Near real-time management of spectral interferences with portable XRF spectrometers: Application to Sc quantification in nickeliferous laterite ores

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

The Interface Characterization of 2-Mercapto-1-methylimidazole Corrosion Inhibitor on Brass

This work presents a detailed surface analytical study and surface characterization, with an emphasis on the X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) analyses of 2‑mercapto‑1‑methylimidazole (MMI) as a corrosion inhibitor for brass. First, the electrochemical measurements demonstrated a corrosion inhibition effect of MMI in a 3 wt.% NaCl solution. Next, the formation of the MMI surface layer and its properties after 1 month of immersion was analyzed with attenuated total reflectance–Fourier-transform infrared spectroscopy, atomic force microscopy, field-emission scanning electron microscopy, and contact angle analysis. Moreover, to gradually remove the organic surface layer, a gas cluster ion beam (GCIB) sputtering source at different accelerated voltages and cluster sizes was employed. After each sputtering cycle, a high-resolution XPS analysis was performed. Moreover, an angle‑resolved XPS analysis was carried out for the MMI-treated brass sample to analyze the heterogeneous layered structure (the interface of the MMI organic/inorganic brass substrate). The interface properties were also investigated in detail using ToF-SIMS for spectra measurements and 2D imaging. Special attention was devoted to the possible spectral interferences for MMI‑related species. The thermal stability of different MMI-related species using molecular-specific signals without possible spectral interferences was determined by performing a cooling/heating experiment associated with ToF-SIMS measurements. It was shown that these species desorbed from the brass surface in the temperature range of 310–370 °C.

Comparing Performance of Deep Convolution Networks in Reconstructing Soliton Molecules Dynamics from Real-Time Spectral Interference

Deep neural networks have enabled the reconstruction of optical soliton molecules with more complex structures using the real-time spectral interferences obtained by photonic time-stretch dispersive Fourier transformation (TS-DFT) technology. In this paper, we propose to use three kinds of deep convolution networks (DCNs), including VGG, ResNets, and DenseNets, for revealing internal dynamics evolution of soliton molecules based on the real-time spectral interferences. When analyzing soliton molecules with equidistant composite structures, all three models are effective. The DenseNets with layers of 48 perform the best for extracting the dynamic information of complex five-soliton molecules from TS-DFT data. The mean Pearson correlation coefficient (MPCC) between the predicted results and the real results is about 0.9975. Further, the ResNets in which the MPCC achieves 0.9906 also has the better ability of phase extraction than VGG which the MPCC is about 0.9739. The general applicability is demonstrated for extracting internal information from complex soliton molecule structures with high accuracy. The presented DCNs-based techniques can be employed to explore undiscovered mechanisms underlying the distribution and evolution of large numbers of solitons in dissipative systems in experimental research.

N₂O isotopocule measurements using laser spectroscopy: analyzer characterization and intercomparison

For the past two decades, the measurement of nitrous oxide (N2O) isotopocules – isotopically substituted molecules 14N15N16O, 15N14N16O and 14N14N18O of the main isotopic species 14N14N16O – has been a promising technique for understanding N2O production and consumption pathways. The coupling of non-cryogenic and tuneable light sources with different detection schemes, such as direct absorption quantum cascade laser absorption spectroscopy (QCLAS), cavity ring-down spectroscopy (CRDS) and off-axis integrated cavity output spectroscopy (OA-ICOS), has enabled the production of commercially available and field-deployable N2O isotopic analyzers. In contrast to traditional isotope-ratio mass spectrometry (IRMS), these instruments are inherently selective for position-specific 15N substitution and provide real-time data, with minimal or no sample pretreatment, which is highly attractive for process studies. Here, we compared the performance of N2O isotope laser spectrometers with the three most common detection schemes: OA-ICOS (N2OIA-30e-EP, ABB – Los Gatos Research Inc.), CRDS (G5131-i, Picarro Inc.) and QCLAS (dual QCLAS and preconcentration, trace gas extractor (TREX)-mini QCLAS, Aerodyne Research Inc.). For each instrument, the precision, drift and repeatability of N2O mole fraction [N2O] and isotope data were tested. The analyzers were then characterized for their dependence on [N2O], gas matrix composition (O2, Ar) and spectral interferences caused by H2O, CO2, CH4 and CO to develop analyzer-specific correction functions. Subsequently, a simulated two-end-member mixing experiment was used to compare the accuracy and repeatability of corrected and calibrated isotope measurements that could be acquired using the different laser spectrometers. Our results show that N2O isotope laser spectrometer performance is governed by an interplay between instrumental precision, drift, matrix effects and spectral interferences. To retrieve compatible and accurate results, it is necessary to include appropriate reference materials following the identical treatment (IT) principle during every measurement. Remaining differences between sample and reference gas compositions have to be corrected by applying analyzer-specific correction algorithms. These matrix and trace gas correction equations vary considerably according to N2O mole fraction, complicating the procedure further. Thus, researchers should strive to minimize differences in composition between sample and reference gases. In closing, we provide a calibration workflow to guide researchers in the operation of N2O isotope laser spectrometers in order to acquire accurate N2O isotope analyses. We anticipate that this workflow will assist in applications where matrix and trace gas compositions vary considerably (e.g., laboratory incubations, N2O liberated from wastewater or groundwater), as well as extend to future analyzer models and instruments focusing on isotopic species of other molecules.