Handheld X-ray Fluorescence Research Articles

Impact of an external radiation field on handheld XRF measurements for nuclear forensics applications

X-ray fluorescence (XRF) is an attractive technique for nuclear forensics applications. We evaluated a handheld XRF device by applying an external radiation field (10 mR/h–17 R/h) using two types of radiography sources: a 60Co radiography camera for high-energy gamma emissions and an 192Ir radiography camera for several low-energy gamma (0.604, 0.468, and 0.317 MeV) and decay daughter X-ray emissions. External radiation tests proved that radiation, in general, has a significant effect on the dead time or background at dose rates over 1 R/h for both the 192Ir and 60Co sources.

Spatial distribution of lead in Sacramento, California, USA.

Chronic exposure to lead remains a health concern in many urban areas; Sacramento, California is one example, with state surveillance data showing nearly 3% of screened children reported with blood lead levels over 4.5 μg/dL in 2009. To investigate the environmental exposure, 91 soil samples were collected and analyzed by ICP-AES and ICP-MS for 14 elements. An additional 28 samples were collected from areas of focus and analyzed by hand-held X-ray fluorescence spectrometry for Pb and Zn. Analysis of the metals data revealed non-normal distributions and positive skewness, consistent with anthropogenic input. In addition, high correlation coefficients (≥0.75) of metal concentrations in Cd-Pb, Cd-Zn, Pb-Zn, and Sb-Sn pairs suggest similarities in the input mechanisms. Semivariograms generated from Pb and associated metals reveal these metals to exhibit spatial correlation. A prediction map of lead concentrations in soil was generated by ordinary kriging, showing elevated concentrations in soil located in the central, older area of Sacramento where historic traffic density and industrial activity have been historically concentrated. XRF analysis of Pb and Zn from additional samples verifies elevated concentrations in the central areas of Sacramento as predicted.

Revisiting the beginnings of tin-opacified Islamic glazes

The generally accepted theory is that the demand for Islamic glazed pottery started in Abbasid Iraq in the 9th century AD with the production of a range of glazed wares in response to the import of Chinese stonewares and porcelains. However, Oliver Watson has recently proposed that the demand for Islamic glazed pottery first occurred in Egypt and Syria in the 8th century AD resulting in the production of opaque yellow decorated wares. Using a combination of SEM analysis of polished cross-sections, and surface analysis using hand-held XRF or PIXE, Coptic Glazed Ware from Egypt, Yellow Glazed Ware from Syria, and comparable wares from Samarra, Kish and Susa have been analysed. The analyses show that the opaque yellow decoration was the result of lead stannate particles in a high lead glaze, which it is suggested was produced using a lead-silica-tin mixture. The use of lead stannate in the production of yellow opaque glazes is explained in terms of technological transfer from contemporary Islamic glassmakers who continued the Byzantine tradition of glassmaking. It is further argued that the introduction of opaque yellow glazed pottery into Mesopotamia could have provided the social context for the sudden emergence of tin-opacified white glazed pottery in Abbasid Iraq in the 9th century AD. However, in view of the very different glaze compositions employed for the yellow and white opaque glazes, it seems probable that the white tin-opacified glazes used for Abbasid cobalt blue and lustre decorated wares represent a separate but parallel technological tradition with its origins in the production of Islamic opaque white glass.

High resolution tephra and U/Pb chronology of the 3.33–3.26 Ga Mendon Formation, Barberton Greenstone Belt, South Africa

The Mendon Formation in the Barberton Greenstone Belt of South Africa marks the boundary between the Onverwacht and Fig Tree Groups. These groups are characterized by mafic to ultramafic volcanism and felsic volcanism with related epiclastic sedimentation, respectively. This transition marks the end of komatiitic volcanism in the Barberton Greenstone Belt and is accompanied by numerous impact-related spherule layers. This study characterizes the upper Mendon Formation texturally and geochemically over a wide areal extent and across structure and facies changes in an attempt to better understand the evolution of tectonic processes at this boundary. A suite of whole rock and handheld X-ray fluorescence analyses are presented in conjunction with textural information, stratigraphic relationships, and U/Pb ages to create a temporal and chemostratigraphic framework for the Mendon Formation. Local and regional stratigraphic variations, including absence of distinctive layers and variation in layer thickness, seen across the Mendon preclude ascription of a single stratigraphy that accurately describes the >1.2km of section present in this formation. These variations indicate diachronous deposition of the Mendon Formation over a wide areal extent and into multiple basins or sub-basins by more than one magmatic source. 204Pb-corrected 206Pb/238U and 207Pb/235U concordia model ages of 3279±9.1Ma and 3287.3±2.9Ma for two samples from upper portions of the Mendon Formation provide temporal context for deposition. Two samples from the basal 10m of the Fig Tree Group, above the S2 spherule bed that marks the boundary between the Onverwacht and Fig Tree Groups, give model ages of 3267.8±6.9Ma and 3261±18Ma. These ages provide added constraints for the Onverwacht-Fig Tree boundary and confirm that the Weltevreden Formation is roughly age-correlative with the uppermost Mendon Formation. While the Mendon and Weltevreden Formations are in part age-correlative and have similar lithologies, they do not appear to be genetically related. The dominance of ultramafic volcanic rocks and the paucity of felsic volcanic and terrigenous sedimentary rocks within the Mendon and Weltevreden Formations indicate that the primary mode of crustal formation was likely plume-related magmatic accretion and not subduction. The relatively sharp transition within the Barberton Greenstone Belt from ultramafic volcanic sequences to more felsic volcanic and epiclastic sedimentary sequences is everywhere marked by impact-related spherule layers, which suggest that major impacts may have played a role in the evolution of early tectonics to more modern, subduction-related styles.

The potential of lacquer-peel soil profiles for palaeo-geochemical analysis using XRF analysis

This paper discusses the suitability of hand-held XRF analysis to extract palaeo-geochemical information from lacquer-peel soil sections that have been taken to document pedological information at geological and archaeological sites. This not only allows the study of sections from archaeological and geological sites that have since disappeared, but can also answer new archaeological questions on the nature of activities undertaken at such sites. Seven lacquer-peels, from different time-periods and different geogenetic backdrops, have been studied with hand-held XRF (Niton XL3t, GOLDD detector). Five of these lacquer-peels were studied to assess possible interference from mounting materials (glues, textiles and framing boards) used. Four of these lacquer-peels were studied for their palaeo-geochemical information. These lacquer-peels were taken from prehistoric agricultural plots and settlement sites, ranging in age from the Neolithic to the Iron Age. Values for Si, K, Al, Fe, Ti, Sr, Zr and Rb reflect lithogenetic and pedological processes. The contents of S, Ca and P were used as a proxy for anthropogenic influence. The lacquer-peels provided consistent and reliable geochemical readings with the hand-held XRF. Observed correspondence between pedological predictions, archaeological hypotheses and the measured results testifies to the suitability of hand-held XRF for palaeo-geochemical characterization. Interference from the primarily organic fixing- and mounting-agents used was absent. Consequently, hand-held XRF analysis allows extraction of palaeo-geochemical information from lacquer-peel soil sections, which opens-up a new potential data-set for reconstructing past pollution and to geochemically re-assess geological and archaeological sites from existent lacquer peels — adding a geochemical dimension to lacquer-peels of pedological, archaeological and geological sites.

Preliminary validation of handheld X-ray fluorescence spectrometry: distinguishing osseous and dental tissue from nonbone material of similar chemical composition.

One of the tasks of a forensic anthropologist is to sort human bone fragments from other materials, which can be difficult when dealing with highly fragmented and taphonomically modified material. The purpose of this research is to develop a method using handheld X-ray fluorescence (HHXRF) spectrometry to distinguish human and nonhuman bone/teeth from nonbone materials of similar chemical composition using multivariate statistical analyses. The sample materials were derived primarily from previous studies: human bone and teeth, nonhuman bone, nonbiological materials, nonbone biological materials, and taphonomically modified materials. The testing included two phases, testing both the reliability of the instrument and the accuracy of the technique. The results indicate that osseous and dental tissue can be distinguished from nonbone material of similar chemical composition with a high degree of accuracy (94%). While it was not possible to discriminate rock apatite and synthetic hydroxyapatite from bone/teeth, this technique successfully discriminated ivory and octocoral.

Application of handheld XRF spectrometers for estimation of Rare Earth Elements content in alkaline intrusions from the East European Craton (NE Poland) preliminary results

The Carboniferous alkaline intrusions, which cut the Precambrian basement of East European Platform are known only from drillings. The massifs are covered by Mesozoic and Cenozoic sediments (600–800 m) and their borders were defined by extensive geophysical investigations. The Tajno alkaline-carbonatite complex, the Elk syenite massif, the Pisz gabbro-syenite complex as well as alkaline rocks recognized as Mlawa or Olsztynek anomaly are the subject of systematic and complex analyses. All of them could be the potential sources for rare earth elements. The massifs were explore by several boreholes (about 12,000 m of drill core material; e.g. Elk IG 1-4, Tajno IG 1-12, Prostki 1-2, Klusy-1, Grajewo IG-1). Thus, the main aim of our study is to precisely identify the perspective drill-core intervals within the Elk IG4 borehole materials for better defining of locations for detailed sampling and further laboratory analysis. For this purpose we had applied handheld XRF DELTA 50 Premium spectrometers equipped with a 4W Ta anode X-ray tube (50 kV). The parameters of spectrometers (higher voltage and multi-beam system) are optimized for rare earth elements (REEs) such as Y, La, Ce, Pr, Nd. Handheld XRF non-destructive analyses allowed the identification of mineralized trends and anomalies within the drill-core material at the ppm level. The previous testing analyses enabled to optimize times of acquisition for each beam and provide fast field analyses (about 100 per day). The contents of La and Ce were chosen as indicators of the REE-bearing minerals occurrence in analyzed rocks. The XRF analyses were performed for each meter of drill core. The graph of these elements content vs. depth of the samples from Elk IG4 borehole exhibited high differentiation. The highest and lowest content of La was 17 ppm and 3241 ppm, respectively (average 167 ppm for 1185 samples, without 78 below the level of detection) and Ce – 24 ppm and 4313 ppm (average 294 ppm for 1214 samples, without 49 below the level of detection). The higher content of REE elements seems to be related to concentration of minerals such as pyroxene, mica, titanite, monazite, zircon, fluoro-carbonate as well as the presence of secondary veins in smaller amounts.

Application of handheld energy-dispersive X-ray fluorescence spectrometry to carbonate studies: opportunities and challenges

In situ rapid quantitative geochemical measurements of carbonate using handheld XRF.

New Tools for Pedologists: Digital Soil Morphometrics

New Tools for Pedologists: Digital Soil Morphometrics

Monitoring of WEEE plastics in regards to brominated flame retardants using handheld XRF

This contribution is focused on the on-site determination of the bromine content in waste electrical and electronic equipment (WEEE), in particular waste plastics from television sets (TV) and personal computer monitors (PC) using a handheld X-ray fluorescence (XRF) device. The described approach allows the examination of samples in regards to the compliance with legal specifications for polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs) directly after disassembling and facilitates the sorting out of plastics with high contents of brominated flame retardants (BFRs). In all, over 3000 pieces of black (TV) and 1600 pieces of grey (PC) plastic waste were analysed with handheld XRF technique for this study. Especially noticeable was the high percentage of pieces with a bromine content of over 50,000ppm for TV (7%) and PC (39%) waste plastics. The applied method was validated by comparing the data of handheld XRF with results obtained by GC–MS. The results showed the expected and sufficiently accurate correlation between these two methods. It is shown that handheld XRF technique is an effective tool for fast monitoring of large volumes of WEEE plastics in regards to BFRs for on-site measurements.

Study of a unique 16th century Antwerp majolica floor in the Rameyenhof castle's chapel by means of X-ray fluorescence and portable Raman analytical instrumentation

The most unique and only known 16th century Antwerp majolica tile floor in Belgium is situated in a tower of the Rameyenhof castle (Gestel, Belgium). This exceptional work of art has recently been investigated in situ by using X-ray fluorescence (XRF) and Raman spectroscopy in order to study the material characteristics. This study reports on the result of the analyses based on the novel combination of non-destructive and portable instrumentation, including a handheld XRF spectrometer for obtaining elemental information and a mobile Raman spectrometer for retrieving structural and molecular information on the floor tiles in the Rameyenhof castle and on a second, similar medallion, which is stored in the Rubens House museum in Antwerp (Belgium). The investigated material, majolica, is a type of ceramic, which fascinated many people and potters throughout history by its beauty and colourful appearance.In this study the characteristic major/minor and trace element signature of 16th century Antwerp majolica is determined and the pigments used for the colourful paintings present on the floor are identified. Furthermore, based on the elemental fingerprint of the white glaze, and in particular on the presence of zinc in the tiles – an element that was not used for making 16th century majolica – valuable information about the originality of the chapel floor and the two central medallions is acquired.

휴대용 XRF와 GIS를 이용한 폐광산 지역의 토양오염에 관한 연구

In this study, soil contamination maps related to Cu and Pb were created at the Busan abandoned mine in Korea using a handheld X-Ray Fluorescence(XRF) and Geographic Information Systems(GIS). Hydrological analysis was performed using the

2014 Atomic Spectrometry Update – a review of advances in X-ray fluorescence spectrometry

This review describes advances in the continued expansion of work using the XRF group of techniques published approximately between April 2013 and March 2014. Specialised laboratory instrumentation, X-ray sources, detector development and data processing continue unabated. It is remarkable how quickly hand-held XRF instrumentation has developed to the point where many examples of its use are included in the various application sections of this review, rather than in the instrumentation section. Several new beam lines and their new end-stations were described in publications from SR research centres around the world. More analysts are attracted to TXRF and related techniques with new sample preparation techniques offered for an expanding range of applications. Nanoparticles and nanomaterials feature throughout this review particularly in clinical, biological and environmental studies. A novel approach for the reuse of industrial by-products described how acid mine drainage sludge and coal fly ash facilitated the problem of the high levels of phosphate present in waste waters (cow dung) from the dairy industry. The archaeological and cultural heritage section often includes good news stories. This year we learn how an XRF mapping technique was used to show that Pablo Picasso used a popular brand of French house paint in his works of art.

A (not so) dangerous method: pXRF vs. EPMA-WDS analyses of copper-based artefacts

Analysis of metal objects with portable and handheld X-ray fluorescence spectrometry has become increasingly popular in recent years. Here, methodological concerns that apply to non-destructive, surface examination with XRF instruments of ancient metal artefacts are discussed based on the comparative analyses of a set of copper-based objects by means of portable X-ray fluorescence (pXRF) and electron probe microanalyser (EPMA). The analytical investigation aims to explore issues of instrument comparability and reliability of the non-invasive pXRF results. The different analytical approaches produce a comparable pattern for the major element concentrations, but substantial variation is evident when it comes to the absolute values for major and minor/trace elements.

Developing Scientific Literacy in Introductory Laboratory Courses: A Model for Course Design and Assessment

ABSTRACTAlthough science educators at all levels have focused on teaching students scientific literacy for nearly five decades, studies indicate that the average student remains far from scientifically literate. To address this issue at the local level, faculty at Trinity University, in San Antonio, Texas, significantly revised the curriculum of an existing introductory physical geology laboratory course. The course, which satisfies general education requirements at Trinity, was revised to provide students learning opportunities in a scientific process context as part of a new science literacy initiative. This effort was spurred by general dissatisfaction with the existing curricular structure of the course as well as a new interdisciplinary, National Science Foundation (NSF)–funded initiative to support the integration of research-grade instrumentation in curricula and undergraduate research across campus. The physical geology laboratory course revision was based on research that demonstrated the efficacy of learning through active participation, interpretation, iteration, and reflection, especially when knowledge and skills are gained within an explicit scientific process context. In addition to significantly revising laboratory activities, we added new activities within the course framework that involved the use of two new, NSF-funded instruments, including a handheld X-ray fluorescence spectrometer (XRF) and an inductively coupled plasma–optical emissions spectrometer (ICP-OES), which we used to improve student understanding of qualitative and quantitative elemental analyses. Finally, we introduced the use of a new course reader that provided both background materials for each activity as well as a new focus on providing a scientific process context for students. To assess student learning, we used in-class observations, student–instructor discussions, pre- and postlearning questionnaires, prelaboratory quizzes, course activities completed during class time, modified postactivity reflection questions, practical examinations, and a final examination. We also included faculty, staff, and administrator perspectives to qualitatively assess the impact of course changes upon student learning. Our results imply that students achieved the primary learning goals we developed for this scientific literacy initiative, including: (1) improved understanding of the scientific process and the nature of science; (2) improved understanding of qualitative and quantitative elemental research methods; and (3) improved understanding of the applicability of scientific research to real-world problems. Importantly, our findings suggest that the integration of research-grade instrumentation into introductory coursework, in a scientific process context, is an effective way to promote scientific literacy as well as to provide opportunities for students to understand and apply the knowledge and skills necessary to perform scientific research. We believe that this example of a significant course redesign provides a model that can be transferred to other geosciences departments as well as to other scientific disciplines.

Applicability of handheld X-Ray fluorescence spectrometry in the exploration and development of carbonatite-related niobium deposits: a case study of the Aley Carbonatite, British Columbia, Canada

This study evaluates the suitability of portable (handheld) X-Ray fluorescence spectrometry (pXRF) in the exploration for Aley-type ‘hard-rock’ (primary) carbonatite-hosted Nb deposits. The assessment consists of comparisons between: (1) results of pXRF analyses on selected pulp samples and results of analyses of the same pulps using traditional laboratory methods; (2) results of averaged, multiple pXRF spot field analyses performed directly on 10 to 15 cm long pieces of core (before pulverization) compared with those of traditional laboratory analyses of the same pieces of core after pulverization; and (3) results of a manual core scanning method compared with the results of conventional analytical methods of the pulps of the corresponding scanned sections. A strong correlation exists between pXRF measurements on pulps and laboratory methods for most specialty metals, such as Nb (r 2 = 0.99), La (r 2 = 0.97), Ce (r 2 = 0.67), Y (r 2 = 0.93), and P (r 2 = 0.89); however, the values of r 2 for Pr and Nd are 0.19 and 0.38, respectively. As expected, textural heterogeneities within sample intervals reduced the quality of pXRF results when multiple spot readings were taken directly on the core. Nevertheless, the data can still be used to identify carbonatite-related Nb (± other specialty metal mineralization) and delimitate potentially economically significant zones within it. The core scanning reduced the degree of variation associated with spot analyses. Scanning is useful during the early exploration stages, but provides data limited by the inability of the operator to maintain constant scanning speed. The scanning results correlate with laboratory methods for Nb (r 2 = 0.88), Th (r 2 = 0.80), Fe (r 2 = 0.84), Sr (r 2 = 0.74), Ba (r 2 = 0.73), Y (r 2 = 0.59), and Zn (r 2 = 0.75). The values of r 2 for La, Ce, Pr, and Nd were only 0.31, 0.26, 0.01 and 0.03, respectively, suggesting that concentrations of these elements were too low, and/or that the light rare earth elements (LREEs) were present not only in the crystal structure of fersmite, pyrochlore and apatite, but also in minor or accessory minerals such as REE-bearing fluorocarbonates or zircon erratically distributed throughout the core. Portable XRF is a robust tool facilitating exploration-related decision-making in the field, assuming that elements of interest such as Nb are present in concentrations within the analytical range of the instrument. The pXRF core scanning reduces the need for sample preparation (no pulps) and can be done directly on the drill-site, but the precision and accuracy of the data are reduced relative to laboratory and pXRF pulp analyses. The multiple spot analyses (no pulps) approach is good for instant verification of unknown, potentially ore-bearing minerals and for analysing discrete homogeneous features, layers, veins, etc; however, under normal circumstances this method is inferior to pulp analyses in precision and accuracy, and to scanning for determining average grade of core intervals.

Handheld XRF analysis of the old Mexican feather headdress in the Weltmuseum Vienna

Within a trans-disciplinary project between Mexico (Instituto Nacional de Antropología e Historia) and Austria (Weltmuseum Wien), the feather headdress, a unique and most renowned pre-Columbian ‘Arte Plumaria’ artifact from the 16th Century was studied extensively. Among other investigations concerning the materiality of the headdress, noninvasive handheld X-ray fluorescence (XRF) analysis was carried out with a handheld instrument to detect the possible presence of inorganic pesticides and pigments and to verify the composition of the metal decorations. The measurements provided rich qualitative and even quantitative information. The use of inorganic pesticides (arsenic, bromide and lead containing compounds), the composition of the original gold decoration plates and the later added brass plates were confirmed. A method was established to define the thickness of the gilding of the later added plates. There was not found evidence on the use of inorganic pigments to produce marks on the constructive parts of the headdress. Handheld XRF measurements can be extremely useful for noninvasive on site investigation of sensitive museum artifacts, but generally require the application of a thorough analytical methodology for the proper interpretation and quantification of the results. Copyright © 2014 John Wiley & Sons, Ltd.

Comparative Study on Nondestructive and Destructive Methods of Evaluating Thicknesses of Hot-dip Galvanized Coatings

Two on-site nondestructive methods, one involving an electromagnetic thickness tester and the other a handheld x-ray fluorescence analysis system, were used to evaluate thicknesses of hot-dip galvanized coatings on steel and compared with destructive analytical methods. They were sufficiently applicable for measuring the remaining thickness or mass of the coatings when the density of the alloy layer or the zinc depth profile was already known.

The Cross & the Crucible: The Production of Carolingian Disc Brooches as Objects of Religious Exchange?

In this article, aspects of the production and exchange of Carolingian/Ottonian disc brooches are examined through an analysis of 281 brooches selected from collections across The Netherlands. The composition of the brooches was measured with a Hand Held-XRF device and the results showed a sharp deviation from the alloys seen in brooches from earlier periods. The results across all geographic areas consisted of a mixture of copper, zinc and lead, but no tin. If recycling practices were present in the making of these brooches, then you might expect an element of tin to enter the mixture, as bronze items entered the alloy-recycling stream. But this appears not to be the case. This consistency rules out production by travelling merchants, or at domestic households and primitive workshops. The results suggest that production was more likely organised on a regional or even super regional scale. An analysis of production at royal estates, emporia and the great abbeys found the latter to be the most likely source of these objects. Furthermore, the Christian nature of these brooches, if produced within monastic centres, may have imbued them with religious meaning, allow for a fresh interpretation of their methods of exchange.

Analysis of Metal Content in Soil in Timis County

Abstract The paper reports on the presence of various metals in soil in Timis county. A set of 18 samples were collected from different points of interest. The metal content of the samples was investigated using a handheld XRF Niton XLp 300 GOLDD analyzer. Special attention was paid to the metals with harmful potential to humans. Based on the obtained results, a set of conclusions on the environment’s health was drawn.