Non-destructive Energy Dispersive X-ray Fluorescence Research Articles

Fabrication and characterization of thin 94Zr target with gold backing for nuclear lifetime measurements using DSAM

For lifetime measurements of excited nuclear states in the sub-picosecond range, a thin target with a thick backing of high-Z material is required. To meet these specifications, a thin isotopic94Zr target of thickness 1.14 ± 0.05 mg/cm2, with backing of 4.7 ± 0.2 mg/cm2 thick Au layer, has been fabricated using the cost-effective cold rolling technique at the target laboratory of Inter-University Accelerator Centre (IUAC), New Delhi. The thickness verification and purity check of the fabricated target have been carried out by non-destructive Energy Dispersive X-ray Fluorescence (EDXRF) and Rutherford Backscattering Spectrometry (RBS) techniques. The results of these measurements are in good agreement with each other. The elemental composition, purity and surface morphology have been explored by Energy Dispersive X-ray Spectrometry (EDS) and Scanning Electron Microscopy (SEM) techniques. The fabricated target has been successfully used with a16O ion beam in a recent γ-ray spectroscopy experiment for lifetime measurements using the Doppler Shift Attenuation Method (DSAM) at IUAC, New Delhi.

Comparisons of Spatial and Temporal Variations in PM2.5-Bound Trace Elements in Urban and Rural Areas of South Korea, and Associated Potential Health Risks

PM2.5-bound trace elements were chosen for health risk assessment because they have been linked to an increased risk of respiratory and cardiovascular illness. Since the Korean national air quality standard for ambient particulate matter is based on PM2.5 mass concentration, there have only been a few measurements of PM2.5 particles together with trace elements that can be utilized to evaluate their effects on air quality and human health. Thus, this study describes the trace elements bound to PM2.5 in Seoul (urban area) and Seosan (rural area) using online nondestructive energy-dispersive X-ray fluorescence analysis from December 2020 to January 2021. At both the Seoul and Seosan sites, S, K, Si, Ca, and Fe constituted most of the PM2.5-bound trace elements (~95%); major components such as S, K, and soil (estimatedcalculatedcalculated based on oxides of Si, Fe, Ca, and Ti) were presumably from anthropogenic and crustal sources, as well as favorable meteorological conditions. During winter, synoptic meteorology favored the transport of particles from severely contaminated regions, such as the East Asian outflow and local emissions. The total dry deposition flux for crustal elements was 894.5 ± 320.8 µg m−2 d−1 in Seoul and 1088.8 ± 302.4 µg m−2 d−1 in Seosan. Moreover, potential health risks from the trace elements were estimated. Cancer risk values for carcinogenic trace elements (Cr, As, Ni, and Pb) were within the tolerable limit (1 × 10−6), suggesting that adults and children were not at risk of cancer throughout the study period in Seoul and Seosan. Furthermore, a potential risk assessment of human exposure to remaining carcinogens (Cr, As, Ni, and Pb) and non-carcinogens (Cu, Fe, Zn, V, Mn, and Se) indicated that these trace elements posed no health risks. Nevertheless, trace element monitoring, risk assessment, and mitigation must be strengthened throughout the study area to confirm that trace-element-related health effects remain harmless. Researchers and policymakers can use the database from this study on spatial and temporal variation to establish actions and plans in the future.

Fabrication of [formula omitted]As targets for heavy ion nuclear reactions

Thin uniform targets of 75As isotope with Pb/Au backing layer were fabricated for nuclear structure studies and sub-picosecond lifetime measurements of nuclear excited states using the Doppler shift attenuation method (DSAM) for nuclei populated in the heavy-ion induced fusion-evaporation reactions. The 75As targets of thickness 2.8–4.0 mg/cm2 (4.9–7.0μm) were prepared by in-vacuo sublimation of the As metal powder on to the backing (∼10 mg/cm2) of Pb (9.4μm) or Au (5.2μm), which were prepared by rolling method. The prepared targets were further rolled to improve their uniformity and avoid any interlayer gaps. The amount 75As material required for target preparation could be significantly reduced to ∼80 mg by increasing vapour flux by replacing the open dimpled tantalum boat with the pinhole tubular form. The uniformity, purity and thickness of As and Pb layers in the fabricated targets were assessed using a non-destructive Energy dispersive X-ray fluorescence (EDXRF) technique set-up. The measured thickness values of As and Pb/Au layers were found to agree within ∼3% with those deduced from the weighing method. The prepared targets have been successfully used with 28Si and 31P ion beams and the in-beam γ-ray spectroscopic studies in excited nuclear states in 98,99Rh, 99,100,101Pd and 102Ag isotopes.

Non-destructive elemental analysis of herbal teas from South Africa

The elemental analysis of tea is essential since it is a commonly consumed beverage around the world. In this paper, non-destructive energy dispersive X-ray fluorescence spectrometry (EDXRF) using a standardless method based on fundamental parameters was applied in honeybush and rooibos analysis. Tea samples were measured directly in the form of loose powders. The observed element concentrations (mg kg−1) were as follows: Ca (1260–3990), Cl (914–7710), K (2270–7190), Mg (374–2510), S (474–1320), P (183−1210), Si (303−1580), Al (92–765), Fe (67–514), Mn (26–163), Cr (1.8–20), Cu (2.2–11.5), Ni (1.1–5), Rb (0.8–8), Sr (5.4–24.5), Ti (4.1–39), and Zn (4.2–18.6). What is more, the determined concentrations (mg kg−1) of selected elements in rooibos and honeybush, are statistically different: Cl (2200–7710 rooibos and 913.7–2160 honeybush); Mg (1232–3465 rooibos and 535.9–1030 honeybush); P (388.0–1566 rooibos and 244.0–403.6 honeybush); Br (12.1–52.8 rooibos and 1.6–5.3 honeybush). Multivariate analysis of variance (ANOVA) was successfully applied to the data, showing statistical significance of the concentration differences for all the elements in both types of tea. The developed method provided good precision (RSD < 6%) with an accuracy of more than 90 %, and LOD ∼ 0.5 mg kg-1- for trace elements. The method was validated using suitable certified reference materials of tea (CRM).

Obsidian Source Use Within the Alföld Linear Pottery culture in Slovakia

This paper reports the results of non-destructive energy dispersive x-ray fluorescence (EDXRF) analysis of 186 obsidian artifacts from eight archaeological sites attributable to the Alföld Linear Pottery Culture (c. 5600-4900 cal BC). This is the largest instrument-based study yet conducted and reported for Alföld Linear Pottery Culture (ALPC) artifacts from Slovakia, where ALPC chipped lithic assemblages are almost entirely composed of obsidian items. Results show that all obsidian artifacts analyzed were manufactured exclusively from a volcanic glass of the Carpathian 1 chemical type, the source of which has been localised in Slovakia. This chemical variety of obsidian appears to have been the most important volcanic glass used by prehistoric communities in East-Central Europe during the Neolithic.

A Direct Non-destructive Method for Determination of Sulfur in Ore Samples Using EDXRF Spectrometry.

A method has been developed for direct non-destructive energy dispersive X-ray fluorescence (EDXRF) determination of sulfur in solid uranium ores and intermediates, obtained from the alkaline recovery process for uranium from its ores. The method involves thorough grinding of a few mg of solid powder samples to fine particle size and mixing the fine powder thus obtained with a few drops of 10% collodion solution in amyl acetate to make a paste. A very small amount of this paste was transferred with the help of the pestle tip, spread uniformly in the form of thin slurry on Mylar films, and dried to make very thin sample specimens on thin Mylar film supports. These specimens were presented for EDXRF measurements. A calibration plot was made by plotting the intensity ratios of S Kα and Rayliegh scattered peak of the excitation source (Ge Kα) against sulphur percent in the certified reference materials (CRMs). It was found that the precision obtained using this methodology was within 5% (±1σ) and the deviation of the EDXRF analytical results from the expected values of CRM was within 7%. The developed method was successfully applied for the determination of sulfur in the samples obtained from the different stages of the uranium ore processing using alkaline based leaching method.

Building ED-XRF datasets for sourcing rhyolite and quartzite artifacts: A case study on the Homa Peninsula, Kenya

Determining the provenance of archeological material is essential for documenting the movement of ancient resources and placing fossils and artifacts in the correct stratigraphic context. Non-destructive geochemical compositional analysis with Energy Dispersive X-ray Fluorescence (ED-XRF) spectrometry has the potential to provide a versatile approach to studying the provenance of archeological material. It is possible to build large regional XRF datasets that are useful for understanding the movements of toolmakers because this technique can be applied to a large number of samples non-destructively. However, incorporating new provenance data into existing datasets poses several potential challenges. Expanded provenance datasets often require the comparison of geochemical data across XRF instruments and settings. In particular the addition of different lithologies requires an understanding of diverse degrees of surface weathering and matrix heterogeneity.On the Homa Peninsula in Kenya, Oldowan tools from Kanjera South were previously linked to primary and secondary sources based on trace element geochemistry determined through ED-XRF. In this study, we established comparability across two ED-XRF instruments and incorporated samples from additional sources of quartzite and rhyolite into the existing raw material sourcing dataset. The new sources revealed regional differences in the geochemistry of rhyolite and quartzite that derive from drainages on and around the Homa Peninsula. This demonstrates the compatibility of quartzite and rhyolite materials with non-destructive ED-XRF sourcing and provides a methodological establishment of cross-study comparison in elemental values derived from non-uniform whole rock samples. This study highlights the importance of calibration using overlapping reference standards and linear regressions to determine offsets necessary for direct comparison.

The determination of the geographic origins of hops (Humulus lupulus L.) by multi-elemental fingerprinting.

For brewers, it is important to know the geographic origins of the hop plants (Humulus lupulus L.) used in their brewing processes since the contents and compositions of the bitter resins and essential oils in them depend on the environmental conditions during their growth. In this study, the multi-elemental profiles of hop plants from each of the world's main growing regions were determined by non-destructive energy dispersive X-ray fluorescence spectrometry (EDXRF). Understanding the multi-element profiles of the plants could be a useful tool in determining the geographic origins of produced hop plants.

Trace element characterization of obsidian from the Transcarpathian Ukraine

Non-destructive energy dispersive X-ray fluorescence (EDXRF) analysis was conducted on geological obsidian references samples from Carpathian 3 localities within the territory of the Ukrainian Transcarpathia. These data augment the trace element “signature” for this chemical variety of obsidian, which we applied to compare with trace element data determined on obsidian artifacts from nearby archaeological sites. The results: 1) document the local use and importance of Carpathian 3 obsidian, and 2) show use of non-local (Carpathian 1) volcanic glass at local geological outcrops of Carpathian 3 obsidian, suggesting prehistoric conveyance of Carpathian 1 volcanic glass in to Ukrainian Transcarpathian archaeological sites during the Upper Paleolithic period.

Gilded copper studied by non-destructive energy-dispersive X-ray fluorescence

Gilded copper studied by non-destructive energy-dispersive X-ray fluorescence

Basalt geochemistry reveals high frequency of prehistoric tool exchange in low hierarchy Marquesas Islands (Polynesia).

Exchange activities, formal or otherwise, serve a variety of purposes and were prominent in many Pacific Island societies, both during island settlement and in late prehistory. Recent Polynesian studies highlight the role of exchange in the region’s most hierarchical polities where it contributed to wealth economies, emergent leadership, and status rivalry in late prehistory. Building on this research, we hypothesized that exchange in low hierarchy chiefdoms (kin-based polities where there are distinctions between commoners and elites but ranking within the latter is lacking, weak, or ephemeral) would differ in frequency and function from that associated with strongly hierarchical polities. We address this hypothesis through geochemical, morphological, and distributional analyses of stone tools on Nuku Hiva, Marquesas Islands. Non-destructive Energy-Dispersive X-ray Fluorescence (EDXRF) and destructive Wavelength-Dispersive X-ray Fluorescence (WDXRF) analyses of 278 complete and broken tools (adzes, chisels, preforms) from four valleys identify use of stone from at least seven sources on three islands: five on Nuku Hiva and one each on Eiao and Ua Pou. A functional analysis demonstrates that no tool form is limited to a particular source, while inter-valley distributions reveal that the proportions of non-local or extra-valley tools (43 to 94%, mean = 77%) approximate or exceed results from other archipelagoes, including those from elite and ritual sites of Polynesian archaic states. Intra-valley patterns also are unexpected, with non-local stone tools being recovered from both elite and commoner residential areas in near-equal proportions. Our findings unambiguously demonstrate the importance of exchange in late prehistoric Marquesan society, at varied social and geographic scales. We propose the observed patterns are the result of elites using non-local tools as political currency, aimed at reinforcing status, cementing client-patron relations, and building extra-valley alliances, consistent with prestige societies elsewhere and early historic accounts from the Marquesan Islands.

On the sources and uses of obsidian during the Paleolithic and Mesolithic in Poland

Eighty-six obsidian artifacts from twenty Paleolithic and Mesolithic archaeological sites in Poland were analyzed using non-destructive energy dispersive x-ray fluorescence (EDXRF) analysis and assigned to parent geological obsidian source (chemical type). Results of the study— the first country-wide survey of its kind—support the conclusion that the geological source of obsidian remained largely unchanged for thousands of years, that obsidian use appears to have been minimal throughout the Paleolithic and Mesolithic regardless of distance to source, that obsidian artifacts were used to perform the same functions as their non-obsidian (flint and radiolarite) counterparts, and that the distinct visual properties of volcanic glass may have contributed to its recognition as unique and exotic in different social contexts.

Use of Monte Carlo Simulation as a Tool for the Nondestructive Energy Dispersive X-ray Fluorescence (ED-XRF) Spectroscopy Analysis of Archaeological Copper-Based Artifacts from the Chalcolithic Site of Perdigões, Southern Portugal.

This work is part of a broader research line that aims to develop and implement a nondestructive methodology for the chemical characterization of archaeological metals based on a protocol that combines energy dispersive X-ray fluorescence spectrometry (ED-XRF) with a Monte Carlo (MC) simulation algorithm. In this paper, the ED-XRF-MC protocol has been applied to estimate the chemical composition of a selected group of 26 copper-based artifacts and fragments recovered at Perdigões, one of the larger Chalcolithic sites of southwest Iberia. All the analyzed artifacts have a multilayered structure composed of the alloy substrate and of a superficial layer common in each metal buried for hundreds of years and consisting of the patina mixed with soil. Due to the difficulty in determining the quantitative composition of these alloys in the presence of this complex patina/encrustation layer, the spectrometric protocol applied in this paper allows to simulate and to determine the composition of the bulk alloy without any prior removal of the overlying corrosion patina layer and soil-derived crust, even in the presence of rough and irregular surfaces, thus preserving the physical integrity of the artifacts. The overall results obtained with the ED-XRF-MC protocol indicates that the artifacts from Perdigões are almost pure coppers with a low amount of arsenic (<3.0 wt%) and reduced concentration of elements such as Pb, Bi, and Sb, in agreement with the third millennium metallurgy known in southwestern Iberia. Also based on previously theoretical-experimental studies, the data presented in this paper show how the applied analytical methodology can be a fast and completely nondestructive analytical tool reliable for routine and large-scale chemical analysis of archaeological metals, thus representing a major advance to be broadly applied within the field of cultural heritage studies.

Macro elemental analysis of food samples by nuclear analytical technique

Energy-dispersive X-ray fluorescence (EDXRF) spectrometry is a non-destructive, rapid, multi elemental, accurate, and environment friendly analysis compared with other detection methods. Thus, EDXRF spectrometry is applicable for food inspection. The macro elements calcium and potassium constitute important nutrients required by the human body for optimal physiological functions. Therefore, the determination of Ca and K content in various foods needs to be done. The aim of this work is to demonstrate the applicability of EDXRF for food analysis. The analytical performance of non-destructive EDXRF was compared with other analytical techniques; neutron activation analysis and atomic absorption spectrometry. Comparison of methods performed as cross checking results of the analysis and to overcome the limitations of the three methods. Analysis results showed that Ca found in food using EDXRF and AAS were not significantly different with p-value 0.9687, whereas p-value of K between EDXRF and NAA is 0.6575. The correlation between those results was also examined. The Pearson correlations for Ca and K were 0.9871 and 0.9558, respectively. Method validation using SRM NIST 1548a Typical Diet was also applied. The results showed good agreement between methods; therefore EDXRF method can be used as an alternative method for the determination of Ca and K in food samples.

Assessing XRF for the geochemical characterization of radiolarian chert artifacts from northeastern North America

The purpose of this paper is to emphasize the benefits of adopting non-destructive energy dispersive X-ray fluorescence (ED-XRF) as a first-order technique to determine chert whole-rock geochemistry for archaeological sourcing. Chemical signatures for the Touladi and La Martre prehistoric quarries from the lower St. Lawrence and Gaspé Peninsula region of Quebec, Canada, are determined and serve as references to test the provenance of regional chert artifacts. Chert experimental flakes, created from quarry geological hand samples, are analyzed and used to validate the method. Archaeological flakes and tools recovered from three archaeological sites are analyzed and tested against quarry samples. Geochemical diagrams and Principal Component Analysis are used to establish artifact-quarry relationships. The effects of surface weathering on the geochemical analysis of archaeological chert artifacts are presented. Sample restoration and research avenues are discussed and proposed to further enhance the robustness of future chert geochemical data sets.

Comparison of two analytical methods for the chemical characterization of flint from Lithuania and Belarus

In this paper, authors present the results of interlaboratory comparison of two different methods of determining the chemical composition of Lithuanian and Belarusian flint: direct current arc emission spectrophotometry (DCAES) and energy dispersive X-ray fluorescence (EDXRF). For this interlaboratory comparison, geological specimens from three Lithuanian and Belarusian flint sources, previously analysed by Baltrūnas et al.(2006a), were sent to the first author for a non-destructive EDXRF analysis. All three sources were important for prehistoric tool manufacturing during Lithuanian prehistory. Non-destructive EDXRF analyses of flint may be preferred in situations where it is important to conserve archaeological artifacts, whereas DCAES is capable of analyzing more elements with precision which may be needed to identify flint with overlapping Ca / Fe compositions that cannot be separated by non-destructive EDXRF. The interlaboratory comparison results we present here illustrate the importance of international cooperation among geoscientists and archaeologists interested in applying chemical and geological methods and data to study the economic, social and cultural processes operating during different times in the prehistoric past. Key words: flint, geochemistry, energy dispersive X-ray fluorescence (EDXRF) analysis, Lithuania, Belarus

Interpolity exchange of basalt tools facilitated via elite control in Hawaiian archaic states

Ethnohistoric accounts of late precontact Hawaiian archaic states emphasize the independence of chiefly controlled territories (ahupua'a) based on an agricultural, staple economy. However, elite control of unevenly distributed resources, such as high-quality volcanic rock for adze production, may have provided an alternative source of economic power. To test this hypothesis we used nondestructive energy-dispersive X-ray fluorescence (ED-XRF) analysis of 328 lithic artifacts from 36 archaeological features in the Kahikinui district, Maui Island, to geochemically characterize the source groups. This process was followed by a limited sampling using destructive wavelength-dispersive X-ray fluorescence (WD-XRF) analysis to more precisely characterize certain nonlocal source groups. Seventeen geochemical groups were defined, eight of which represent extra-Maui Island sources. Although the majority of stone tools were derived from Maui Island sources (71%), a significant quantity (27%) of tools derived from extraisland sources, including the large Mauna Kea quarry on Hawai'i Island as well as quarries on O'ahu, Moloka'i, and Lāna'i islands. Importantly, tools quarried from extralocal sources are found in the highest frequency in elite residential features and in ritual contexts. These results suggest a significant role for a wealth economy based on the control and distribution of nonagricultural goods and resources during the rise of the Hawaiian archaic states.

Discriminating authentic Nostoc flagelliforme from its counterfeits by applying alternative ED-XRF and FTIR techniques

Nostoc flagelliforme is an edible blue-green algae belonging to the Nostocaceae family. It is recognised as a Chinese delicacy in south-eastern Asia and is widely consumed. Due to its high economic value and diminishing supply, as a result of overharvesting, counterfeits have often been found in the retail markets. Methods involving microscopy and histochemistry were conventionally applied to differentiate the authentic N. flagelliforme from its counterfeits. In this paper, we report an alternative analytical approach, using a combination of non-destructive energy dispersive X-ray fluorescence (ED-XRF) and Fourier-transform infrared (FTIR) spectroscopy, to achieve the objective of authentic N. flagelliforme verification. In view of the scarcity of this Chinese delicacy, such a non-destructive methodology would be ideal to preserve the integrity of the sample and yet provide a means to discriminate between authentic and counterfeit samples.

Characterization of elemental and firing-dependent properties of Phlegrean ceramics by non-destructive ED-XRF and NMR techniques

A combination of energy dispersive X-ray fluorescence (ED-XRF) and 2D proton nuclear magnetic resonance ( 1H NMR) relaxometry was employed for the characterization of two groups of similar ceramic fragments from the high-medieval production of the Phlegrean area (Miseno and Cuma, Southern Italy). Both methods are based on the use of non-destructive and portable instruments. This approach allows to correlate complementary microstructural features of ceramics, both dependent and independent of the firing technique. The ED-XRF analysis has shown up the degree of elemental homogeneity of these two ceramic populations and has lead to reasonable hypotheses about continuity in raw clay source utilization and manufacturing methods over the time period of this Phlegrean ceramic production (VI–XIII centuries A.D.), which have proven coherent with literature data. The NMR investigation has allowed to reveal the structural differences among findings, concerning pore space topology and the magnetic attributes of pore walls. Such differences have been associated to the peculiar interplay between temperature and duration of firing and have proven in step with the temperature assignments provided by archaeologists. This way the usefulness of the proposed methodology for the characterization of the microstructural fingerprint of ancient ceramics has been clearly shown and reliable conclusions about the technological evolution of and the mutual influence between the investigated ceramic productions have been drawn.

Science and Sensitivity: A Geochemical Characterization of the Mauna Kea Adze Quarry Complex, Hawai'I Island, Hawaii

The Mauna Kea Adze Quarry Complex is the largest-known prehistoric quarry in the Pacific Basin. The main extraction areas are located at an extreme altitude (3,800 m), near the summit of Hawaii's tallest mountain. The Mauna Kea summit region and the quarry are considered by many Hawaiians to be a sacred landscape and archaeologists must consider the ethical tensions involved in conducting Western science in these areas. Although provenance studies of basalt adzes are integral to the examination of pre-contact Hawaiian economics, former studies of Hawaiian adze distribution have been limited in scope, and conventionally relied on destructive petrography and petrology for the analyses. Published geochemical data on the quarry are derived from only eight samples analyzed with destructive methods. In order to better define the variation within the quarry, and to develop a more culturally sensitive approach, we employed nondestructive energy dispersive X-ray fluorescence (EDXRF) of whole-rock samples to characterize 820 flakes and 47 geological samples from the quarry complex. This study offers the first reliable estimation of the overall range of geochemical variability in the complex. These results suggest that nondestructive EDXRF can be used to differentiate Mauna Kea basalts from other known Hawaiian quarries, but more characterization of other quarries is necessary to confirm exclusive separation of sources. The results further demonstrate that EDXRF is capable of detecting intra-site geochemical variation in Mauna Kea quarry material.