The use of a portable X-ray fluorescence spectrometer for measuring nickel in plants: sample preparation and validation.

X-ray fluorescence is a fast, cost-effective, and eco-friendly method for elemental analyses. Portable X-ray fluorescence spectrometers (pXRF) have proven instrumental in detecting metals across diverse matrices, including plants. However, sample preparation and measurement procedures need to be standardized for each instrument. This study examined sample preparation methods and predictive capabilities for nickel (Ni) concentrations in various plants using pXRF, employing empirical calibration based on inductively coupled plasma optical emission spectroscopy (ICP-OES) Ni data. The evaluation involved 300 plant samples of 14 species with variable of Ni accumulation. Various dwell times (30, 60, 90, 120, 300 s) and sample masses (0.5, 1.0, 1.5, 2.0 g) were tested. Calibration models were developed through empirical and correction factor approaches. The results showed that the use of 1.0 g of sample (0.14 g cm-2) and a dwell time of 60 s for the study conditions were appropriate for detection by pXRF. Ni concentrations determined by ICP-OES were highly correlated (R2 = 0.94) with those measured by the pXRF instrument. Therefore, pXRF can provide reliable detection of Ni in plant samples, avoiding the digestion of samples and reducing the decision-making time in environmental management.

Evaluating the portable X-ray fluorescence reliability for metal(loid)s detection and soil contamination status.

Marginalized communities experience barriers that can prevent soil monitoring efforts and knowledge transfer. To address this challenge, this study compared two analytical methods: portable X-ray fluorescence spectroscopy (pXRF, less time, cost) and inductively coupled plasma mass spectrometry (ICP-MS, "gold standard"). Surface soil samples were collected from residential sites in Arizona, USA (N = 124) and public areas in Troy, New York, USA (N = 33). Soil preparation differed between groups to account for community practice. Statistical calculations were conducted, paired t test, Bland-Altman plot, and a two-way ANOVA indicated no significant difference for As, Ba, Ca, Cu, Mn, Pb, and Zn concentrations except for Ba in the t test. Iron, Ni, Cr, and K were statistically different for Arizona soils and V, Ni, Fe, and Al concentrations were statistically different for New York soils. Zinc was the only element with high R2 and low p value. Pollution load index (PLI), enrichment factors (EF), and geo-accumulation index (Igeo) were calculated for both methods using U.S. Geological Survey data. The PLI were > 1, indicating soil pollution in the two states. Between pXRF and ICP-MS, the Igeo and EF in Arizona had similar degree of contamination for most elements except Zn in garden and Pb in yard, respectively. For New York, the Igeo of As, Cu, and Zn differed by only one classification index between the two methods. The pXRF was reliable in determining As, Ba, Ca, Cu, Mn, Pb, and Zn in impacted communities. Therefore, the pXRF can be a cost-effective alternative to using ICP-MS techniques to screen soil samples for several environmentally relevant contaminants to protect environmental public health.

Measurement of elements by portable x-ray fluorescence spectrometry for the study of adsorption processes: the case of Pb2+adsorption on soybean straw biochar.

This study evaluated the reliability of portable X-ray fluorescence (pXRF) in Pb2+adsorption kinetics and isotherm experiments using soybean straw biochar. The research aimed to compare pXRF results with those obtained through traditional atomic absorption spectrometry (AAS). Soybean straw biochar, produced at 400 °C, was employed as the adsorbent for Pb2+. The efficiency of adsorption was assessed using Langmuir and Freundlich models. The kinetics of Pb2+adsorption was analysed through pseudo-first-order and pseudo-second-order models. The pseudo-second-order model described the kinetics of Pb2+adsorption on biochar better than the pseudo-first order model. Importantly, the pXRF technique demonstrated comparable results to those of AAS, making it a reliable and resource-efficient method for studying Pb2+kinetics. The results of the isotherm analyses fit the Langmuir model, indicating a desirable and irreversible adsorption of Pb2+on biochar. PXRF measurements on biochar allowed simultaneous observations of Pb2+adsorption and K+and Ca2+desorption, highlighting ionic exchange as the primary adsorption mechanism. In conclusion, our results showcased the applicability of pXRF for Pb+2adsorption studies in biochars, offering a valuable alternative to traditional methods. The findings contribute to the understanding of biochar as an effective adsorbent for heavy metals, emphasizing the potential of pXRF for cost-effective and efficient environmental research. In this study, we present a novel and detailed procedure that will allow other researchers to continue their studies on Pb2+adsorption on biochar or similar matrices, significantly reducing the resources and time used and enabling the simultaneous study of the behavior of other ions participating in the process.

Hazardous elements in plastic and rubber granules as infill material from sports facilities? Field Portable-XRF spectroscopy as 'white analytical technique' reveals hazardous elements in fall sports facilities in Rzeszów (Podkarpackie, Poland).

Plastic and rubber granules are commonly used as infill material in all-weather sports facilities, providing an ideal activity surface for millions of Europeans on a daily basis. However, concerns have been raised about the presence of hazardous elements in these granules, which can pose risks both to the environment and human health. Our study focusses on the elemental composition of rubber granules used in fall sports facilities in Rzeszów, (Podkarpackie, Poland) using field portable X-ray fluorescence (FP-XRF) as a non-destructive and 'white analytical technique'. The results show the content of Zn, Fe, Cr, Ba, Br, Ti, Cu, Cd, As, Au, Bi, Pb, Ni, Sb, and Sn in the rubber granule samples. This study highlights the need for stringent quality control measures and regulations to ensure the safety of all-weather sports facilities and protect the well-being of sportsman. When modern FP-XRF spectrometry is employed as a "white analytical technique," for the first time it becomes possible to identify the presence of hazardous elements, addressing the pressing concerns highlighted by the ECHA and enabling proactive measures to mitigate potential risks. This approach ensures the protection of the health and sustainability of sports facilities, contributing to the ongoing hot topics in the field.

A two-way analytical investigation of ancient gold coins: Elemental and colorimetric description of precious materials.

The investigation of ancient artifacts is often constrained by their scarce availability and high protection and custody protocols. Among these, coinage represents an especially valuable kind-of-samples given their uniqueness and the subjacent information that is hidden behind their composition. Their analysis are often carried out using non-destructive techniques in order to avoid any alteration of the samples. In the field of Cultural Heritage analysis, smartphone-based methodologies have experienced a significant increase during the last few years, given their wide availability and ability to yield fast results. However, their analytical application demands a thorough and careful tuning during the methodology optimization. In this work, 21 historical gold and golden coins spanning a historical period of more than 2000 years have been analytically investigated. To that end, a two-fold approach has been implemented: first, the elemental composition has been analysed using portable X-ray fluorescence; and second, an innovative smartphone-based imaging method has been applied to measure their colour. Results allowed to describe the coins from their elemental profile, identifying some potentially debased ones, as well as some others not containing any gold. When possible, the results have been compared to previously reported cases, but our samples include some previously unreported cases representing new insights. All in all, this article provides new analytical data on unanalysed unique historical samples, in terms of their elemental profile and colorimetric properties, making use of an innovative, non-invasive nor destructive, fast and affordable colorimetric smartphone-based method to characterise historical coins.

Non-Invasive Raman Classification Comparison with pXRF of Monochrome and Related Qing Porcelains: Lead-Rich-, Lead-Poor-, and Alkali-Based Glazes.

Chinese porcelain with an optically clear colored glaze, imported to Europe from the Kangxi period (1662-1722, Qing Dynasty) onwards was highly collected by the French Elite of the 18th century. The bright colors with a clear, shiny glaze were unlike anything produced in Europe at that time. The colors of enamelled artifacts (on biscuits or already glazed porcelain) can be fully monochrome or consist of associations of large monochromatic areas with or without application of gilding. Non-invasive portable XRF and mobile Raman analyses have previously shown their effectiveness in the characterization of (colored) glassy silicates. In this study, we compare the Raman signatures of twenty-one Chinese artifacts fully-or with major monochrome area (sancai)-decorated with blue, turquoise (or celectian blue), honey-yellow, green, eggplant, and red color. Different types of glazes are identified and confirmed by pXRF: lead-rich, lead-poor-alkali, lead-doped alkali, and alkali-based compositions. However, an unexpected low level of lead is observed in the turquoise glazes, likely to optimize the gloss. Raman spectroscopy appears more reliable to compare the Pb content than pXRF. This work presents Raman spectral signatures of glazes that can potentially be used for non-invasive object classification and counterfeit detection.

A multisensor approach coupled with multivariate statistics and geostatistics for assessing the status of land degradation: The case of soils contaminated in a former outdoor shooting range.

Soil contamination in outdoor shooting ranges (OSRs) is a major threat for human health, particularly when, after the end of activities, the land is used for recreational areas or agricultural production. The status of land degradation of an OSR in southern Italy was assessed using a multisensor approach. It was based on: i) proximal sensors, including electromagnetic induction (EMI) for measuring soil electrical conductivity (ECa) and magnetic susceptibility (MSa), γ-ray spectrometry for K, eU and eTh analyses and ultrasonic penetrometry detecting cone index (CI) data representative of soil's strength, ii) field surveys on soil thickness (ST), and iii) laboratory analyses of potentially-toxic-elements (PTEs) by portable X-ray fluorescence spectrometry and polycyclic aromatic hydrocarbons (PAHs) by gas-chromatography. Spatial variability of measurements was modelled and mapped using geostatistical methods. The most densely measured covariate (i.e., the ECa of the topsoil) was used within kriging with external drift to improve the PTEs predictions. The PTEs maps were complemented by maps of spatial uncertainty. A robust multivariate principal component analysis (rPCA) was applied to proximal sensor and laboratory data and allowed to identify associations of PAHs, lead, CI with the topsoil ECa along the first component (PC1), highlighting the correlation between land anthropogenic effects and EMI measures; while the association between the ST (estimating the depth of underground travertine hard-layers) and the bottom soil ECa and MSa along the second component (PC2) evidenced the influence of soil stratigraphy on the EMI measures. This study demonstrates that the simultaneous use of different proximal sensors associated with laboratory analysis can allow to assess and model the spatial variability of the land degradation status of an OSR, including soil compaction, organic and inorganic contamination. The correlation between EMI data with the PTEs content highlights the potential of this technique in the field of soil contamination.

Terahertz time-domain spectro-imaging and hyperspectral imagery to investigate a historical Longwy glazed ceramic.

In this paper, we present the potential of Terahertz Time-Domain Imaging (THz-TDI) as a tool to perform non-invasive 3D analysis of an ancient enamel plate manufactured by Longwy Company in France. The THz data collected in the reflection mode were processed using noise filtering procedures and an advanced imaging approach. The results validate the capability to identify glaze layers and the thickness of ceramic materials. To characterize the nature of the pigments, we also use with X-ray images, visible near-infrared hyperspectral imaging spectroscopy, and p-XRF (portable X-ray fluorescence) to qualitatively and quantitively identify the materials used. The obtained information enables a better understanding of the decoration chromogens nature and, thus, to determine the color palette of the artists who produced such decorative object. We also establish the efficiency of a focus, Z-tracker, which enables to perform THz imaging on non-flat samples and to attenuate artifacts obtained with a short focus lens. Then, 3D images are extracted and generated, providing a real vision. We also report the evaluation of the internal damage state through the detection of fractures.