In general, the detection of F and other halogens is challenging through conventional techniques. In this paper, various approaches for the qualitative and quantitative analysis of F using the laser-induced breakdown spectroscopy (LIBS) technique were demonstrated. In LIBS, fluorine detection can be realized by means of atomic lines and molecular bands. For the purposes of our experiment, two sets of pellets with various contents of CaF2, CaCO3 and cellulose were analyzed using a lab-based LIBS system under a He atmosphere. The fluorine atomic line at 685.60 nm was correlated with CaF signals proving their close relationship. Consequently, the limits of detection were determined for both analytical signals. Moreover, conditions necessary for the quantification of F via CaF band signals were estimated. The dependence of the CaF signal on the varying ratio of Ca and F contents was investigated. Finally, a chip of a real CaF2 crystal was prepared and its surface was mapped with Raman and LIBS systems. The obtained elemental and molecular maps showed good numerical correlations. Thus, the yielded results validated the possibility to substitute the fluorine atomic line by non-conventional CaF molecular bands in the qualitative and quantitative LIBS analysis of fluorine.

Laser-Induced Breakdown Spectroscopy; Uranium ore; Elements distribution; Self-organizing maps;

This paper presents a novel approach for processing the spectral information obtained from high-resolution elemental mapping performed by means of Laser-Induced Breakdown Spectroscopy. The proposed methodology is aimed at the description of possible elemental associations within a heterogeneous sample. High-resolution elemental mapping provides a large number of measurements. Moreover, typical laser-induced plasma spectrum consists of several thousands of spectral variables. Analysis of heterogeneous samples, where valuable information is hidden in a limited fraction of sample mass, requires special treatment. The sample under study is a sandstone-hosted uranium ore that shows irregular distribution of ore elements such as zirconium, titanium, uranium and niobium. Presented processing methodology shows the way to reduce the dimensionality of data and retain the spectral information by utilizing self-organizing maps (SOM). The spectral information from SOM is processed further to detect either simultaneous or isolated presence of elements. Conclusions suggested by SOM are in good agreement with geological studies of mineralization phases performed at the deposit. Even deeper investigation of the SOM results enables discrimination of interesting measurements and reveals new possibilities in the visualization of chemical mapping information. Suggested approach improves the description of elemental associations in mineral phases, which is crucial for the mining industry.

Laser-Induced Breakdown Spectroscopy; Uranium; principal component analysis; Chemical mapping; Sandstone-hosted deposit; X-ray Fluorescence;

The goal of this work is to provide high resolution mapping of uranium in sandstone-hosted uranium ores using Laser-Induced Breakdown Spectroscopy (LIBS) technique. In order to obtain chemical image with highest possible spatial resolution, LIBS system in orthogonal double pulse (DP LIBS) arrangement was employed. Owing to this experimental arrangement the spot size of 50 μm in diameter resulting in lateral resolution of 100 μm was reached. Despite the increase in signal intensity in DP LIBS modification, the detection of uranium is challenging. The main cause is the high density of uranium spectral lines, which together with broadening of LIBS spectral lines overreaches the resolution of commonly used spectrometers. It results in increased overall background radiation with only few distinguishable uranium lines. Three different approaches in the LIBS data treatment for the uranium detection were utilized: i) spectral line intensity, ii) region of apparent background and iii) multivariate data analysis. By utilizing multivariate statistical methods, a specific specimen features (in our case uranium content) were revealed by processing complete spectral information obtained from broadband echelle spectrograph. Our results are in a good agreement with conventional approaches such as line fitting and show new possibilities of processing spectral data in mapping. As a reference technique to LIBS was employed X-ray Fluorescence (XRF). The XRF chemical images used in this paper have lower resolution (approximately 1–2 mm per image point), nevertheless the elemental distribution is apparent and corresponds to presented LIBS experiments.

Electrochemical Detection; Double-pulse LIBS; Laser-induced breakdown spectroscopy; Fluorescence Microscopy; Elemental Distribution; Mass Spectrometry;

Laser-Induced Breakdown Spectroscopy (LIBS) in double pulse configuration (DP LIBS) was used for scanning elemental spatial distribution in annual terminal stems of spruce (Picea abies (L.) Karsten). Cross sections of stems cultivated in Cu2+ solution of different concentrations were prepared and analyzed by DP LIBS. Raster scanning with 150 µm spatial resolution was set and 2D (2-dimentional) maps of Cu and Ca distribution were created on the basis of the data obtained. Stem parts originating in the vicinity of the implementation of the cross sections were mineralized and subsequently Cu and Ca contents were analyzed by inductively coupled plasma mass spectrometry (ICP-MS). The results provide quantitative information about overall concentration of the elements in places, where LIBS measurements were performed. The fluorescence pictures were created to compare LIBS distribution maps and the fluorescence intensity (or the increase in autofluorescence) was used for the comparison of ICP-MS quantitative results. Results from these three methods can be utilized for quantitative measurements of copper ions transport in different plant compartments in dependence on the concentration of cultivation medium and/or the time of cultivation.

Laser-induced breakdown spectroscopy; LIBS; LA-ICP-MS; elemental mapping;

Laser induced breakdown spectroscopy (LIBS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) have been applied for high-resolution mapping of accumulation and distribution of heavy metal (lead) and nutrition elements (potassium, manganese) in leaves of Capsicum annuum L. samples. Lead was added in a form of Pb(NO3)2 at concentration up to 10 mmol L−1 into the vessels that contained tap water and where the 2-months old Capsicum annuum L. plants were grown another seven days. Two dimensional maps of the elements are presented for both laser-assisted Analytical Methods. Elemental mapping performed on fresh (frozen) and dried Capsicum annuum L. leaves are compared.

Laser Induced Breakdown Spectroscopy (LIBS); Picea abie; heavy metals;

This work is focused on application of LIBS technique for the study of plant samples. The elemental mapping on cross section throughout the annual terminal twigs of Picea abies was performed using double pulse Laser Induced Breakdown Spectroscopy (DP LIBS). 2D maps were created, where distribution of Cu and Ca in the plant tissue was observed. After mineralization of twig parts originated in the vicinity of the implementation of cross section, ICP-MS analysis was used for determination of total content of investigated elements.

Bio-mineral structures, i.e., bones, teeth or kidney stones have been found to be excellent ""archives"" related to nutrition, living habits and exposure to changing environmental conditions. More specifically, formation of urolithic concrements (uroliths) represents specific biomineralization of living organism. Line scans of the concrement cross sections may provide information about the accumulation history of the elements of interest. Analytical Methods which can map the presence of different elements are e.g. Laser Induced Breakdown Spectroscopy (LIBS) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). Both of these methods have proven to be suitable for mapping the matrix elements, so further work is concerned with their use for the mapping of trace elements.