sculptures were classified into three groups according to their patina chromaticity, reflectivity, and chemical composition. The corrosion characteristics were found to be copper oxide and sulfide patinas. Chromaticity and reflectivity investigations revealed that the chemical composition changes of the patinas corresponded to the formation of corrosion products, thus showing a high potential for the identification of the type of corrosion. Portable XRF spectroscopy showed that the low error rate of Cu make its compositional behavior a good indicator in identifying the type of corrosion of sulfide and chloride patinas. Portable Raman spectroscopy was able to detect basic sulfides such as brochantite, antlerite, and cuprite. The corrosion types and corrosion products on the bronze sculptures could be identified using chromaticity and reflectivity, portable X-ray fluorescence, and portable Raman spectroscopy. The rapid insitu diagnosis of these corrosion attributes is expected to contribute to establishing conservation treatment plans in the future. [ABSTRACT FROM AUTHOR]

This work addresses the authenticity issue of fake potteries circulating in the illicit art market, imitating ancient artefacts, by an interdisciplinary and a multi‐analytical approach. In faking manufacture, unscrupulous forgers use increasingly advanced skills to mimic ancient materials and technologies and to produce artificial ageing. Despite the phenomenon of archaeological objects' forgery is considered a crime and a source of illicit earnings, there are not enough works in the literature to support the difficult unmasking of archaeological fake objects. In this work, a pair of ointment vases mimicking the "Etruscan‐Corinthian" style, seized thanks to the police activity of the Carabinieri Headquarters for the Protection of Cultural Heritage (Comando Carabinieri Tutela Patrimonio Culturale, TPC) and studied within "Laboratorio del Falso" at Roma Tre University, are analysed from the archaeological viewpoint, and then scientific investigations are carried out to understand materials and techniques used by the forger. The aim of this work is to provide useful tools for the study of similar fake objects by reconstructing the forger recipe and in particular identifying errors he committed with respect to the original manufactures, invisible to the eye. The characterization of raw materials is carried out by combining X‐ray fluorescence spectroscopy (XRF) and micro‐Raman spectroscopy techniques, in order to determine the composition of surface decoration, encrustations and surface deposits. By this simple protocol, it was possible to consistently clarify the aspects characterizing the modus operandi of the forger, through the identification of anachronisms, that is, materials and techniques incompatible with the hypothesized ancient manufacture. In particular, modern pigments of synthetic origin are found in decorations, such as cobalt‐based black pigment and Mars red pigments with the addition of a polymer to enhance the adhesion to the vases' body. [ABSTRACT FROM AUTHOR]

To quickly identify maritime sites polluted by heavy metal contaminants, reductions in the size of instrumentation have made it possible to bring an X‐ray fluorescence (XRF) analyzer into the field and in direct contact with various samples. The choice of source‐sample‐detector geometry plays an important role in minimizing the Compton scattering noise and achieving a better signal‐to‐noise ratio (SNR) in XRF measurement conditions, especially for analysis of wet sediments. This paper presents the influence of geometrical factors on a prototype, designed for in situ XRF analysis of mercury (Hg) in wet sediments using a 57Co excitation source and an X‐ray spectrometer. The unique XRF penetrometer prototype has been constructed and tested for maritime wet sediment. The influence on detection efficiency and SNR of various geometrical arrangements have been investigated using the combination of Monte Carlo simulations and laboratory experiments. Instrument calibration was performed for Hg analysis by means of prepared wet sediments with the XRF prototype. The presented results show that it is possible to detect Hg by K‐shell emission, thus enabling XRF analysis for underwater sediments. Consequently, the XRF prototype has the potential to be applied as an environmental screening tool for analysis of polluted sediments with relatively high concentrations (e.g., >2880 ppm for Hg), which would benefit in situ monitoring of maritime pollution caused by heavy metals. [ABSTRACT FROM AUTHOR]

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Abandoned sterile dumps can be a significant source of environmental pollution, therefore the distribution of trace elements throughout mining is vital. Monitoring environmental factors in closed mining perimeters aims to track the quality of discharged waters in the emissary and assess acid mine drainage, the quality of the soil and vegetation, stability, and the condition of the land surfaces within the perimeter of the sterile deposits. One of the primary sources of land, water and air pollution is sterile mining dumps. Knowing the source of pollution is the first step in adequately managing the affected areas. This paper investigates the physical–chemical properties and the concentrations of heavy metals in sterile dumps resulting from mining. We studied one sterile dump that was the result of ore processing and whose surface was covered with abandoned mixed ore concentrate (Pb, Zn), located in the Băiuț mining area (Romania), and a second sterile mining dump that was the result of exploration and exploitation work in the Ilba mining area (Romania). In order to determine the physicochemical characteristics of the studied sterile dumps and to determine the concentration of heavy metals, 27 sterile samples and one soil sample were taken from the Băiuț dump. Additionally, 10 sterile samples and one soil sample were collected from the Ilba dump. Aqua regia extractable concentrations of heavy metals were determined by inductively coupled plasma optical emission spectrometry. At the same time, using a portable XRF, we analyzed selected samples from each site for total metal concentrations. Furthermore, from each site, one sample was analyzed by FT–IR spectrometry. The pH values in both sterile dumps were highly acidic (≤3.5) and the content of heavy metals was generally increased. [ABSTRACT FROM AUTHOR]

Abstract The Regional Archive of Cusco in Peru guards valuable history collections with exceptional regional and international value dating from the sixteenth century to the present. Historical manuscripts are part of the identity of all people; they constitute a tangible cultural heritage that must be studied, valued, and protected. In this sense, the objective of this research was to identify the chemical compositions of inks and paper, with the goals of setting the background of their originality, identifying relationships between them, and glimpsing antecedents that generated degradation due to the compositions of the inks. This study is the first of its kind in Peru and reveals the chemical elements present in the writing ink, the seal, and the paper of five documents from the late eighteenth and early nineteenth centuries. Duplicate in situ nondestructive analyses were carried out using a hand-held X-ray fluorescence spectrometer under ambient conditions in soil mode, configured with three sequential shots, and energies from zero to 40, 40, and 15 keV, respectively. The elements S and Fe were present as components of iron gall inks. Cu and Zn were less abundant; probably, they provided less corrosion and more color intensity to the inks. The minor elements Pb, As, and especially Ag in all manuscripts differentiate them from European inks of the same period. Additionally, the five documents reflect the same elemental compositions but with different concentrations. This could mean that writers used local raw materials and Spanish ink recipes. Finally, the analyses of standard reference material, SRM 1646a and SRM 196b, gave results with acceptable precision. Graphical Abstract

This article presents the preliminary results of analyses by two non-destructive, portable and relatively economical methods in terms of investment/measurement time, on African Red Slip Ware: colorimetry and portable X-ray fluorescence. Alone or in combination, they allow to distinguish between the different productions of African Red Slip Ware as well as the different known workshops in Tunisia. These promising results encourage the further development of these approaches, which could be applied in situ to ceramics from consumption sites as well as to museum collections.

Roman wall paintings at Ostia Antica were studied for the first time in situ in an integrated approach using nuclear magnetic resonance (NMR) depth profiling, portable X-ray fluorescence (XRF), and visible induced luminescence (VIL) in order to explore the materials used in their construction and gain insight into the evolution of the Roman painting technique over time. NMR revealed the signatures of covered wall paintings through details of the structure of the top painted mortar layers, and the loss of this information that can be encountered when paintings are detached from the wall for preservation purposes. XRF provided information about the pigment composition of the paintings, and VIL was used to identify Egyptian Blue. Egyptian Blue was only found in the earlier wall paintings studied dating from 1st century B.C.E. to the 1st century C.E. The pigment palette seems to become limited to iron-based pigments in the later paintings, whereas the palette of the earlier paintings appears to be more varied including mercury, lead, and copper-based pigments.

The Altar Stone at Stonehenge in Wiltshire, UK, is enigmatic in that it differs markedly from the other bluestones. It is a grey–green, micaceous sandstone and has been considered to be derived from the Old Red Sandstone sequences of South Wales. Previous studies, however, have been based on presumed derived fragments (debitage) that have been identified visually as coming from the Altar Stone. Portable X-ray fluorescence (pXRF) analyses were conducted on these fragments (ex situ) as well as on the Altar Stone (in situ). Light elements (Z<37) in the Altar Stone analyses, performed after a night of heavy rain, were affected by surface and pore water that attenuate low energy X-rays, however the dry analyses of debitage fragments produced data for a full suite of elements. High Z elements, including Zr, Nb, Sr, Pb, Th and U, all occupy the same compositional space in the Altar Stone and debitage fragments, and are statistically indistinguishable, indicating the fragments are derived from the Altar Stone. Barium compares very closely between the debitage and Altar Stone, with differences being related to variable baryte distribution in the Altar Stone, limited accessibility of its surface for analysis, and probably to surface weathering. A notable feature of the Altar Stone sandstone is the presence of baryte (up to 0.8 modal%), manifest as relatively high Ba in both the debitage and the Altar Stone. These high Ba contents are in marked contrast with those in a small set of Old Red Sandstone field samples, analysed alongside the Altar Stone and debitage fragments, raising the possibility that the Altar Stone may not have been sourced from the Old Red Sandstone sequences of Wales. This high Ba 'fingerprint', related to the presence of baryte, may provide a rapid test using pXRF in the search for the source of the Stonehenge Altar Stone. [ABSTRACT FROM AUTHOR]

Black manganese-rich crusts are found worldwide on the façades of historical buildings. In this study, they were studied exemplarily on the façade of the Freiburger Münster (Freiburg Minster), Germany, and measured in-situ by portable X-ray fluorescence (XRF). The XRF was calibrated to allow the conversion from apparent mass fractions to Mn surface density (Mn mass per area), to compensate for the fact that portable XRF mass fraction measurements from thin layers violate the assumption of a homogeneous measurement volume. Additionally, 200-nm femtosecond laser ablation-inductively coupled plasma-mass spectrometry (fs LA-ICP-MS) measurements, scanning transmission X-ray microscopy-near edge X-ray absorption fine structure spectroscopy (STXM-NEXAFS), Raman spectroscopy, and imaging by light microscopy were conducted to obtain further insight into the crust material, such as potential biogenic contributions, element distributions, trace element compositions, and organic functional groups. While black crusts of various types are present at many places on the minster's facade, crusts rich in Mn (with a Mn surface density >150 μg cm−2) are restricted to a maximum height of about 7 m. The only exceptions are those developed on the Renaissance-Vorhalle (Renaissance Portico) at a height of about 8 m. This part of the façade had been cleaned and treated with a silicon resin as recently as 2003. These crusts thus accumulated over a period of only 12 years. Yet, they are exceptionally Mn-rich with a surface density of 1200 μg cm−2, and therefore require an accumulation rate of about 100 μg cm−2 Mn per year. Trace element analyses support the theory that vehicle emissions are responsible for most of the Mn supply. Lead, barium, and zinc correlate with manganese, indicating that tire material, brake pads, and resuspended road dust are likely to be the element sources. Microscopic investigations show no organisms on or in the Mn-rich crusts. In contrast, Mn-free black crusts sampled at greater heights (>8 m) exhibited fungal and cyanobacterial encrustation. Carbon-rich spots were found by STXM-NEXAFS underneath one of the Mn-rich crusts. However, these carbon occurrences originate from soot and polycyclic aromatic hydrocarbons (PAHs) deposited on top of the crust, rather than from organisms responsible for the crust's formation, as shown by STXM-NEXAFS and Raman spectroscopic measurements. Our results suggest that the crusts develop abiogenically, with vehicle emissions as dominant element sources.

Black manganese-rich crusts are found worldwide on the façades of historical buildings. In this study, they were studied exemplarily on the façade of the Freiburger Münster (Freiburg Minster), Germany, and measured in-situ by portable X-ray fluorescence (XRF). The XRF was calibrated to allow the conversion from apparent mass fractions to Mn surface density (Mn mass per area), to compensate for the fact that portable XRF mass fraction measurements from thin layers violate the assumption of a homogeneous measurement volume. Additionally, 200-nm femtosecond laser ablation-inductively coupled plasma-mass spectrometry (fs LA-ICP-MS) measurements, scanning transmission X-ray microscopy-near edge X-ray absorption fine structure spectroscopy (STXM-NEXAFS), Raman spectroscopy, and imaging by light microscopy were conducted to obtain further insight into the crust material, such as potential biogenic contributions, element distributions, trace element compositions, and organic functional groups. While black crusts of various types are present at many places on the minster's facade, crusts rich in Mn (with a Mn surface density >150 μg cm−2) are restricted to a maximum height of about 7 m. The only exceptions are those developed on the Renaissance-Vorhalle (Renaissance Portico) at a height of about 8 m. This part of the façade had been cleaned and treated with a silicon resin as recently as 2003. These crusts thus accumulated over a period of only 12 years. Yet, they are exceptionally Mn-rich with a surface density of 1200 μg cm−2, and therefore require an accumulation rate of about 100 μg cm−2 Mn per year. Trace element analyses support the theory that vehicle emissions are responsible for most of the Mn supply. Lead, barium, and zinc correlate with manganese, indicating that tire material, brake pads, and resuspended road dust are likely to be the element sources. Microscopic investigations show no organisms on or in the Mn-rich crusts. In contrast, Mn-free black crusts sampled at greater heights (>8 m) exhibited fungal and cyanobacterial encrustation. Carbon-rich spots were found by STXM-NEXAFS underneath one of the Mn-rich crusts. However, these carbon occurrences originate from soot and polycyclic aromatic hydrocarbons (PAHs) deposited on top of the crust, rather than from organisms responsible for the crust's formation, as shown by STXM-NEXAFS and Raman spectroscopic measurements. Our results suggest that the crusts develop abiogenically, with vehicle emissions as dominant element sources.

A method for estimating the composition of the metal core in historical and archaeological artifacts using surface X-ray fluorescence (XRF) data is described. The method is based on the combination of fluorescence data recorded at points of the object with different degrees of corrosion exploiting the general phenomenon of demetallation of the less noble components of the metal alloy. A theoretical approach is provided using the Johnson–Mehl–Avrami–Erofeev-Kolmogorov (JMAEK) formalism to describe demetallation. Experimental data for binary Zn Cu brass and Pb- and Sn-containing brass from Hofkirche in Innsbruck agree satisfactorily with the model. [Display omitted] • XRF data on historical metallic artifacts are treated. • Data from brass statues objects are representative of dezincication processes. • Such data can be described in terms of the Johnson–Mehl–Avrami–Erofeev-Kolmogorov (JMAEK) equation. • The JMAEK formalism is applied to determine the composition of the metal core. [ABSTRACT FROM AUTHOR]

Featured Application: Fast, cost efficient and non-invasive assessment of spatial variability of soil chemical and physical degradation phenomena. A combination of indirect soil investigation by proximal soil sensors (PSS), based on geophysical (ARP, EMI), physical (Cone Index –CI– by ultrasound penetrometry) and spectrometric (γ-rays) techniques, as well as pedological surveys, was applied in the field to assess the spatial variability of soil pollution and physical degradation in an automobile-battery recycling plant in southern Italy. Five homogeneous zones (HZs) were identified by the PSS and characterized by soil profiles. CI measurements and field analysis showed clear features of physical (i.e., soil compaction, massive structure) degradation. XRF in situ (on profiles) analysis using portable equipment (pXRF) showed Pb, Cd and As concentrations exceeding the contamination thresholds provided by the Italian regulation for industrial land use up to 20 or 100 cm of depth. Hence, a validation procedure, based on pXRF field survey, was applied to the PSS approach used for the HZs identification. High consistency was found between the HZs and the PTEs in the most contaminated areas. Significant negative Pearson correlation coefficients were found between γ-rays dose rate and Pb, Cu, Zn, As and Ni; positive ones were found between γ-rays and autochthonous lithogenic elements (V, Ti, Mn, K, Sr, Nb, Zr, Rb, Th), confirming that higher radionuclide activity correlated with lower pollution levels. [ABSTRACT FROM AUTHOR]

Abandoned sterile dumps can be a significant source of environmental pollution, therefore the distribution of trace elements throughout mining is vital. Monitoring environmental factors in closed mining perimeters aims to track the quality of discharged waters in the emissary and assess acid mine drainage, the quality of the soil and vegetation, stability, and the condition of the land surfaces within the perimeter of the sterile deposits. One of the primary sources of land, water and air pollution is sterile mining dumps. Knowing the source of pollution is the first step in adequately managing the affected areas. This paper investigates the physical–chemical properties and the concentrations of heavy metals in sterile dumps resulting from mining. We studied one sterile dump that was the result of ore processing and whose surface was covered with abandoned mixed ore concentrate (Pb, Zn), located in the Băiuț mining area (Romania), and a second sterile mining dump that was the result of exploration and exploitation work in the Ilba mining area (Romania). In order to determine the physicochemical characteristics of the studied sterile dumps and to determine the concentration of heavy metals, 27 sterile samples and one soil sample were taken from the Băiuț dump. Additionally, 10 sterile samples and one soil sample were collected from the Ilba dump. Aqua regia extractable concentrations of heavy metals were determined by inductively coupled plasma optical emission spectrometry. At the same time, using a portable XRF, we analyzed selected samples from each site for total metal concentrations. Furthermore, from each site, one sample was analyzed by FT–IR spectrometry. The pH values in both sterile dumps were highly acidic (≤3.5) and the content of heavy metals was generally increased.

Roman wall paintings at Ostia Antica were studied for the first time in situ in an integrated approach using nuclear magnetic resonance (NMR) depth profiling, portable X-ray fluorescence (XRF), and visible induced luminescence (VIL) in order to explore the materials used in their construction and gain insight into the evolution of the Roman painting technique over time. NMR revealed the signatures of covered wall paintings through details of the structure of the top painted mortar layers, and the loss of this information that can be encountered when paintings are detached from the wall for preservation purposes. XRF provided information about the pigment composition of the paintings, and VIL was used to identify Egyptian Blue. Egyptian Blue was only found in the earlier wall paintings studied dating from 1st century B.C.E. to the 1st century C.E. The pigment palette seems to become limited to iron-based pigments in the later paintings, whereas the palette of the earlier paintings appears to be more varied including mercury, lead, and copper-based pigments. [ABSTRACT FROM AUTHOR]

The Regional Archive of Cusco in Peru guards valuable history collections with exceptional regional and international value dating from the sixteenth century to the present. Historical manuscripts are part of the identity of all people; they constitute a tangible cultural heritage that must be studied, valued, and protected. In this sense, the objective of this research was to identify the chemical compositions of inks and paper, with the goals of setting the background of their originality, identifying relationships between them, and glimpsing antecedents that generated degradation due to the compositions of the inks. This study is the first of its kind in Peru and reveals the chemical elements present in the writing ink, the seal, and the paper of five documents from the late eighteenth and early nineteenth centuries. Duplicate in situ nondestructive analyses were carried out using a hand-held X-ray fluorescence spectrometer under ambient conditions in soil mode, configured with three sequential shots, and energies from zero to 40, 40, and 15 keV, respectively. The elements S and Fe were present as components of iron gall inks. Cu and Zn were less abundant; probably, they provided less corrosion and more color intensity to the inks. The minor elements Pb, As, and especially Ag in all manuscripts differentiate them from European inks of the same period. Additionally, the five documents reflect the same elemental compositions but with different concentrations. This could mean that writers used local raw materials and Spanish ink recipes. Finally, the analyses of standard reference material, SRM 1646a and SRM 196b, gave results with acceptable precision. [ABSTRACT FROM AUTHOR]

Since the development of portable X-ray fluorescence (pXRF) spectrometers, few studies have been conducted on the influence of spectral interferences between chemical elements. This study aims to improve the management of these interferences to obtain more reliable geochemical analyses. We specifically investigate Ca-related interferences on Sc analysis for the case of Ni-rich laterite samples using the Niton XL3t GOLDD + pXRF analyser. Three quantification methods were tested on 59 pelletized samples using the 'Soil' mode. The first, named 'Manufacturer', represents the elemental quantification directly provided by the device based on regions of interest and multilinear corrections of spectral interferences configured during the spectrometer design. The second, the '20 Cu' method, is based on spectral fitting using the PyMCA software. The third, the '18 Fe' method, combines spectral fitting with modified experimental conditions. For each, a quantification methodology was developed, establishing (i) Ca and Sc calibration lines and (ii) Ca/Sc threshold values delimiting fields of 'reliable', 'to be confirmed' and 'unreliable' measurements. The '20 Cu' and '18 Fe' methods greatly extend the 'reliable measurements' field concerning the Ca/Sc ratio compared to the 'Manufacturer' method. The '18 Fe' method was also found to provide the most negligible measurement dispersion. Supplementary material: Figures A–F and Tables A and B are available at https://doi.org/10.6084/m9.figshare.c.5511838 [ABSTRACT FROM AUTHOR]

A series of pottery samples from the Iranian site Tol-e Kamin, ranging from pre-historical period to the New Elamite, were analyzed in order to study the geochemical variability of the pottery assemblage. A total amount of 168 measurements were obtained using a portable XRF device and were statistically handled. The results could successfully distinguish the geochemical composition of potteries from the chalcolithic to the New Elamite periods in the Kur River Basin. A major shift in the use of different clay sources could be detected since the Proto Elamite period and afterward, in which the carbonated and marl content clays represented by Ca, Ba and Sr shifted to clay sources with a tendency to non-carbonate silty clay Al, Ti, and Fe from a different geological background. The results stress the importance of further provenance studies to address issues of trade and exchange possibilities in southwestern Iran.

Cobalt was commonly used as a colourant in the Egyptian glass industries of the 18th dynasty, dark blue glass being a regular find at palatial and settlement sites, including Amarna and Malqata. The main source of cobalt ore used during this period has been identified in the Egyptian western desert, around the oases of Kharga and Dakhla. In order to better understand the chaîne opératoire of Late Bronze Age glass production and -working, in particular with regard to cobalt ore, at Amarna, chemical analysis by portable X-Ray fluorescence was carried out in the field. This was done on contextualised archaeological material excavated at the site of Amarna, which cannot be exported from Egypt for analysis. The results of this study demonstrate how cobalt ore was used in the various known workshop sites at Amarna, resulting in a deeper understanding of raw materials use and exchange across this settlement.

Abstract An unidentified white substance was observed on the exterior parts of the southern side of Hopperstad Stave Church, located in Vik in Sogn and Fjordane (Norway). One of the 28 remaining stave churches in the country, Hopperstad Stave Church was built between 1130 and 1150 and it constitutes an important part of Norwegian cultural heritage. Such a substance was observed for the first time in 2009 and serious concerns about its harmfulness and origin have been raised. A comprehensive study involving non-invasive (portable XRF) and micro-invasive analyses (SEM, ICP-OES, TOC) was undertaken to investigate the physico-chemical nature of this white substance. Tarring, salt migration from the nearby cemetery, atmospheric agents, leakages from the roof, biological infestation, previous treatments with pesticides are among the possible causes of the phenomenon. This work—employing a unique approach in conservation/conservation science—indicates that the white substance is mainly inorganic and crystalline. It was, therefore, possible to exclude some of the possible causes, hence, clarifying some of the conservation issues of the church.

The accurate characterization of mafic and ultramafic rocks is a challenging but necessary task given the spatial and genetic relationship of mineralization with specific lithologies (e.g. komatiite hosted nickel-sulfides preferentially associated with cumulate-rich ultramafic rocks). Rock classification is further complicated as most mafic and ultramafic rocks have undergone varying degrees of alteration. The accuracy and reproducibility of characterization can be significantly improved by using portable energy dispersive X-ray fluorescence (pXRF) chemical data with portable visible and near-infrared (pVis-NIR) mineralogical data. A new workflow using pXRF and pVis-NIR is presented and used to reliably characterize mafic and ultramafic rocks from the Yilgarn Craton, Western Australia. The workflow involves six steps: (1) Mitigate and identify compound processing and closure issues. For example, we used a pXRF with helium flush to reliably and rapidly measure light elements and mitigate closure, i.e. problems related to data failing to sum to 100%. (2) Identify and exclude geochemically heterogeneous samples. Heterogeneity may be unrelated to alteration and caused by veining or small-scale structure interleaving of different rock types. Geochemical heterogeneity was evaluated using skewness and kurtosis of SiO2 data. (3) Relate rocks from similar magmatic, weathering and alteration events. This was achieved by interpreting data grouping of Vis-NIR ferric and ferrous iron data via a 852 nm/982 nm reflectance v. 651 nm/982 nm reflectance plot and the ferrous abundance index. Unrepresentative data were omitted. (4) Correct XRF iron data, and characterize lithology and alteration. Values ascribed to regions in the TAS (total alkali silica) diagram were used to approximate FeO and Fe2O3. Subsequently, geochemical indices (e.g. Mg#) were used to characterize the alteration box plot. (5) Characterize fractionation in detail. Fractionation variation diagrams were used to interpret fractionation, e.g. MgO v. Al2O3, Ca/Al v. Al2O3, Ni/Cr v. Ni/Ti, and MgO v. Cr. (6) Identify and quantify talc alteration and serpentinization. This included the use of a new alteration plot (Mg# v. 1410 nmRAD/Albedo) to estimate serpentinization and identify relationships between serpentine, carbonate, chlorite and talc abundances. The results and observations contained in this contribution have important implications for progressive technologies such as core logging platforms that are equipped with pXRF and pVis-NIR instruments. [ABSTRACT FROM AUTHOR]

A combination of indirect soil investigation by proximal soil sensors (PSS), based on geophysical (ARP, EMI), physical (Cone Index –CI– by ultrasound penetrometry) and spectrometric (γ-rays) techniques, as well as pedological surveys, was applied in the field to assess the spatial variability of soil pollution and physical degradation in an automobile-battery recycling plant in southern Italy. Five homogeneous zones (HZs) were identified by the PSS and characterized by soil profiles. CI measurements and field analysis showed clear features of physical (i.e., soil compaction, massive structure) degradation. XRF in situ (on profiles) analysis using portable equipment (pXRF) showed Pb, Cd and As concentrations exceeding the contamination thresholds provided by the Italian regulation for industrial land use up to 20 or 100 cm of depth. Hence, a validation procedure, based on pXRF field survey, was applied to the PSS approach used for the HZs identification. High consistency was found between the HZs and the PTEs in the most contaminated areas. Significant negative Pearson correlation coefficients were found between γ-rays dose rate and Pb, Cu, Zn, As and Ni; positive ones were found between γ-rays and autochthonous lithogenic elements (V, Ti, Mn, K, Sr, Nb, Zr, Rb, Th), confirming that higher radionuclide activity correlated with lower pollution levels.

The lack of accurate locational information on abandoned medieval and later graveyards constitutes a considerable challenge to national and local bodies tasked with their protection and management. These sites are increasingly in danger of destruction due to climatic changes, intensified farming schemes or developmental encroachment, and there is an ever-growing need to develop nonintrusive methods to ensure their detection and delineation so that they can be protected. In 2014, the Norwegian Directorate for Cultural Heritage received alarming information on the worsening state of the medieval church site at Furulund, in the southeast of the country. A successful, cost-effective campaign using high-resolution, large-scale georadar surveys in conjunction with geochemical mapping using portable XRF was undertaken in order to delineate and characterise the graveyard so that remedial actions could be initiated and the graveyard protected. Whilst the interpretations are unique to the site, the method combination has the potential to effectively resolve detection and protection of other, similar sites in Norway and beyond.

This research is concerned with the investigation of Egyptian and Egyptianizing artifacts dating back to the period comprised between the 10th century BC and the first half of 6th century BC, which were found in some archaeological sites of eastern-central Sicily. The examined Aegyptiaca include thirt-four items consisting of scarabs, funerary statuettes, figurines and unguentaria, which are mostly preserved at the regional archeology museum "Paolo Orsi" in Syracuse and, only in part, at the regional Aeolian museum "Luigi Bernabò Brea" in the Lipari island. Some of the investigated objects are made of faience (a glazed non-clay ceramic material, coated with an alkali-based glaze), while some others are in steatite or other stones. Through the chemical investigation of the selected artifacts, the study aims to extend the compositional dataset available on Aegyptiaca, as well as to identify the colorants used for the preparation of the investigated glazes. For such a scope, non-destructive bulk chemical analyses through portable x-ray fluorescence spectrometry (pXRF) were carried out on both the bodies and the overlying coloured glazes. A rather variable chemical composition was found in terms of both bodies and glazes, thus pointing to the use of different recipes and/or workshops for the investigated artifacts. The results obtained demonstrate the validity of this analytical technique in revealing the elemental composition of artifacts belonging to museum collections. [ABSTRACT FROM AUTHOR]

Cobalt was commonly used as a colourant in the Egyptian glass industries of the 18th dynasty, dark blue glass being a regular find at palatial and settlement sites, including Amarna and Malqata. The main source of cobalt ore used during this period has been identified in the Egyptian western desert, around the oases of Kharga and Dakhla. In order to better understand the chaîne opératoire of Late Bronze Age glass production and -working, in particular with regard to cobalt ore, at Amarna, chemical analysis by portable X-Ray fluorescence was carried out in the field. This was done on contextualised archaeological material excavated at the site of Amarna, which cannot be exported from Egypt for analysis. The results of this study demonstrate how cobalt ore was used in the various known workshop sites at Amarna, resulting in a deeper understanding of raw materials use and exchange across this settlement. [ABSTRACT FROM AUTHOR]

A series of pottery samples from the Iranian site Tol-e Kamin, ranging from pre-historical period to the New Elamite, were analyzed in order to study the geochemical variability of the pottery assemblage. A total amount of 168 measurements were obtained using a portable XRF device and were statistically handled. The results could successfully distinguish the geochemical composition of potteries from the chalcolithic to the New Elamite periods in the Kur River Basin. A major shift in the use of different clay sources could be detected since the Proto Elamite period and afterward, in which the carbonated and marl content clays represented by Ca, Ba and Sr shifted to clay sources with a tendency to non-carbonate silty clay Al, Ti, and Fe from a different geological background. The results stress the importance of further provenance studies to address issues of trade and exchange possibilities in southwestern Iran. [ABSTRACT FROM AUTHOR]

Portable EDXRF (Energy Dispersive X-Ray Fluorescence) spectrometer with the ability to perform rock tests in a helium atmosphere was applied to prepare unique calibration coefficients and mineralogical models. These data could be used for the chemical profiling, chemostratigraphy, gamma-ray, TOC and lithological interpretation of borehole geological profile. The measurements were conducted on 19 samples of sandstones and compared to the XRF data without helium flow. The acquired dataset was calibrated to the chemical laboratory tests (ICP-MS), gamma-ray spectrometry measurements (RT-50) and combined with the mineralogical data (XRD). The new methodology enables the measurement of sodium and enhances the possibility of detecting magnesium, thorium and uranium, compared to standard handheld XRF spectrometers. The applied method is dedicated to whole cores (without sample preparation) or cuttings which must be cleaned, dried, milled and pressed. [ABSTRACT FROM AUTHOR]

Light element data are required for robust and accurate lithogeochemical interpretations and are important components in the study of hydrothermal alteration and mineralization processes. In this contribution we review the latest available portable energy dispersive X-Ray Fluorescence (pXRF) technologies exclusively in the context of light element analysis, with focus on the acquisition of data for Na, Mg, Al and Si. We discuss pXRF hardware design limitations, quantify variables that attenuate X-ray energies through numerical modelling, including common pXRF configurations, and empirically investigate modern pXRF technologies used to mitigate X-ray attenuation and improve light element analysis. The void between the sample and detector is a key issue regarding the success of pXRF light element analysis. Dry-air (normal conditions), vacuum purge and helium flush systems are evaluated. Modelled data that use a nominal sample-detector void of 10 mm show that using helium in lieu of air improves X-ray transmission effectiveness from ≈2% to ≈99% for Na and ≈10% to ≈100% for Mg. Modelled detector window data show that using a graphene detector window in lieu of a traditional beryllium detector window improves X-ray transmission effectiveness for Na from ≈38% to ≈64% and ≈57% to ≈77% for Mg. Progressive X-ray transmission effectiveness equates to ≈63% Na and ≈76% Mg when using a helium-graphene pXRF configuration v. ≈1% for Na and ≈6% Mg when using a traditional in-air beryllium pXRF arrangement (i.e. without sample or X-ray entrance window media). Empirically determined improvements of the resolved signal are more modest than those of modelled X-ray transmission effectiveness data. Instrument noise, spectral overlaps and random counting errors are unavoidable and inherent with the limitations of modern detector technologies. However, the employment of helium with graphene detector window technology allows very precise data to be obtained at significantly shorter scan times (i.e. 20 s, instead of the traditional 60–180 s, i.e. 3–9 times faster): a scan time of 20 s can achieve a precision of ≈18% @ ≈0.4% Na and ≈8% @ ≈0.3% Mg for elemental interference-free samples. Precision will improve with increasing analyte concentration. [ABSTRACT FROM AUTHOR]

The "Marmi Mischi" (mixed glass mosaic tesserae) are artificial calcium-rich glass decorations, typically used in southern Italy and Sicily during the Baroque period (1600-1700) to decorate walls and altars of religious edifices. In this study, we provide new archaeometric information on the raw materials, pigments and opacifying agents used to produce "Marmi Mischi" of "Pallium altaris" from the Messina Regional Museum. To reach this objective, all the studied glass decorations were analysed by means of non-destructive portable X-ray fluorescence (pXRF). Some of the decorations were further subjected to Environmental scanning electron microscopy (ESEM) and X-ray powder diffraction (XRPD) in the laboratory. Two types of glasses were recognised. The first one - bluish green in colour - is a basic or slightly modified "carcara glass", characterized by high concentrations of P. The second type - dark blue, turquoise, light turquoise and red in colour - is a "carcara glass" modified by craftsmen, containing high amounts of colouring agents (Cu, Pb, Sn, Sb). The presence of schreibersite in some of the analysed samples indicates that forming occurred in extremely reducing conditions and proves that the glasses were produced in CaO furnaces called "carcara" and used to produce lime. Moreover, our results suggest that: i) the dark blue, turquoise and bluish green nuances are as a result of Fe2+, with minor contribution by Cu and Co; ii) the light turquoise nuance is related to Fe2+ and Cu2+, with minor contribution by Co; and iii) the red colour is as a result of the reduction of copper to the metallic state by Sn and Pb. Ca-antimonate (Ca2Sb2O7) was identified as an opacifying agent for the blue glassy decorations, whereas metallic Cu was identified for the red. The overall results of the chemical and physical characterization of the "Pallium altaris" glassy decorations from the Messina Regional Museum suggest that the used raw material was "carcara glass," to which various chemical elements were suitably added to obtain the desired nuances. [ABSTRACT FROM AUTHOR]

During urgent archaeological excavations in the city of Plovdiv (South Bulgaria), a Roman pottery workshop was found, including several dome kilns, ceramic sherds, and a large clay deposit incorporating yellow and gray clay layers. A set of the ceramic specimens (kitchenwares and tablewares) and raw clay samples were investigated using a portable device for X‐ray fluorescence and laboratory equipment for magnetic measurements, aiming to provide specific information about the origin and firing technology of the pottery. Despite significant difference in calcium content between local raw clay and pottery samples, we conclude that local natural clay sources were used and the initial stages of production involved clay purification, although we cannot rule out the procurement of more distant clay sources. Magnetic susceptibility testing allowed for determination of the maximum firing temperatures, showing that the pottery were fired predominantly at 780°C, with some samples being fired at temperatures up to 860°C. Magnetic analyses show that kitchenwares were fired under more uniform conditions than the tablewares, which undoubtedly reflected in the quality of the vessels produced. [ABSTRACT FROM AUTHOR]

A portable X-ray fluorescence probe (pXRF) is a tool that is used to measure many elements quickly and efficiently in various samples, without any pretreatment. However, each type of sample generally requires different calibrations to be accurate. To overcome this, our work evaluated the efficacy of determining several elements in forage plant samples using the ‘Soil Nutrient and Metal’ calibration in a commercially available pXRF probe, envisioning that a single calibration can be used to measure samples of different matrixes. For this, the net intensity of the pXRF probe was determined in place of the concentration values that are obtained directly from measurements. Elemental concentrations (P, K, Ca, Mg, S, Cu, Fe, Zn, and Mn) from forage plant samples, collected across Oklahoma, US, were assessed in a representative number of ‘modeling’ and ‘validation’ (independent dataset) samples. Linear regression (LR) associated with the d-index, polynomial regression (PR), and power regression (PwR) were tested for predictions, producing many statistical parameters associated with the models that were used for comparison goals. The pXRF elemental data provided highly reliable predictions of K, S, Zn, and Mn regardless of the regression model. Although all models can be reliable in prediction of Ca and Fe concentrations, the PwR provided better root mean square error (RMSE) values. The predictions of Mg concentrations were less reliable, although highly significant; however, the P and Cu predictions were not acceptable. Our work successfully showed that, once established, a single calibration curve that covers a wide range of concentrations of several elements in soils and plant tissues enables both soil and plant samples to be analyzed. This suggests that manufacturers can develop a new calibration model for a commercially available pXRF probe that covers a wide variety of heterogeneous samples.

This study explores the authentication of a bronze statue by means of the evaluation of technical evidence and investigation of patinas formation. The statue was identified by the police as a product of illicit excavation and handed to the Archaeological Museum of Thessaloniki. The visual examination reveals technical features that are consistent with those commonly found on ancient bronze statues while the physicochemical character of the corrosion was in accordance with typical bronze corrosion mechanisms (decuprification). Original features like the metal microstructure were detected on the corrosion layers, showing the complexity and long lasting character of their formation. The metal composition was determined by XRF and the corrosion products were analysed by XRF and SEM-EDS.

Abstract The Preah Vihear monument in Cambodia, located close to the border with Thailand, was one of the Khmer temples registered on the UNESCO World Heritage List as a Cultural Property in 2008. It consists of masonry buildings constructed of siliceous sandstone blocks. In this study, the construction sequence of its buildings was inferred from the chemical composition, magnetic susceptibility, and size of the sandstone blocks, along with pediment end style, and the presence or absence of reliefs on the tympana of adjacent buildings. Five construction stages were identified. We revealed that the Western Annex Hall (N2) is the oldest edifice in the Preah Vihear monument. We also reconfirmed that the Preah Vihear monument was constructed over a range of years, spanning the Bakheng style period to the Angkor Wat style period (the end of the 9th century to the end of 12th century). It was clarified that during the construction of Preah Vihear, the style of pediment ends changed from pediments ending in scrolls made from one block, to pediments ending in scrolls made from two blocks, and finally to pediments ending in five-headed nagas. Over the same time span, the size of the sandstone blocks used in construction increased markedly.

Abstract There are multiple challenges in analysing pigments in historic watercolour paintings on paper, and typically non-invasive, in situ methods are required. Recent developments in portable analytical instrumentation have made this more accessible to heritage institutions, but many commercial systems are not optimised for the specific requirements of manuscripts and works on paper. This paper describes the successful use of Raman spectroscopy, X-ray fluorescence spectroscopy (XRF) and hyperspectral imaging to identify and map watercolour pigments used by the eighteenth century botanical illustrator, Ferdinand Bauer, and demystify the unusual colour code system found in his sketches. The value, delicate nature and large size of these paintings necessitated the use of using in situ, non-contact methods of analysis. A portable, bespoke Raman spectrometer specifically designed for analysing pigments from works on paper was used together with a bespoke portable Fibre optic reflectance spectrometer, portable X-Ray Fluorescence spectrometer and a hyperspectral imaging sensor. The results demonstrate that although there is a significant compromise between achieving good Raman spectroscopic results from artists’ pigments and using sufficiently low laser power densities so as not to cause damage to the pigments, good results could be obtained with this portable system, particularly when combined with XRF, fibre optic reflectance spectroscopy (FORS) and hyperspectral imaging. Eight pigments were identified unequivocally from 125 watercolour paintings analysed, suggesting that Bauer used a more traditional and more limited palette than previously considered, and that his palette changed significantly in his later paintings. Similar pigments identified by the authors on colour chart that was discovered in 1999 in Madrid and attributed to Bauer, add weight to the attribution of this chart to Bauer. The data provides a much deeper insight into Bauer’s colour annotations, and how he was able to achieve such an impressive degree of colour fidelity in his work.

Cobalt was commonly used as a colourant in the Egyptian glass industries of the 18th dynasty, dark blue glass being a regular find at palatial and settlement sites, including Amarna and Malqata. The main source of cobalt ore used during this period has been identified in the Egyptian western desert, around the oases of Kharga and Dakhla. In order to better understand the chaîne opératoire of Late Bronze Age glass production and -working, in particular with regard to cobalt ore, at Amarna, chemical analysis by portable X-Ray fluorescence was carried out in the field. This was done on contextualised archaeological material excavated at the site of Amarna, which cannot be exported from Egypt for analysis. The results of this study demonstrate how cobalt ore was used in the various known workshop sites at Amarna, resulting in a deeper understanding of raw materials use and exchange across this settlement. [ABSTRACT FROM AUTHOR]

Compared to elsewhere in Oceania, the history and character of stone axe‐adze production and exchange in the Bismarck Archipelago is very poorly known. To explore the feasibility of using geochemical analysis to trace past social interaction, we conducted a non‐destructive portable XRF study of 97 ground stone artefacts from archaeological contexts in New Britain and the ethnographic collection at the Australian Museum. The study capitalised on the well‐documented spatial distribution of geochemical variation resulting from the plate‐tectonic history of the region. The results indicate that prehistoric communities in New Britain specialised in goods such as ground stone tools or obsidian in order to facilitate social interaction over a large region. [ABSTRACT FROM AUTHOR]

The fundamentals of X-ray physics are well understood, and many workers have commented on the poor performance and poor reproducibility of atomically-light elements by portable X-ray fluorescence (pXRF). However, the physics responsible for this is rarely discussed in the pXRF literature. Furthermore, it is well known that analysing samples through calico (cotton fabric) or paper bags results in lower concentrations reported by the pXRF instrument but, again, the physics of this is seldom discussed. This paper addresses these shortcomings by presenting X-ray transmission modelling and empirical data to show that the effects reported by many workers are entirely consistent with the physics of X-rays passing through matter, and thus that they are entirely predictable. [ABSTRACT FROM AUTHOR]

Abstract A collection of Prime Cultural Heritage artefacts consisting of Egyptian late Middle Kingdom figurines (c. 1850–1700 BCE), made of unfired clay and covered in inscriptions, is kept at the Royal Museums of Art and History (RMAH) in Brussels, Belgium. Several of these hieratic inscriptions curse enemies of the Egyptian state, including Canaanite, Nubian and Libyan entities; thus providing invaluable information for Middle Bronze topography in ancient Near Eastern studies. What makes the extensive Brussels group even more exceptional, is the fact that these figurines were discovered in a closed archaeological context in Saqqara, Lower Egypt. Defining and classifying clay and ancient ceramic provenance groups in Egypt is highly complex due to variability in Nile and marl clay deposits. Chemical characterization of this figurine assemblage (n = 91) allows to effectively study the potential direct use of clays in the vicinity of Saqqara and characterize the nature of the raw materials used. Additionally, it aims to assess the validity of portable XRF spectrometry for this type of materials and its provenance resolution. Analyses show that very similar clays were used to produce the different morphological types of figurines in the assemblage. The chemical profile indicates the use of a mixed source at Saqqara rather than pure marl or Nile clays, which are common for ancient pottery production. Highlights • The unfired clay figurines are attributed to Nile silt clay sources enriched in calcium carbonates from Saqqara. • Geochemical characterization of prime cultural heritage artefacts from ancient Saqqara • Determination of a chemical fingerprint and local Saqqara origin for unfired clay objects • pXRF as a suitable comparative tool to determine Egyptian marl and Nile silts deposits and clay-based objects • No correspondence between figurine typology and chemical group signatures indicate no specialized production. [ABSTRACT FROM AUTHOR]

Lead (Pb), Zinc (Zn) and Cadmium (Cd) levels on soils surrounding of Lakhouat mine (North-West of Tunisia) were measured. The total concentration of these elements in the soil samples was determined by portable X-ray fluorescence (XRF) in situ and compared to the traditional digestion method using inductively coupled-plasma optical emission spectroscopy (ICP-OES). Statistical analyses were performed to determine if significant differences existed between the instrumental techniques, which included simple correlations by the regression lines and t-test for mean comparison. The statistical analysis demonstrated that no statistically significant differences were observed for the Pb concentrations; however, for the Zn and Cd concentrations, t-test showed significant differences between the inst

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