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.

Multivariate data analysis (MVDA) is getting popular across the spectroscopic community. To assess accurate results, the obtained data should be preprocessed prior to utilization of any MVDA algorithm. The process of data normalization or “internal standardization” is widely used across a broad range of applications. In this manuscript we investigate the utilization of Laser-Induced Breakdown Spectroscopy (LIBS) coupled with MVDA. However, many articles regarding the use of MVDA on data from LIBS do not provide any information about the data pretreatment. This work describes the impact of LIBS data normalization approaches on MVDA classification accuracy. Also, the impact of classical data preprocessing (mean centering and scaling) exploiting the prior utilization of MVDA was studied. This issue was investigated exploiting simple soft independent modelling of class analogies algorithm. The findings were generalized for three sample matrices (steel, Al alloys, and sedimentary ores). Furthermore, the selection of an appropriate normalization algorithm is not trivial since the spectrum of each sample matrix is composed of a different number of elements and corresponding elemental lines.

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; Raman spectroscopy; Chemometrics; Bacteria;

In this work, we investigate the impact of data provided by complementary laser-based spectroscopic methods on multivariate classification accuracy. Discrimination and classification of five Staphylococcus bacterial strains and one strain of Escherichia coli is presented. The technique that we used for measurements is a combination of Raman spectroscopy and Laser-Induced Breakdown Spectroscopy (LIBS). Obtained spectroscopic data were then processed using Multivariate Data Analysis algorithms. Principal Components Analysis (PCA) was selected as the most suitable technique for visualization of bacterial strains data. To classify the bacterial strains, we used Neural Networks, namely a supervised version of Kohonen's self-organizing maps (SOM). We were processing results in three different ways - separately from LIBS measurements, from Raman measurements, and we also merged data from both mentioned methods. The three types of results were then compared. By applying the PCA to Raman spectroscopy data, we observed that two bacterial strains were fully distinguished from the rest of the data set. In the case of LIBS data, three bacterial strains were fully discriminated. Using a combination of data from both methods, we achieved the complete discrimination of all bacterial strains. All the data were classified with a high success rate using SOM algorithm. The most accurate classification was obtained using a combination of data from both techniques. The classification accuracy varied, depending on specific samples and techniques. As for LIBS, the classification accuracy ranged from 45% to 100%, as for Raman Spectroscopy from 50% to 100% and in case of merged data, all samples were classified correctly. Based on the results of the experiments presented in this work, we can assume that the combination of Raman spectroscopy and LIBS significantly enhances discrimination and classification accuracy of bacterial species and strains. The reason is the complementarity in obtained chemical information while using these two methods.

Quantum dots; Laser-induced breakdown spectroscopy; Chemical mapping; Filtration paper; Fluorescence microscopy;

In this study, the feasibility of Quantum dots (QDs) 2D distribution mapping on the substrate by Laser-Induced Breakdown Spectroscopy (LIBS) was examined. The major objective of this study was to describe phenomena occurring after applying aqueous solutions of QDs onto filtration paper. Especially, the influence of pH and presence of Cu2 + cations in QDs solutions on LIBS signal was investigated. Cadmium Telluride QDs (CdTe QDs) were prepared by formation of nanosized semiconductor particles in so called “one-pot” synthesis. CdTe QDs were capped by glutathione or by 3-mercaptopropionic acid. The technique described in this work allows detection of QDs injected on the selected substrate – filtration paper. Results obtained from LIBS experiments were collated with a comparative method, fluorescence microscopy, which showed variations in the distribution of QDs on the substrate surface and possibilities for quenching. Due to the immediate signal response, relatively simple instrumentation and automatization possibility, LIBS offers promising and fast alternative to other techniques, as it is able to detect also nanoparticles with no visible luminescence.

Laser-Induced Breakdown Spectroscopy; Silver nanoparticles; Low pressure conditions; Sensitivity improvement;

In this work we studied the effect of vacuum (low pressure) conditions on the behavior of laser-induced plasma (LIP) created on a sample surface covered with silver nanoparticles (Ag-NPs), i.e. Nanoparticles-Enhanced Laser-Induced Breakdown Spectroscopy (NELIBS) experiment in a vacuum. The focus was put on the step by step optimization of the measurement parameters, such as energy of the laser pulse, temporally resolved detection, ambient pressure, and different content of Ag-NPs applied on the sample surface. The measurement parameters were optimized in order to achieve the greatest enhancement represented as the signal-to-noise ratio (SNR) of NELIBS signal to the SNR of LIBS signal. The presence of NPs involved in the ablation process enhances LIP intensity; hence the improvement in the analytical sensitivity was yielded. A leaded brass standard was analyzed with the emphasis on the signal enhancement of Pb traces. We gained enhancement by a factor of four. Although the low pressure had no significant influence on the LIP signal enhancement compared to that under ambient conditions, the SNR values were noticeably improved with the implementation of the NPs.

Laser-Induced Breakdown Spectroscopy; ;

In this work, we proposed a new data acquisition approach that significantly improves the repetition rates of Laser-Induced Breakdown Spectroscopy (LIBS) experiments, where high-end echelle spectrometers and intensified detectors are commonly used. The moderate repetition rates of recent LIBS systems are caused by the utilization of intensified detectors and their slow full frame (i.e. echellogram) readout speeds with consequent necessity for echellogram-to-1D spectrum conversion (intensity vs. wavelength). Therefore, we investigated a new methodology where only the most effective pixels of the echellogram were selected and directly used in the LIBS experiments. Such data processing resulted in significant variable down-selection (more than four orders of magnitude). Samples of 50 sedimentary ores samples (distributed in 13 ore types) were analyzed by LIBS system and then classified by linear and non-linear Multivariate Data Analysis algorithms. The utilization of selected pixels from an echellogram yielded increased classification accuracy compared to the utilization of common 1D spectra.

Laser-induced breakdown spectroscopy; Silver nanoparticles; Distribution; Root tissues;ARABIDOPSIS-THALIANA; PLANT-SAMPLES; ACCUMULATION; CADMIUM; MATRIX; SIZE

The manuscript presents a procedure for optimal sample preparation and the mapping of the spatial distribution of metal ions and nanoparticles in plant roots using laser-induced breakdown spectroscopy (LIBS) in a double-pulse configuration (DP LIBS) in orthogonal reheating mode. Two Nd:YAG lasers were used; the first one was an ablation laser (UP-266 MACRO, New Wave, USA) with a wavelength of 266 nm, and the second one (Brilliant, Quantel, France), with a fundamental wavelength of 1064 nm, was used to reheat the microplasma. Seedlings of Vicia faba were cultivated for 7 days in CuSO4 or AgNO3 solutions with a concentration of 10 mu mol 1(-1) or in a solution of silver nanoparticles (AgNPs) with a concentration of 10 mu mol 1(-1) of total Ag, and in distilled water as a control. The total contents of the examined metals in the roots after sample mineralization as well as changes.in the concentrations of the metals in the cultivation solutions were monitored by ICP-OES. Root samples embedded in the TissueTek medium and cut into 40 gm thick cross sections using the Cryo-Cut Microtome proved to be best suited for an accurate LIBS analysis with a 50 gm spatial resolution. 2D raster maps of elemental distribution were created for the emission lines of Cu(I) at 324.754 nm and Ag(I) at 328.068 nm. The limits of detection of DP LIES for the root cross sections were estimated to be 4 pg for Cu, 18 pg for Ag, and 3 pg for AgNPs. The results of Ag spatial distribution mapping indicated that unlike Ag+ ions, AgNPs do not penetrate into the inner tissues of Vicia faba roots but stay in their outermost layers. The content of Ag in roots cultivated in the AgNP solution was one order of magnitude lower compared to roots cultivated in the metal ion solutions. The significantly smaller concentration of Ag in root tissues cultivated in the AgNP solution also supports the conclusion that the absorption and uptake of AgNPs by roots of Vicia faba is very slow. LIBS mapping of root sections represents a fast analytical method with sufficient precision and spatial resolution that can provide very important information for researchers, particularly in the fields of plant science and ecotoxicology.

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.

Laser-Induced Breakdown Spectroscopy; Multivariate classification; Echelle spectrometer; Czerny-Turner spectrometer;

The objective of this work was to assess a part of echelle Laser-Induced Plasma spectra (ranging from 200 to 1000 nm) that could be most effectively employed for rocks classification. Therefore, a 60 nm wide spectral window mask was iteratively moved over the broadband echelle spectra. Each created narrow artificial spectral windows (60 nm) was used for the classification of rock samples using various Multivariate Data Analysis (MVDA) algorithms, reaching more than 99% of the overall accuracy in certain cases. Afterwards, the Czerny-Turner spectrometer (having higher sensitivity compared to the echelle spectrometer) was aligned to the a priori selected and the most effective spectral regions and rocks samples were re-measured. Consequently the MVDA analyses were utilized again, providing also satisfying classification results yielding more than 99% of the overall accuracy. Measurements of 28 sedimentary ores (certified reference materials) were done utilizing commercially available X-Trace device (AtomTrace), where spectrometers in both configurations (echelle and Czerny-Turner) were exploited.

Laser-induced breakdown spectroscopy; Generalized extreme value distribution; shot-to-shot statistics ;

The purpose of this work is to provide detailed study of statistical behavior of different types of analytical signals in typical of Laser-Induced Breakdown Spectroscopy (LIBS) measurements. The main goal of this work is to justify usage of arithmetic mean and standard deviation as statistical estimates of expected value of selected analytical signal. In contrary to the general assumption that LIBS data show Gaussian distribution, this paper deals with the hypothesis that the data rather demonstrate Generalized Extreme Value Distribution. The study is realized on 10 selected lines measured on NIST glass standard. In order to cover wide range of possible applications three different spectra internal standardization techniques and their influence on distribution were studied. Finally, assuming that the data comes from a single distribution and the central limit theorem is valid, the influence of accumulations on the line distribution is examined and discussed. Statistical tools used and described in this paper can be utilized by other researchers to confirm their hypotheses and verify utilization of Gaussian distribution or even novel data processing methods.

Laser-Induced Breakdown Spectroscopy, LIBS; Outlier filtering; Principal Component Analysis, PCA; Linear correlation; Total spectral intensity; Soft Independent Modelling of Class Analogies, SIMCA;

In this manuscript we highlight the necessity of outlier filtering prior the multivariate classification in Laser-Induced Breakdown Spectroscopy (LIBS) analyses. For the purpose of classification we chose to analyse BAM steel standards that possess similar composition of major and trace elements. To assess the improvement in figures of merit we compared the performance of three outlier filtering approaches (based on Principal Component Analysis, linear correlation and total spectral intensity) already separately discussed in the LIBS literature. The truncated data set was classified using Soft Independent Modelling of Class Analogies (SIMCA). Yielded results showed significant improvement in the performance of multivariate classification coupled to filtered data. The best performance was observed for the total spectral intensity filtering approach gaining the analytical figures of merit (overall accuracy, sensitivity, and specificity) over 98%. It is noteworthy that the results showed relatively low sensitivity and high specificity of the SIMCA algorithm regardless of the presence of outliers in the data sets. Moreover, it was shown that the variance in the data topology of training and testing data sets has a great impact on the consequent data classification.

Laser-induced breakdown spectroscopy; Fluid jets; Laser ablation; Copper; Plasma jets;

A complex optimization of geometrical and temporal parameters of a jet system (developed in Laser-induced breakdown spectroscopy (LIBS) laboratory of Brno University of Technology) for direct elemental analysis of samples in a liquid state of matter using LIBS was carried out. First, the peristaltic pump was synchronized with the flashlamp of the ablation laser, which reduced variation of the ablated sample amount. Also, the fluctuation of the laser ray angle incident on the jet surface was diminished. Such synchronization reduced signal standard deviations and thus increased repeatability of the measurements. Then, laser energy and distance of the focusing lens from the sample were optimized. The gate delay time and the gate width were optimized for single pulse (SP) experiments; the gate delay time and the inter-pulse delay were optimized for the use of double pulse (DP) variant. Results were assessed according to the highest signal to noise ratios and the lowest relative standard deviations of the signal. The sensitivity of the single pulse and the double pulse LIBS for the detection of heavy metals traces, copper (Cu i at 324.754 nm) and lead (Pb i at 405.781 nm), in aqueous solution of copper (ii) sulfate and lead (ii) acetate, was estimated in terms of limits of detection (LODs). As a result, sensitivity improvement of DP LIBS system was observed, the LOD of Cuobtained with DP was calculated 40% lower than LOD gained from SP technique.

Braking tracks; Forensic; LIBS; Tire treads; Laser-Induced Breakdown Spectroscopy;

Identification of the position, length and mainly beginning of a braking track has proven to be essential for determination of causes of a road traffic accident. With the introduction of modern safety braking systems and assistance systems such as the Anti-lock Braking System (ABS) or Electronic Stability Control (ESC), the visual identification of braking tracks that has been used up until the present is proving to be rather complicated or even impossible. This paper focuses on identification of braking tracks using a spectrochemical analysis of the road surface. Laser-Induced Breakdown Spectroscopy (LIBS) was selected as a method suitable for fast in-situ element detection. In the course of detailed observations of braking tracks it was determined that they consist of small particles of tire treads that are caught in intrusions in the road surface. As regards detection of the “dust” resulting from wear and tear of tire treads in the environment, organic zinc was selected as the identification element in the past. The content of zinc in tire treads has been seen to differ with regard to various sources and tire types; however, the arithmetic mean and modus of these values are approximately 1% by weight. For in-situ measurements of actual braking tracks a mobile LIBS device equipped with a special module was used. Several measurements were performed for 3 different cars and tire types respectively which slowed down with full braking power. Moreover, the influence of different initial speed, vehicle mass and braking track length on detected signal is discussed here.

We present a report on the potential use of the Laser-Induced Breakdown Spectroscopy (LIBS) technique for direct investigation of Mg corrosion and related optimization of the table-top LIBS system. Moreover, the preliminary study to prove the capability of this LIBS technique for the estimation of corrosion grade is given. In order to simulate the real corrosive environment, Mg samples were prepared in a constant climate chamber. We show that the corrosive layer on the sample surface significantly affects the properties of laser–matter interactions, i.e. among other parameters causing the matrix effect. Consequently, the properties and persistence of laser-induced plasmas (LIPs) and their composition, generated on such degraded surfaces, essentially differ. Collected radiation of LIP is then analysed and ratios of ionic to atomic Mg spectral lines are correlated with the grade of magnesium corrosion, i.e. content of Mg(OH)2 on the sample surface. The content of Mg(OH)2 is also correlated with plasma temperature as well as with the electron number density of LIP. Additionally, X-ray diffraction (XRD) analysis and optical profilometry were utilized to obtain more comprehensive information about the degradation grade of high purity Mg samples.

LIBS; Laser-induced breakdown spectroscopy; Tire tread; Optimization ;

The objective of this paper is a study of the potential of laser induced breakdown spectroscopy (LIBS) for detection of tire tread particles. Tire tread particles may represent pollutants; simultaneously, it is potentially possible to exploit detection of tire tread particles for identification of optically imperceptible braking tracks at locations of road accidents. The paper describes the general composition of tire treads and selection of an element suitable for detection using the LIBS method. Subsequently, the applicable spectral line is selected considering interferences with lines of elements that might be present together with the detected particles, and optimization of measurement parameters such as incident laser energy, gate delay and gate width is performed. In order to eliminate the matrix effect, measurements were performed using 4 types of tires manufactured by 3 different producers. An adhesive tape was used as a sample carrier. The most suitable adhesive tape was selected from 5 commonly available tapes, on the basis of their respective LIBS spectra. Calibration standards, i.e. an adhesive tape with different area content of tire tread particles, were prepared for the selected tire. A calibration line was created on the basis of the aforementioned calibration standards. The linear section of this line was used for determination of the detection limit value applicable to the selected tire. Considering the insignificant influence of matrix of various types of tires, it is possible to make a simple recalculation of the detection limit value on the basis of zinc content in a specific tire.

Stand-off LIBS; Laser-induced breakdown spectroscopy; Classification; PCA; LDA; Cultural heritage;

Focusing on historical aspect, during archeological excavation or restoration works of buildings or different structures built from Brick it is important to determine, preferably in-situ and in real-time, the locality of Brick origin. Fast classification of Brick on the base of Laser-Induced Breakdown Spectroscopy (LIBS) spectra is possible using multivariate statistical methods. Combination of principal component analysis (PCA) and linear discriminant analysis (LDA) was applied in this case. LIBS was used to classify altogether the 29 brick samples from 7 different localities. Realizing comparative study using two different LIBS setups — stand-off and table-top it is shown that stand-off LIBS has a big potential for archeological in-field measurements.

Laser-induced breakdown spectroscopy; Cadmium; Quantum dot; Metallothionein; Immunoassay;

The technique described in this paper allows detection of quantum dots (QDs) specifically deposited on the polystyrene surface by laser-induced breakdown spectroscopy (LIBS). Using LIBS, the distribution of QDs or their conjugates with biomolecules deposited on the surface can be observed, regardless of the fact if they exhibit fluorescence or not. QDs deposited on the specific surface of polystyrene microplate in the form of spots are detected by determination of the metal included in the QDs structure. Cd-containing QDs (CdS, CdTe) stabilized with mercaptopropionic (MPA) or mercaptosuccinic (MSA) acid, respectively, alone or in the form of conjugates with metallothionein (MT) biomolecule are determined by using the 508.58 nm Cd emission line. The observed absolute detection limit for Cd in CdTe QDs conjugates with MT in one spot was 3 ng Cd. Due to the high sensitivity of this technique, the immunoanalysis in combination with LIBS was also investigated. Cd spatial distribution in sandwich immunoassay was detected.

Laser-Induced Breakdown Spectroscopy; LIBS; Laser-Ablation Inductively Coupled Plasma coupled with Mass Spectroscopy and Optical Emission Spectroscopy; LA-ICP-MS; LA-ICP-OES; ICP-OES; Raman spectroscopy; algae; algal biomass; biofuel; bioremediation;

Algal biomass that is represented mainly by commercially grown algal strains has recently found many potential applications in various fields of interest. Its utilization has been found advantageous in the fields of bioremediation, biofuel production and the food industry. This paper reviews recent developments in the analysis of algal biomass with the main focus on the Laser-Induced Breakdown Spectroscopy, Raman spectroscopy, and partly Laser-Ablation Inductively Coupled Plasma techniques. The advantages of the selected laser-based analytical techniques are revealed and their fields of use are discussed in detail.

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; Mapping; Trace elements; Phytoremediation; Cancer; Plant; Bacteria; Animal tissues;

Laser-Induced Breakdown Spectroscopy (LIBS) is a sensitive optical technique capable of fast multi-elemental analysis of solid, gaseous and liquid samples. Since the late 1980s LIBS became visible in the analytical atomic spectroscopy scene; its applications having been developed continuously since then. In this paper, the use of LIBS for trace element determination in different matrices is reviewed. The main emphasis is on spatially resolved analysis of microbiological, plant and animal samples.

Stand‐off LIBS; Laser-induced breakdown spectroscopy; PCA; LDA; ANN; Biomineral; Geomaterial; Archaeology;

The goal of this paper is to compare two selected statistical techniques used for identification of archeological materials merely on the base of their spectra obtained by stand-off laser-induced breakdown spectroscopy (stand-off LIBS). Data processing using linear discriminant analysis (LDA) and artificial neural networks (ANN) were applied on spectra of 18 different samples, some of them archeological and some recent, containing 7 types of material (i.e. shells, mortar, Brick, soil pellets, ceramic, teeth and bones). As the input data PCA scores were taken. The intended aim of this work is to create a database for simple and fast identification of archeological or paleontological materials in situ. This approach can speed up and simplify the sampling process during archeological excavations that nowadays tend to be quite damaging and time-consuming.

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.

Single pulse (SP) LIBS setup was modified to DP setup to achieve more accurate analytical sensitivity and spatial resolution. All parameters, like interpulse delay, acquisition delay or energy of ablation and excitation laser pulses were optimized.

laser induced breakdown spectroscopy; heavy meta;, spatial distribution; phytoremediation; soil; plant;

In numerous biological experiments, there is no information about the spatial distribution of elements, especially metals, which could further serve for understanding the biochemical mechanism of their distribution and transportation. Laser induced breakdown spectroscopy (LIBS) is a useful technique for determining the spatial distribution of metals in various types of samples. Given the potential of this technique to analyze solid, liquid and gaseous samples (including aerosols), which may or may not be conductive, LIBS is used for both qualitative and quantitative purposes in many areas. In some applications, the unique properties of this technique, as the ability of micro-analysis, the possibility of analyzing a sample at a distance and in situ and quasi-non-destructive nature of analysis, are used. In this study, the basic principle of technology and its application for analysis of soils and plant tissues are discussed.

Laser-induced breakdown spectroscopy (LIBS) and laser ablation (LA) inductively coupled plasma (ICP) mass spectrometry (MS) were utilized for microspatial analyses of a prehistoric bear (Ursus arctos) tooth dentine. The distribution of selected trace elements (Sr, Ba, Fe) was measured on a 26 mm×15 mm26 mm×15 mm large and 3 mm3 mm thick transverse cross section of a canine tooth. The Na and Mg content together with the distribution of matrix elements (Ca, P) was also monitored within this area. The depth of the LIBS craters was measured with an optical profilometer. As shown, both LIBS and LA-ICP-MS can be successfully used for the fast, spatially resolved analysis of prehistoric teeth samples. In addition to micro chemical analysis, the sample hardness was calculated using LIBS plasma ionic-to-atomic line intensity ratios of Mg (or Ca). To validate the sample hardness calculations, the hardness was also measured with a Vickers microhardness tester.

The development of a remote laser-induced breakdown spectroscopy (LIBS) setup with an off-axis Newtonian collection optics, Galilean-based focusing telescope, and a 532 nm532 nm flattop laser beam source is presented. The device was tested at a 6 m6 m distance on a slice of bone to simulate its possible use in the field, e.g., during archaeological excavations. It is shown that this setup is sufficiently sensitive to both major (P, Mg) and minor elements (Na, Zn, Sr). The measured quantities of Mg, Zn, and Sr correspond to the values obtained by reference laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) measurements within an approximately 20% range of uncertainty. A single point calibration was performed by use of a bone meal standard . The radial element distribution is almost invariable by use of LA-ICP-MS, whereas the LIBS measurement showed a strong dependence on the sample porosity. Based on these results, this remote LIBS setup with a relatively large (350 mm350 mm) collecting mirror is capable of semiquantitative analysis at the level of units of mg kg-1.

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.

Laser-ablation based spectrochemical Analytical Methods could be used in applications in which the capability for spatially resolved analysis is required. Such analysis gives a 2-D or 3-D map of the monitored chemical elements. Here we introduce automation of a 2-D surface analysis in the laser-induced breakdown spectroscopy setup by implementation of an autofocus algorithm based on the evaluation of the image sharpness. The most suitable algorithm with respect to its speed, accuracy, and durability against digital noise is chosen by testing different gradient-based methods and methods working in the frequency domain.

phytoremediation; heavy metals; sunflower; lead ions; high performance liquid chromatography with electrochemical detection; spectrometry; laser induced breakdown spectroscopy;

In this study, the influence of lead (II) ions on sunflower growth and biochemistry was investigated from various points of view. Sunflower plants were treated with 0, 10, 50, 100 and/or 500 µM Pb-EDTA for eight days. We observed alterations in growth in all experimental groups compared with non-treated control plants. Further we determined total content of proteins by a Bradford protein assay. By the eighth day of the experiment, total protein contents in all treated plants were much lower compared to control. Particularly noticeable was the loss of approx. 8 µg/mL or 15 µg/mL in shoots or roots of plants treated with 100 mM Pb-EDTA. We also focused our attention on the activity of alanine transaminase (ALT), aspartate transaminase (AST) and urease. Activity of the enzymes increased with increasing length of the treatment and applied concentration of lead (II) ions. This increase corresponds well with a higher metabolic activity of treated plants. Contents of cysteine, reduced glutathione (GSH), oxidized glutathione (GSSG) and phytochelatin 2 (PC2) were determined by high performance liquid chromatography with electrochemical detection. Cysteine content declined in roots of plants with the increasing time of treatment of plants with Pb-EDTA and the concentration of toxic substance. Moreover, we observed ten times higher content of cysteine in roots in comparison with shoots. The observed reduction of cysteine content probably relates with its utilization for biosynthesis of GSH and phytochelatins, because the content of GSH and PC2 was similar in roots and shoots and increased with increased treatment time and concentration of Pb-EDTA. Moreover, we observed oxidative stress caused by Pb-EDTA in roots where the GSSG/GSH ratio was about 0.66. In shoots, the oxidative stress was less distinctive, with a GSSG/GSH ratio 0.14. We also estimated the rate of phytochelatin biosynthesis from the slope of linear equations plotted with data measured in the particular experimental group. The highest rate was detected in roots treated with 100 µM of Pb-EDTA. To determine heavy metal ions many analytical instruments can be used, however, most of them are only able to quantify total content of the metals. This problem can be overcome using laser induced breakdown spectroscopy, because it is able to provide a high spatial-distribution of metal ions in different types of materials, including plant tissues. Data obtained were used to assemble 3D maps of Pb and Mg distribution. Distribution of these elements is concentrated around main vascular bundle of leaf, which means around midrib.

Metallomics and metalloproteomics are emerging fields addressing the role, uptake, transport and storage of trace metals essential for life. There are several main approaches that are being developed in metallomics and metalloproteomics including both detection of levels and spatial distribution of heavy metals and determination of heavy-metal-contained proteins. The aim of this work is detection of copper and zinc in healthy and tumour tissues of miniature pigs by using of the laser induced breakdown spectroscopy (LIBS). Concentration of heavy metal transporting protein metallothionein (MT) was determined by Brdicka reaction. Tissue cryosections were obtained from the MeLiM strain of miniature pigs with hereditary melanoma, particularly from healthy skin, cutaneous nodular melanomas and metastases in the liver, spleen and lymph nodes. Using LIBS we measured maps of spatial distribution of the essential heavy metals in cryosections and found that the maps of healthy and tumour cryosection markedly differed. The highest content of MT was determined in the tumours localised on the back of animals and was nearly 500 ug of MT per gram of tissue.

laser induced breakdown spectroscopy; LIBS; Acoustic signal; Normalization; Internal standard; Ceramic tile; Depth profiling;

An acoustic signal was used for the internal standardization of laser-induced breakdown spectroscopy (LIBS) of a glazed wall tile. For the LIBS analyses, 1064 nm and 532 nm wavelengths of the Nd:YAG laser were utilized. The tile was depth profiled by a single-spot ablation from the glaze into the substrate. Some lines of major elements Si(I) 252.418, Si(I) 252.851, Al(I) 257.509, Cr(I) 295.368, Al(I) 309.271 nm and Ti(II) 334.904 nm were monitored. The decrease in the optical emissions during the ablation was successfully compensated for by normalization to the square power of the acoustic signal in the interval of 290–340 nm. This approach failed for the lines between 250–270 nm. The results were the same for both lasing wavelengths despite different irradiances. The acquired profiles are in good agreement with the reference X-ray fluorescence measurement.

Silver; Heavy metals; Plant biosensor; Sensors; Biochemical marker;

The aim of this work is to investigate sunflower plants response on stress induced by silver(I) ions. The sunflower plants were exposed to silver(I) ions (0, 0.1, 0.5, and 1 mM) for 96 h. Primarily we aimed our attention to observation of basic physiological parameters. We found that the treated plants embodied growth depression, coloured changes and lack root hairs. Using of autofluorescence of anatomical structures, such as lignified cell walls, it was possible to determine the changes of important shoot and root structures, mainly vascular bungles and development of secondary thickening. The differences in vascular bundles organisation, parenchymatic pith development in the root centre and the reduction of phloem part of vascular bundles were well observable. Moreover with increasing silver(I) ions concentration the vitality of rhizodermal cells declined; rhizodermal cells early necrosed and were replaced by the cells of exodermis. Further we employed laser induced breakdown spectroscopy for determination of spatial distribution of silver(I) ions in tissues of the treated plants. The Ag is accumulated mainly in near-root part of the sample. Moreover basic biochemical indicators of environmental stress were investigated. The total content of proteins expressively decreased with increasing silver(I) ions dose and the time of the treatment. As we compare the results obtained by protein analysis-the total protein contents in shoot as well as root parts-we can assume on the transport of the proteins from the roots to shoots. This phenomenon can be related with the cascade of processes connecting with photosynthesis. The second biochemical parameter, which we investigated, was urease activity. If we compared the activity in treated plants with control, we found out that presence of silver(I) ions markedly enhanced the activity of urease at all applied doses of this toxic metal. Finally we studied the effect of silver(I) ions on activity of urease in in vitro conditions.

Laser induced Breakdown Spectroscopy (LIBS) offers a new unique tool to detect heavy metal ions in biological samples without any sample preparation. The technique was utilized for determination of lead in leaves of sugar beet plants treated with lead chelate.