Search Results (21)

Citriculture has worldwide importance, and monitoring the nutritional status of plants through leaf analysis is essential. Recently, proximal sensing has supported this process, although there is a lack of studies conducted specifically for citrus. The objective of this study was to evaluate the application of portable X-ray fluorescence spectrometry (pXRF) combined with machine learning algorithms to predict the nutrient content (B, Ca, Cu, Fe, K, Mg, Mn, P, S, and Zn) of citrus leaves, using inductively coupled plasma optical emission spectrometry (ICP-OES) results as a reference. Additionally, the study aimed to differentiate 15 citrus scion/rootstock combinations via pXRF results and investigate the effect of the sample condition (fresh or dried leaves) on the accuracy of pXRF predictions. The samples were analyzed with pXRF both fresh and after drying and grinding. Subsequently, the samples underwent acid digestion and analysis via ICP-OES. Predictions using dried leaves yielded better results (R² from 0.71 to 0.96) than those using fresh leaves (R² from 0.35 to 0.87) for all analyzed elements. Predictions of scion/rootstock combinations were also more accurate with dry leaves (Overall accuracy = 0.64, kappa index = 0.62). The pXRF accurately predicted nutrient contents in citrus leaves and differentiated leaves from 15 scion/rootstock combinations. This can significantly reduce costs and time in the nutritional assessment of citrus crops. Full article

The detection of available Cr(VI) in soil is critical due to its high uptake by plants, which enables it to enter the food chain and pose significant health risks to humans. Traditional detection methods are often time-consuming and labor-intensive, limiting their suitability for rapid, on-site measurements. This study introduces a novel approach for the rapid detection of available Cr(VI) in soil, utilizing portable X-ray fluorescence spectrometry (pXRF) in combination with ion-exchange resin. The method was validated using soil samples from three distinct regions, representing three different soil types. Compared to conventional laboratory methods, the detection rates for Cr(VI) ranged from 80.73% to 124.14%, with relative standard deviations for repeated analyses ranging from 3.05% to 5.73%, both of which comply with national standards. Regression analysis confirms a strong linear relationship between spectral values and Cr(VI) concentration in standard solutions (R² = 0.9986). Through resin enrichment, the detection limit (LoD) for Cr(VI) in soil solution reaches 0.070 mg/kg, facilitating trace-level detection of available Cr(VI) in soil. In contrast to traditional methods, the pXRF-ion-exchange resin approach minimizes secondary environmental contamination, is cost-effective and time-efficient, and does not require complex soil pretreatment. Consequently, it is highly suitable for rapid, on-site soil analysis. This study presents an innovative method for the detection of available Cr(VI) in soils. This approach effectively reduced analysis time and simplified sample pretreatment, and thus holds substantial potential for practical application. Full article

The most common scientific analysis of archaeological ceramics aims to determine the raw material source and/or production technology. Scientists and archaeologists widely use XRF-based techniques as a tool in a provenance study. After conducting XRF analysis, the results are often analyzed using multivariate analysis in addition to interpretation and conclusions. Various multivariate techniques have already been applied in archaeological ceramics provenance studies to reveal different raw material sources, identify imported pieces, or determine different production recipes. This study aims to evaluate the results of multivariate analysis in the provenance study of ceramics that belong to three cultures that settled in the same area during various prehistoric periods. Portable energy-dispersive X-ray fluorescence spectrometry (pEDXRF) was used to determine the elemental composition of the ceramic material. The ceramic material was prepared in two different ways. The ceramic body material was ground into powder, homogenized, and then pressed into tablets. After that, the same fragments are polished in suitable places. Quantitative and qualitative analyses were performed on the tablets and polished pieces. The results were subjected to both unsupervised and supervised multivariate analysis. Based on the results, it was concluded that qualitative analysis of the well-prepared shards’ surface using EDXRF spectrometry could be utilized in provenance studies, even when the ceramic assemblages were made of similar raw materials. Full article

The Hispanic Society Museum & Library (HSML) holds a collection of nine viceregal barniz de Pasto objects, made by Indigenous artisans in the 17th and 18th centuries. Designed to imitate Asian lacquers and intended for European aesthetic tastes, barniz de Pasto is an example of Indigenous technique and knowledge that has survived to the present day. An in-depth analysis of five of these barniz de Pasto objects, dated to the first half and last quarter of the 17th century based on their iconography, was carried out through a combination of non-invasive and micro-invasive techniques, including portable X-ray fluorescence (pXRF) spectroscopy to investigate the possible presence of inorganic pigments, and fiber-optics reflectance spectroscopy (FORS) and reflectance imaging spectroscopy (RIS) to provide molecular information on colorants and their distributions across the objects. Dyes and pigments were also identified using Raman spectroscopy, Fourier-transform infrared (FTIR) spectroscopy, and liquid chromatography/mass spectrometry (LC/MS). The nature of the resin was determined by FTIR and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), while the decoration stratigraphy and composition were analyzed by scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS). This paper confirms the use of mopa mopa, the resin used in the barniz de Pasto technique, in two objects not previously analyzed, and identifies indigo, insect-based red, calomel, lead white, and an unknown flavonol-based yellow dye, and challenges the use of calomel as a temporal marker for these works. Taken together, these results expand our understanding of the material use and explorations undertaken by artists during this time period to create such elaborate and enduring objects. Full article

Several techniques, such as chemical methods and inductively coupled plasma mass spectrometry (ICP-MS), are available to accurately determine element content. However, they are time-consuming, labor-intensive, or expensive. Portable X-ray fluorescence spectrometry (pXRF) can be applied in various scenarios, with significantly higher efficiency and cost-effectiveness than laboratory methods. However, it also has limitations such as lower detection capability, relatively high detection limits, and lower accuracy than laboratory methods. In this study, we focused on applying pXRF to determine the elemental content of sediment samples and investigate its use in mineral exploration. A variety of factors influencing the results of pXRF analysis were analyzed. Our results showed that pXRF could detect more than 30 elements in stream sediments. The reliability of pXRF’s measurements was affected by factors such as the kind of element, sediment particle size, sample grinding treatment, count time, averaged element content, standard deviation of content, and range of content variation. The combination of pXRF analysis and laboratory analysis of partial samples is adequate for establishing a multi-element content inference equation. With this equation, it is possible to effectively infer the content gradient of elements, which will provide valuable support for mineral resource exploration. Full article

The use of gold for artefact productions underwent substantial developments during Iron Age in western Europe, with the diversification of alloy compositions and the introduction of new technologies and aesthetics. This work presents a detailed study of a Late Iron Age earring from the western Iberian Peninsula and a discussion taking into consideration the alloys and technologies used at the time. The earring has a complex structure, composed of block- and strip-twisted wires and granulation. Characterization by multifocus optical microscopy, portable X-ray fluorescence spectrometry (pXRF), micro-XRF and scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS) were performed to obtain information on the chemical composition and manufacturing techniques. Results show that the earring was manufactured with wires and granules made of a silver-rich alloy, covered with a gold-rich layer 45 $\mathsf{\mu }$m thick on average, which acted as an external coating making the entire earring resemble gold. This is a rare example of an Iron Age gilded earring, and its detailed study provides further information on the manufacturing solutions adopted by the Iron Age goldsmiths. Full article

Preserving and analytically examining daguerreotypes is particularly challenging because of their multi-material and multi-component structure. Various sensors have been exploited to examine mainly the image plates of the daguerreotypes even though the degradation goes beyond this component. Micro-analyses have been the preferred method due to the nanoscale structure of the image particles. In this work, we propose comprehensive multi-modal non-invasive sensing to investigate the corrosion products present in nine daguerreotypes from the Fondazione Alinari per la Fotografia (FAF, Florence, Italy). The methodology proposed includes chemical and morphological analyses: portable X-ray fluorescence spectrometry (pXRF), Raman microspectroscopy (μ-Raman), and micro-Fourier transform infrared spectroscopy in reflection mode (μ-rFTIR) for the chemical identification. For the first time, optical coherence tomography (OCT) was deployed to record the cross-sectional and morphological data of the relevant corrosion formations on daguerreotypes in a contactless way. The results allowed the characterization, in a non-invasive mode at a microscopic level, of a wide range of degradation products produced by the interaction of the different elements present in the structure of the daguerreotypes. The aim was to verify the performance of the proposed methodology and to link the chemical and physical complexity of the entire structure, disclosed by the state-of-art sensors, to the daguerreotype degradation. The results draw attention to the need to monitor not only the image condition but the whole object as a partially closed system in constant interaction internally and with the environment. Full article

Yves Klein (1928–1962) is best known for his intensely blue monochromatic works made with International Klein Blue (IKB), a synthetic ultramarine blue pigment bound in a poly(vinyl acetate) binder. However, he also made monochromes in other colors, including red and pink, the pigments of which have never been elucidated. Analysis of one sculpture, three paintings, and one screenprint by micro-Fourier transform infrared spectroscopy (µ-FTIR), Raman and surface-enhanced Raman (SERS) spectroscopies, portable X-ray fluorescence spectroscopy (p-XRF), and scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectrometry (EDX), revealed that Klein used, knowingly or unknowingly, a variety of pink and red pigments, including Para Red, rhodamine 6G, rhodamine B, eosin Y, and alizarin lakes. The unexpected variety of pigments contrasts with his use of a single blue pigment and suggests he may not have held a singular vision of what constituted an iconic red or pink color. Full article

Quartz is one of the most common minerals in soils, mostly present in sand and silt fractions. Although quartz is basically formed of SiO₂, other elements can be easily detected and assessed nowadays using a portable X-ray fluorescence (pXRF) spectrometer. Our study aims to evaluate the chemical composition of different quartz varieties, identifying their main elements, and relating them to soil attributes. Six quartz varieties (hyaline, amethyst, milky, rose, smoky, and ferriferous) were analyzed via pXRF and 13 oxides/trace elements were identified and used for quartz discrimination (Al₂O₃, CaO, P₂O₅, SiO₂, Cl, Cr, Fe, K₂O, Mn, Rb, S, Ti, and V). Hyaline quartz was characterized by the highest SiO₂ and the lowest contents of other elements. Al₂O₃ was the second-highest compound present in all varieties of quartz, reaching 21,547 mg kg⁻¹ in the smoky variety. S, P₂O₅, Cl, SiO₂, and K₂O were the main components determined by Random Forest algorithm for discriminating quartz varieties. Some elements detected may serve as a reserve of nutrients to plants to be released in soils along weathering, depending on quartz particle size, soil texture, leaching, and associated attributes. pXRF enhanced the information on chemical characterization of quartz varieties, without the generation of chemical pollutants. Full article

Several materials have been characterized using proximal sensors, but still incipient efforts have been driven to plant tissues. Eucalyptus spp. cultivation in Brazil covers approximately 7.47 million hectares, requiring faster methods to assess plant nutritional status. This study applies portable X-ray fluorescence (pXRF) spectrometry to (i) distinguish Eucalyptus clones using pre-processed pXRF data; and (ii) predict the contents of eleven nutrients in the leaves of Eucalyptus (B, Ca, Cu, Fe, K, Mg, Mn, N, P, S, and Zn) aiming to accelerate the diagnosis of nutrient deficiency. Nine hundred and twenty samples of Eucalyptus leaves were collected, oven-dried, ground, and analyzed using acid-digestion (conventional method) and using pXRF. Six machine learning algorithms were trained with 70% of pXRF data to model conventional results and the remaining 30% were used to validate the models using root mean square error (RMSE) and coefficient of determination (R²). The principal component analysis clearly distinguished developmental stages based on pXRF data. Nine nutrients were accurately predicted, including N (not detected using pXRF spectrometry). Results for B and Mg were less satisfactory. This method can substantially accelerate decision-making and reduce costs for Eucalyptus foliar analysis, constituting an ecofriendly approach which should be tested for other crops. Full article

Large-scale, high-density geochemical explorations entail enormous workloads and high costs for sample analysis, but, for early mineral exploration, absolute concentrations are not essential. Geochemists require ranges, dynamics of variation, and correlations for early explorations rather than absolute accuracy. Thus, higher work efficiency and lower costs for sample analysis are desirable for geochemical exploration. This study comprehensively analyzed the reliability and applicability of portable X-ray fluorescence (pXRF) spectrometry in geochemical exploration. The results show that pXRF can be applied effectively to rock and rock powder samples, and sample preparation and a longer detection time have been shown to increase the precision of the pXRF results. When pXRF is used on rock samples, if less than 30% of the samples are assessed as containing an element, the element is usually undetectable using pXRF when these rock samples are prepared as rock powders, indicating that the data about the detected element are unreliable; thus, it is suggested that some representative samples should be selected for testing before starting to use a pXRF in a geochemical exploration project. In addition, although the extended detection time increased the reliability of the analysis results, an increase in detection time of more than 80 s did not significantly affect the accuracy of the results. For this reason, the recommended detection time for the pXRF analysis of rock powder samples is 80 s for this study. pXRF has the advantages of being low-cost, highly efficient, and stable, and its results are reliable enough to exhibit the spatial distribution of indicator elements (arsenic, nickel, lead, sulfur, titanium, and zinc) in polymetallic mineralization exploration. Therefore, pXRF is recommendable for practical use in geochemical exploration. Full article

Despite the increasing adoption of proximal sensors worldwide, rare works have coupled proximal with remotely sensed data to spatially predict soil properties. This study evaluated the contribution of proximal and remotely sensed data to predict soil texture and available contents of micronutrients using portable X-ray fluorescence (pXRF) spectrometry, magnetic susceptibility (MS), and terrain attributes (TA) via random forest algorithm. Samples were collected in Brazil from soils with high, moderate, and low weathering degrees (Oxisols, Ultisols, Inceptisols, respectively), and analyzed by pXRF and MS and for texture and available micronutrients. Seventeen TA were generated from a digital elevation model of 12.5 m spatial resolution. Predictions were made via: (i) TA; (ii) TA + pXRF; (iii) TA + MS; (iv) TA + MS + pXRF; (v) MS + pXRF; and (vi) pXRF; and validated via root mean square error (RMSE) and coefficient of determination (R²). The best predictions were achieved by: pXRF dataset alone for available Cu (R² = 0.80) and clay (R² = 0.67) content; MS + pXRF dataset for available Fe (R² = 0.68) and sand (R² = 0.69) content; TA + pXRF + MS dataset for available Mn (R² = 0.87) content. PXRF data were key to the best predictions. Soil property maps created from these predictions supported the adoption of sustainable soil management practices. Full article

Findings of Iron Age metallurgical activities related to tin metal and mining are very rare. In the present work, we present a detailed study of the Outeiro de Baltar hillfort, dated to the Late Iron Age/Early Roman period, located in a place where 20th century tin mining work took place. Elemental and microstructural analysis by portable, micro and wavelength dispersive X-ray fluorescence spectrometry (pXRF, micro-XRF and WDXRF) and scanning electron microscopy with energy dispersion spectrometer (SEM-EDS) showed that metallurgical debris found at the archaeological site is related to tin smelting and binary and ternary bronze productions. Analysis of the artefacts of diverse typologies found at the site showed that a variety of metals and alloys were in circulation and use. Samples of tin ores (cassiterite) from the region were analyzed for comparison with an archaeological tin slag from the site. The analytical results point to the production of tin metal using local cassiterite and the production of bronze by directly adding cassiterite into a smelting process. Furthermore, data of remote sensing (airborne Light Detection and Ranging (LiDAR) and historical aerial imagery) and Geographical Information System (GIS) mapping were combined with archival mining documentation and maps to retrieve a landscape context for the site. The study showed that the place of the Outeiro de Baltar hillfort (NW Iberia) was mined periodically over time. Full article

Portable X-ray fluorescence spectrometry (pXRF) is an analytical technique that can be used for rapid and non-destructive analysis in the field. However, the testing accuracy and precision for trace elements are significantly affected by the matrix effect, which comes mainly from major elements that constitute most of the matrix of a sample. To solve this problem, many methods based on linear regression models have been proposed, but when extreme values or outliers occur, the application of these methods will be greatly affected. In this study, 16 certified reference materials were collected for pXRF analysis, and the major elements most closely related to the elements to be measured were employed as correction indicators to calibrate the analysis results through the application of multiple linear regression analysis. Some statistical parameters were calculated to evaluate the correction results. Compared with the calibration data obtained from simple linear regression analysis without taking major elements into account, those corrected by the new method were of higher quality, especially for elements of Co, Zn, Mo, Ta, Tl, Pb, Cd and Sn. The results show that the new method can effectively suppress the influence of the matrix effect. Full article

This article discusses the assessment of groundwater quality using a hybrid technique that would aid in the convenience of groundwater (GW) quality monitoring. Twenty eight (28) GW samples representing 62 barangays in Calapan City, Oriental Mindoro, Philippines were analyzed for their physicochemical characteristics and heavy metal (HM) concentrations. The 28 GW samples were collected at suburban sites identified by the coordinates produced by Global Positioning System Montana 680. The analysis of heavy metal concentrations was conducted onsite using portable handheld X-Ray Fluorescence (pXRF) Spectrometry. Hybrid machine learning—geostatistical interpolation (MLGI) method, specific to neural network particle swarm optimization with Empirical Bayesian Kriging (NN-PSO+EBK), was employed for data integration, GW quality spatial assessment and monitoring. Spatial map of metals concentration was produced using the NN-PSO-EBK. Another, spot map was created for observed metals concentration and was compared to the spatial maps. Results showed that the created maps recorded significant results based on its MSEs with values such as 1.404 × 10⁻⁴, 5.42 × 10⁻⁵, 6.26 × 10⁻⁴, 3.7 × 10⁻⁶, 4.141 × 10⁻⁴ for Ba, Cu, Fe, Mn, Zn, respectively. Also, cross-validation of the observed and predicted values resulted to R values range within 0.934–0.994 which means almost accurate. Based on these results, it can be stated that the technique is efficient for groundwater quality monitoring. Utilization of this technique could be useful in regular and efficient GW quality monitoring. Full article