This study first reveals the matrix effect mechanism of filter fixation on laser-induced breakdown spectroscopy (LIBS) quantitative analysis of algae, providing a methodological reference for in situ environmental detection.

Lead nanoparticles (PbNPs) in air pollution pose a significant threat to human health, especially due to their neurotoxic effects. In this study, we exposed mice to lead(II) oxide nanoparticles (PbONPs) in inhalation chambers to mimic real-life exposure and assess their impact on the brain. PbONPs caused the formation of Hirano bodies and pathological changes related to neurodegenerative disorders through cytoskeletal disruptions without the induction of inflammation. Damage to astrocytic endfeet and capillary endothelial cells indicated a compromised blood-brain barrier (BBB), allowing PbONPs to enter the brain. Additionally, NPs were detected along the olfactory pathway, including fila olfactoria, suggesting that at least a proportion of PbNPs enter the brain directly by passing through the olfactory epithelium. PbNP inhalation severely damaged the apical parts of olfactory epithelial cells, including the loss of microtubules in their ciliary distal segments. Inhalation of PbONPs led to the rapid accumulation of lead in the brain, while more soluble lead(II) nitrate NPs did not accumulate significantly until 11 weeks of exposure. PbNPs induced disruption of the BBB at multiple levels, ranging from ultrastructural changes to functional impairments of the barrier; however, they did not induce systemic inflammation in the brain. The clearance ability of the brain to remove Pb was very low for both types of NPs, with significant pathological effects persisting even after a long clearance period. Cation-binding proteins (ZBTB20 and calbindin1) were distributed unevenly in the brain, with the strongest signal located in the hippocampus, which exhibited the greatest defects in nuclear architecture, indicating that this area is the most sensitive structure for PbNP exposure. PbNP exposure also altered the PI3K/Akt/mTOR signaling pathway, and tau phosphorylation in the hippocampus and inhibition of tau phosphorylation by GSK-3 inhibitor rescued the negative effect of PbONPs on the intracellular calcium level in trigeminal ganglion cultures. In zebrafish larvae, PbONPs affected locomotor activity and reduced calcium levels in the medium enhanced negative effect of PbONP on animal mobility, even increasing lethality. These findings suggest that cytoskeletal disruption and calcium dysregulation are key factors in PbNP-induced neurotoxicity, providing potential targets for therapeutic intervention to prevent neurodegenerative changes following PbNP exposure.

Inhaled cadmium oxide nanoparticles (CdONPs) represent an underrecognized environmental and occupational hazard because of their potential for systemic bioaccumulation and organ-specific toxicity. In this study, mice were exposed to subchronic inhalation of CdONPs, and cadmium distribution, clearance, and tissue responses were assessed over a 21-day recovery period using atomic absorption spectrometry, laser ablation inductively coupled plasma mass spectrometry, histopathology, and gene expression analysis. Cadmium accumulated predominantly in the lungs, where clearance was slow and accompanied by persistent inflammation and foam cell formation. The intestines exhibited efficient cadmium reduction, likely due to high epithelial turnover, while the liver showed minimal accumulation and no overt damage. By contrast, the kidneys retained cadmium primarily in the cortex, with partial clearance and ultrastructural changes, including mitochondrial disorganization and lipid accumulation. Bone tissues demonstrated differential retention: jaw bones effectively cleared cadmium, whereas femurs showed sustained or increased levels, suggesting redistribution from other organs. Gene expression analysis revealed moderate but consistent upregulation of Abca1, Apoe, and Ptch1 in the kidneys of clearance groups, indicating adaptations in lipid metabolism and membrane transport. These findings highlight organ-specific clearance kinetics and molecular responses to inhaled CdONPs, underscoring the need for tissue-targeted risk assessment frameworks in nanoparticle toxicology.

This technical note demonstrates the potential of inductively coupled plasma mass spectrometry with a quadrupole analyzer (ICP-QMS) for lead isotope ratio determination offering a step-by-step guide for laboratories aiming to achieve reliable precision without access to multi-collector instrumentation. Key instrumental parameters such as dwell time, number of replicates, sweeps per replicate, pump speed and nebulizer gas flow were systematically optimized. Special attention was given to the influence of detector mode selection (Auto vs. Analog) and its impact on low-abundance isotopes such as Pb-204. The optimized procedure yielded precision of 0.08-0.10 % RSD for Pb-206/Pb-207 and Pb-208/Pb-206 ratios and 0.10-0.12 % RSD for Pb-206/Pb-204 as a minimum, which is sufficient for selected applications. The optimized method was validated using NIST SRM 981 and archaeological metal samples previously analyzed by MC-ICP-MS. Results show good agreement in isotope ratios between ICP-QMS and MC-ICP-MS, with deviations expressed as delta values <0.3 % in most cases, for Pb-206/Pb-204 < 1.5 %. Although the method does not aim to replace MC-ICP-MS for high-precision work, it offers a robust and cost-effective alternative for applications requiring moderate precision, especially in laboratories without access to multi-collector instrumentation.

The nickel and zinc contamination of algae on a cellulose filter was studied with double pulse 1064-1064 nm laser-induced breakdown spectroscopy (LIBS). Samples of the green alga Desmodesmus subspicatus were contaminated with zinc and nickel. The surface concentrations on the filter calculated from the reference Inductively Coupled Plasma Mass Spectrometry analysis were 25 and 64 ng cm-2 for nickel and zinc respectively. The algae are resting on the filter after drying and a double adhesive tape was used to fix the sample on the microscopic glass. During optimization method a compromise of 23-30 mJ pulse energies were set for maintaining a detectable or highest signal intensity of the analyte and not destroying the filter. Best conditions for maximum analyte signal and minimum deviation between the spectral behaviour of the analyte and the compared line of Na I, K I, Mg I, Mg II, Mn I, Mn II, Ca I, Ca II, and C I was 700 ns gate delay and 0 s interpulse delay. The deviation was rather more influenced with the signal-to-noise ratio of the analyte line than the closeness of the upper-level energies of the compared lines. The filter without algae showed systematically lower electron number density and total emissivity by units of percents than the filter with algae.

The aim of this study was to determine whether the degree of pulse overlap affects the analytical response of LA-ICP-MS when utilized in scanning mode. The investigation focused not only on the analytical signal but also on the properties of the generated aerosol and the morphology of ablation craters. Ablation was carried out using a nanosecond ablation system on single-element samples of metals and metalloids, specifically Cr, Hf, Sb, Si, Ta, and W. Pure single-element standards were selected to eliminate elemental fractionation and ensure the chemical composition of the generated aerosol was consistent across all particle sizes. The effect was studied on the surfaces of the samples prepared in various ways, including polished and two types of roughened finishes. It was found that the degree of laser pulse overlap significantly influences the quantity of generated particles, their size, and consequently the measured analytical signal, altering it by tens of percent. Slightly different properties were observed in the groups of metal and metalloid samples. For metals, an increasing overlap of pulses resulted in a decrease in the analytical signal across all types of surfaces. For metalloids, the results were different on polished surfaces. The study shows that adjusting the pulse overlap by combining the scan speed and laser repetition rate can have a significant effect on the LA-ICP-MS analysis results.

Stroke, myocardial infarction, and pulmonary embolism represent a significant health burden for modern society, with their primary causes being blood clots and damage to the endothelial lining of blood vessels. Accurate and rapid diagnosis of these clots, particularly determining their age, is crucial for optimal treatment selection, such as thrombolysis (pharmacological dissolution of the clot) or thrombectomy (mechanical removal of the clot). However, existing diagnostic methods do not achieve the required levels of accuracy and efficiency. This article explores the potential of iodinated nanoparticles (IoNPs) based on polyiodinated biodegradable polymers, which can selectively target specific components such as fibrin, thereby enabling visualization of blood clots using X-ray imaging techniques like computed tomography (CT) or fluoroscopy. The nanoparticles have the capability not only to visualize clots but also to estimate their age, which could significantly support a modern theranostic approach that combines diagnosis and therapy. The article also demonstrates the possibilities of testing the pharmacokinetics of these theranostics using a model organism (rat), employing the method of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). This approach contributes to a better understanding of the biodegradability of potential therapeutics and represents a key step in preclinical evaluation.

Background: Pseudohyperphosphatemia in patients with multiple myeloma is described in literature as analytical interference or phosphates binding to monoclonal protein.We suspected pseudohyperphosphatemia in 69 years-old patient with IgG kappa type of multiple myeloma (Phosphates >3 mmol/L, normal concentrations of creatinine, parathormon and vitamin D).The aim was to prove pseudohyperphosphatemia and to determine its origin.Methods: Inorganic phosphate was measured by routine molybdate method in untreated serum and after deproteination by sulfosalycilic acid.Correlation coefficient of phosphate in untreated serum and monoclonal immunoglobulin concentrations between September 2016 and February 2018 was calculated.The reaction was manually simulated and the detailed record of measurement from the analyzer was scrutinized retrospectively.Total phosphorus concentration was measured by mass spectrometry in untreated and deproteined serum of this patient, as well as in control group of 10 samples.Results: Inorganic phosphate concentrations were 3.38 mmol/L in untreated and 1.17 mmol/L in deproteined serum.Correlation coefficient R2=0.8948 between phosphate and monoclonal immunoglobulin was measured.Formation of turbidity during manual simulation and gradual increase in absorbance in measurement record were observed.Total phosphorus concentrations were 3.60 mmol/L before and 1.20 mmol/L after deproteination, within 95% confidence interval of control group (3.01-4.12mmol/L untreated; 0.79-1.28mmol/L deproteined samples). Conclusion:Noticeable difference in phosphates in untreated and deproteined serum together with the normal results of total phosphorus confirm pseudohyperphosphatemia caused by analytical interference rather than binding to monoclonal protein.Rising numbers of patients with myeloma, shows necessity to check for possible interferences and adopt appropriate measures.

A new experiment using laser ablation with inductively coupled plasma mass spectrometry (LA-ICP-MS) was designed for chemistry undergraduate students. While most analytical methods only provide information on the amount of the analyte, LA-ICP-MS allows extra information on the distribution of the element in the sample. Because it achieves excellent limits of detection (sub mu g center dot g-1) and high spatial resolution (micrometer scale), it is a powerful technique for imaging any sample. A thin section of mouse tissue was used as a model sample to demonstrate these abilities. The student's task was to determine the distribution of the essential elements Zn, Cu, and Pt (Pt introduced into the tumor tissue from the cytostatic drug (cis Pt)) and quantify their amount.

Effective detection and sensitive quantification of disease markers enable a better understanding of processes leading to disease development.

The main aim of this work is to demonstrate the potential of LIBS as a complementary technique to electron probe microanalysis (EPMA) for distinguishing and characterizing uranium mineralizations. Combining both methods can help estimate uranium oxidation states and monitor the possible mobilization of uranium in the environment by detecting oxygen and hydrogen using LIBS. It was confirmed that the LIBS signal of oxygen is proportional to oxygen content and that the strength of the oxygen signal is closely related to the oxidation state of uranium. The second assumption that the hydrogen signal is closely related to water (or hydroxyl group) content was also confirmed by detecting a stronger hydrogen signal from the presumed secondary mineralization. In contrast, hydrogen was not found in uraninite and quartz.When superimposed, images obtained with LIBS and EPMA show a clearly visible contrast between primary and secondary uranium mineralizations. Images of uranium obtained with the two techniques match perfectly, while the LIBS image of oxygen confirms the presence of an oxidized form of secondary uranium minerals (uranophane). The LIBS image of hydrogen clearly shows mineral phases containing water or a hydroxyl group, confirming that uranophane and other associated minerals contain greater amounts of hydrogen (water).

In the past couple of years, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been widely used for trace element analysis in solid samples and the study of their distribution.

The chromium and copper contamination of algae on a filter was directly monitored with laser-induced breakdown spectroscopy (LIBS) as a demonstration of LIBS capabilities. Liquid samples of the green alga Desmodesmus subspicatus were intentionally contaminated with chromium, incubated, filtered, and the filters with the algae were analysed. Inductively coupled plasma mass spectrometry (ICP-MS) was used as a reference method. One half of the filter with the algae was dissolved and analysed as a solution with ICP-MS and the second half was subjected to the LIBS and laser ablation-ICP-MS analysis. Chromium and copper were attributable to the algae contamination and detectable with LIBS. The results from the LIBS provided almost equivalent information about the relative changes of the Cr and Cu concentration in the algae. The sensitivity of LIBS with a Czerny-Turner spectrometer was fully comparable with the ICP-MS procedure. The trends from LIBS were more similar to the LA-ICP-MS ones. It means that the algae growth inhibition in dependence on the chromium or copper content can be alternatively monitored with LIBS instead of the complicated decomposition procedure in ICP-MS analysis.

We report a new technique for the digital mapping of biomarkers in tissues based on desorption and counting intact gold nanoparticle (Au NP) tags using infrared laser ablation single-particle inductively coupled plasma mass spectrometry (IR LA SP ICP MS). In contrast to conventional UV laser ablation, Au NPs are not disintegrated during the desorption process due to their low absorption at 2940 nm. A mass spectrometer detects up to 83% of Au NPs. The technique is demonstrated on mapping a proliferation marker, nuclear protein Ki-67, in three-dimensional (3D) aggregates of colorectal carcinoma cells, and the results are compared with confocal fluorescence microscopy and UV LA ICP MS. Precise counting of 20 nm Au NPs with a single-particle detection limit in each pixel by the new approach generates sharp distribution maps of a specific biomarker in the tissue. Advantageously, the desorption of Au NPs from regions outside the tissue is strongly suppressed. The developed methodology promises multiplex mapping of low-abundant biomarkers in numerous biological and medical applications using multielemental mass spectrometers.

Drug efficacy determined in preclinical research is difficult to transfer to clinical practice. This is mainly due to the use of oversimplified models omitting the effect of the tumor microenvironment and the presence of various cell types participating in the formation of tumors in vivo. In this study, we used robust three-dimensional models including spheroids grown from colon cancer cell lines and organotypic cultures prepared from the colorectal carcinoma tissue to test novel therapeutic strategies. We developed a multi-modal approach combining brightfield and fluorescence microscopy for evaluating drug effects on organotypic cultures. Combined treatment with 5-fluorouracil and disulfiram/copper efficiently eliminated cancer cells in these 3D models. Moreover, disulfiram/copper down-regulated the expression of markers associated with 5-fluorouracil resistance, such as thymidylate synthase and CD133/CD44. Thus, we propose combined therapy of 5-fluorouracil and disulfiram/copper for further testing as a treatment for colorectal carcinoma. In addition, we show that organotypic cultures are suitable models for anti-cancer drug testing.

The great potential in combining two elemental imaging techniques - Laser Induced Breakdown Spectroscopy (LIBS) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) is demonstrated for uranium ore sample investigation. Dual imaging provides the advantages of both methods – high speed, large area imaging and additional evaluation of the whole spectrum for LIBS, and high resolution, low detection limits and isotopic imaging for LA-ICP-MS. Special software, ILAPS, was created for data processing to ensure the consistency of the resulting element images and the possibility of their combination. This new method for merging LIBS and LA-ICP-MS imaging data allows the display of detailed structures on the background of the overall sample image. Information contained in the detailed structures together with an overall view of the sample was displayed in one image to visualise the complete data from both methods. The effectiveness and usefulness of this new approach were demonstrated in identifying the structures responsible for elements migration in the uranium ore sample.

The major and trace element composition of the main HFSE-bearing phases from highly evolved miaskitic syenites has been investigated to assess their stability, an important control on HFSE retention and mobility during post-magmatic hydrothermal activity. The major HFSE carrier, abundant zircon (up to 5 vol%), has undergone intensive metamictization, caused by high initial U and Th along with the presence of early magmatic U-thorite inclusions. Subsequent to metamictization, zircon experienced pervasive fluid-driven alteration, as evidenced by strong depletion in Zr and Si, enrichment in non-formula elements (Ca, Fe, Al, P), deficient EMPA analytical totals, high porosity, and low BSE-intensities of strongly altered crystal interiors. Element maps suggest that extensive HFSE remobilization from altered zircon was controlled by interaction with oxidized aqueous solutions circulating through abundant microfractures that formed by volume expansion due to zircon metamictization. Enhanced HFSE mobility in hydrothermal fluids is reflected by the presence of a hydrated amorphous Zr-Th-U-Si-phase, filling microveinlets intimately associated with metamict zircons. In addition to HFSE remobilization from altered zircon, titanite released a significant amount of REE during interaction with the hydrothermal fluids that concurrently caused a fractionation of Eu in titanite, producing increased Eu-N/Eu-N* (4.16-22.2) in altered crystals. Extensively altered titanite grains with elevated Eu-N/Eu-N* are considerably depleted in Sigma REE + Y compared to unaffected crystals, showing that degree of positive Eu anomalies, relating to post-magmatic metasomatic overprint, appears to be a sensitive indicator for an intensity of hydrothermal alteration and even the total amount of released incompatible elements. Pronounced LREE enrichment accompanied by HREE depletion in the strongly altered crystals indicates greater LREE retention in titanite and higher HREE mobility in the hydrothermal system probably caused by complexing with fluoride ligands. Fluorine was most likely supplied through amphibole and biotite chloritization, as suggested by notably low F in the mafic silicates along with the formation of secondary F-rich titanite at the expense of altered biotite. Moreover, the dissolution of zircon and titanite and resistance of apatite to pervasive alteration indicates that remobilization of HFSE and REE from these phases occurred under alkaline conditions (pH 8-12), presumably controlled by potassium-dominated complexes transporting HFSE along with REE over long distances, as indicated by a close spatial linkage of syenite outcrops with U-mineralization. Our results clearly demonstrate: (1) extensive chemical dissolution of zircon controlled by its self-induced radiation damage; (2) high solubility of titanite and metamict zircon under alkaline conditions; (3) enhanced mobility and long-distance transport of HFSE and REE in alkali- and F-rich hydrothermal systems.

In this work we discuss how sample surface topography can significantly influence the laser ablation (LA) process and, in turn, the analytical response of the LA Inductively Coupled Plasma Mass Spectrometr y (LA-ICP-MS) method. Six different surface topographies were prepared on a certified aluminiu m alloy sample BAM 311 and SRM NIST 610 to investigate the phenomenon. A l l the samples were repetitively measured by LA-ICP-MS using a spot by spot analysis. The effect oflaserfluence in the range of 1-13 J/cm(2) was studied . For majority ofmeasured isotopes, the ICP-MS signal was amplified with roughening of the sample surface. A stronger effect was observed on the Al alloy sample, where the more than sixty-time enhancement was achieved in comparison to the polished surface of the sample. Since the effect of surface topography is different for each analyte, it can be stated that surface properties affect not only the ICP-MS response, but also elemental fractionation in LA . The presented results show that different surface topographies may lead to misleading data interpretation because even when applying ablation preshots, the signal of individual elements changes. The utmost care must be taken when preparing the surface for single shot analysis or chemical mapping. On the other hand, by roughening the sample surface, it is possible to significantly increase the sensitivity of the method for individual analytes and supress a matrix effect.

Immunochemical methods are used not only in clinical practice for the diagnosis of a wide range of diseases but also in basic and advanced research. Based on the unique reaction between the antibody and its respective antigens, it serves to specifically recognize target molecules in biological complex samples. Current methods of labelling antibodies with elemental labels followed by detection by inductively coupled plasma mass spectrometry (ICP-MS) allow detection of multiple antigens in parallel in a single analysis. Using the laser ablation (LA) modality (LA-ICP-MS), it is also possible to monitor the spatial distribution of biogenic elements. Moreover, the employment of metal nanoparticle-labeled antibodies expands the applicability also to molecular imaging by LA-ICP-MS. In this work, conjugates of model monoclonal antibody (DO-1, recognizing p53 protein) with various metal nanoparticles-based labels were created and utilized in dot-blot analysis in order to compare their benefits and disadvantages. Based on experiments with the p53 protein standard, commercial kits of gold nanoparticles proved to be the most suitable for the preparation of conjugates. The LA-ICP-MS demonstrated very good repeatability, wide linear dynamic range (0.1–14 ng), and limit of detection was calculated as a 1.3 pg of p53 protein.