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In this work, a novel method of antimony fire assay (Sb-FA) enrichment combined with laser ablation ICP-MS (LA-ICP-MS) for the determination of ultra-trace platinum group elements (PGEs) in geological samples was established. The purification and recycling technology of ultra-clean and high-purity fire assay collector Sb 2 O 3 was proposed, in addition, high-purity quartz crucible was developed to replace the usual clay crucible, then the blank values of PGEs were as low as 0.0007-0.0028 ng g -1 (for 20 g sample). 190 Os isotopic diluent was used as internal standard (IS) and quantitatively added into the fire assay ingredients, and fully mixed and balanced with the PGEs in the real samples by means of high temperature melting, cupellation and horizontal rotation of crucible and dish. Both 190 Os and PGEs in the real sample were pre-concentrated in microgram level Sb granules (100 mg) through Sb-remaining cupellation. After grinding and polishing, 195 Pt, 105 Pd, 101 Ru, 103 Rh, 193 Ir, total 189 Os and 190 Os enriched in Sb slices were determined by LA-ICP-MS, 190 Os in the internal standard was calculated by isotope dilution equations. The Certified Reference Materials (CRMs) for PGEs were treated by the same procedure to obtain completely matrix matched Sb slices to solve the problem of no internationally recognized uniform PGEs standard materials for LA-ICP-MS determination. Due to the similar distribution trends of different PGEs in Sb slices by LA-ICP-MS imaging, then matrix-matched internal standard calibration strategy was used to reduce the element fractionation effect and improve the determination precision and accuracy of LA-ICP-MS. The laser frequency, energy density, denudation diameter and dwell times were optimized. Under the optimal conditions, empirical coefficient method was used to fit the standard curve and excellent curve fitting of PGEs were obtained with the correlation coefficient between 0.9990 and 0.9999. The method detection limits (LODs) for PGEs ranged from 0.00042 to 0.010 ng g -1 . The established method was successfully applied to analyze real geochemical samples and various matrix Certified Reference Materials (CRMs) domestic and international, the determined values were in good agreement with the results of Sb-FA ICP-MS and the certified values., Competing Interests: Declaration of competing interest No conflict of interest exits in the submission of this manuscript, and manuscript is approved by all authors for publication., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Breast cancer (BC) is the leading cause of cancer death among women worldwide, making the discovery and quantification of new biomarkers essential for improving diagnostic and preventive strategies to limit dissemination and improve prognosis. Essential trace metals such as Fe, Cu, and Zn may play critical roles in the pathophysiology of both benign and malignant breast tumors. However, due to the high metabolic activity and reduced element selectivity of cancer cells, also non-essential elements may be taken up and may even be implicated with disease progression. This study investigates the spatial distribution and concentrations of both essential and non-essential elements in breast tissues, assessing their potential for diagnostic applications. Laser ablation (LA)-inductively coupled plasma-mass spectrometry (ICP-MS) with a time-of-flight (ToF) mass analyzer (LA-ICP-ToF-MS) was used to inquire the distribution of almost all elements across the periodic table and their abundance in metastatic (n = 11), non-metastatic (n = 7), and healthy (n = 4) breast tissues. Quantification was achieved using gelatine-based standards for external calibration to quantitatively map various elements. Overall, the Fe, Cu, Zn, Sr, and Ba levels were significantly increased in tumor samples with Sr and Ba showing strong correlation, likely due to their similar chemistry. Comparison of calibrated LA-ICP-ToF-MS data with a histologic staining demonstrated the possibility to clearly differentiate between various tissue types and structures in breast tissues such as tumor niche and stroma. The levels of the studied elements were significantly higher in the tumor niche areas compared to the stroma, and for Fe, a significant accumulation was observed in the tumor niche areas from the metastatic patient group relative to the levels found in the same areas of the non-metastatic group., Competing Interests: Declarations. Ethical approval: This study was conducted in accordance with national regulations and received approval from the Ethics and Investigation Committee of the Hospital de Jove Foundation (PI02/2018). Competing interests: The authors declare no competing interests., (© 2024. The Author(s).)

Calibrations in LA-ICP-MS are typically very time-consuming and complex, as they need to be matched to the samples being measured and sectioned on a microtome. Alternatively, gelatin can be in droplet form or as a section, which is a more recent development. In this study, we report on investigations where hot multi-element gelatin solutions are placed in a linear fashion on microscopic slides to conduct comparative statistical observations between doped tissue homogenates from the liver and lung. The tissue homogenates served as both samples (complete ablation) and calibration standards (partial ablation) for verification purposes. We explored the effects of different laser fluences (0.50-1.50 J/cm 2 ), gelatin contents (0.3-20.0%) and section thicknesses (10-30 µm). To do this, we evaluated the samples by calculating median and mean values over the entire section with and without removal of elementary spikes (de-spiking). A reduction in distribution was achieved with averaging. The data was normalized using 13 C as an internal standard. In these experiments and under these measurement conditions, it was observed that the selected laser fluences, gelatin contents, and section thicknesses did not visibly affect the results, making them comparable. Each sample could be assessed with each gelatin calibration, allowing for determination of expected reference values. Despite interruptions in the measurement operation, due to the high number of measurements, where samples and calibrations could not be analyzed in one measurement run, no negative effects of stopping and starting the LA-ICP-MS were observed., Competing Interests: Declarations. Conflict of interest: The authors have declared no conflict of interest., (© 2024. The Author(s).)

Azurite, a historical blue mineral pigment, has previously been described to contain certain elemental impurities. These may originate from host rocks, vein fillings, or the primary copper ore mineralization. In this study, azurites (and also green malachites) from three important Central European deposits with a potential of being exploited for pigment usage already in the Middle Ages have been studied, together with azurite from Chessy, France, with a different geological setting. Using electron probe microanalysis and, more importantly, laser ablation inductively coupled plasma mass spectroscopy for trace elemental analysis, several indicators were pinpointed as important for provenance: characteristic elemental fingerprint of the deposit, e.g., elevated lead (Pb) in combination with rare earth elements, may be combined with zinc (Zn)/arsenic (As) ratio (indicating sources of excess Zn in the primary deposit) and the overall amount of metal impurities (suggesting the source mineral of copper for azurite formation). In addition, malachites from the same deposits were found to preferentially incorporate primary ore metal elements as well as Cd, Mg, Mn, or U. Therefore, if azurite pigment contains an elevated amount of malachite as an impurity, it may significantly influence the overall elemental composition. The results obtained on geological samples were applied to two micro-samples of works of art containing azurite-rich layers originating from the 13th-14th and 16th centuries. It was shown that it is highly beneficial to focus on the overall trace elemental composition of the paint layer and not on the admixed mineral grains, as their presence, especially in minute micro-samples, is largely accidental and thus not representative. Although a higher number of samples need to be studied in the future, the newly described criteria made it possible to exclude some of the localities of the employed azurite pigment. This confirmed the key importance of trace elements analysis of mineral pigments for the provenance studies of fine arts., Competing Interests: Declaration of Conflicting InterestsThe authors declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.

Correlative imaging of cutaneous tumors provides additional information to the standard histopathologic examination. However, the joint progress in the establishment of analytical techniques, such as Laser-Induced Breakdown Spectroscopy (LIBS) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) in clinical practice is still limited. Their combination provides complementary information as it is also shown in our study in terms of major biotic (Ca, Mg, and P) and trace (Cu and Zn) elements. To elucidate changes in the elemental composition in tumors, we have compiled a set of malignant tumors (Squamous Cell Carcinoma, Basal Cell Carcinoma, Malignant Melanoma, and Epithelioid Angiosarcoma), one benign tumor (Pigmented Nevus) and one healthy-skin sample. The data processing was based on a methodological pipeline involving binary image registration and affine transformation. Thus, our paper brings a feasibility study of a practical methodological concept that enables us to compare LIBS and LA-ICP-MS results despite the mutual spatial distortion of original elemental images. Moreover, we also show that LIBS could be a sufficient pre-screening method even for a larger number of samples according to the speed and reproducibility of the analyses. Whereas LA-ICP-MS could serve as a ground truth and reference technique for preselected samples., Competing Interests: Declaration of competing interest All authors hereby declare that they have no conflict of interest with regard to the presented study. Moreover, the ethical issues related to the handling and analysis of clinical samples (biopsies of human cutaneous tumors and healthy skin) were done under the approval of the ethical committee of the Hradec Králové University Hospital (ref. number 201805 S08P) where the patients were treated., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Background: Spatial elemental analysis of deciduous tooth dentin combined with odontochronological estimates can provide an early life (in utero to ~2 years of age) history of inorganic element exposure and status., Objective: To demonstrate the importance of data normalization to a certified reference material to enable between-study comparisons, using populations with assumed contrasting elemental exposures., Methods: We used laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) of dentin to derive a history of elemental composition from three distinct cohort studies: a present day rural cohort, (the New Hampshire Birth Cohort Study (NHBCS; N = 154)), an historical cohort from an urban area (1958-1970), (the St. Louis Baby Tooth Study (SLBT; N = 78)), and a present-day Nigerian cohort established to study maternal HIV transmission (Dental caries and its association with Oral Microbiomes and HIV in young children-Nigeria (DOMHaIN; N = 31))., Results: We report Li, Al, Mn, Cu, Zn, Sr, Ba and Pb concentrations (µg/g) and qualitatively examine As, Cd and Hg across all three cohorts. Rates of detection were highest, both overall and for each cohort individually, for Zn, Sr, Ba and Li. Zinc was detected in 100% of samples and was stably present in teeth at a concentration range of 64 - 86 µg/g. Mercury, As and Cd detection rates were the lowest, and had high variability within individual ablated spots. We found the highest concentrations of Pb in the pre- and postnatal dentin of the SLBT cohort, consistent with the prevalent use of Pb as an additive to gasoline prior to 1975. The characteristic decline in Mn after the second trimester was observed in all cohorts., Impact: Spatially resolved elemental analysis of deciduous teeth combined with methods for estimating crown formation times can be used to reconstruct an early-life history of elemental exposure inaccessible via other biomarkers. Quantification of data into absolute values using an external standard reference material has not been conducted since 2012, preventing comparison between studies, a common and highly informative component of epidemiology. We demonstrate, with three contrasting populations, that absolute quantification produces data with the lowest variability, compares well with available data and recommends that future tooth biomarker studies report data in this way., Competing Interests: Competing interests: The authors declare no competing interests. ETHICAL APPROVAL: NHBCS: Participants received a detailed description of the study procedures before consenting to participate. Study materials and protocols for NHBCS were approved by the Committee for the Protection of Human Subjects at Dartmouth College. Data from the first analyzed NHBCS teeth (n = 154) are included in this study., (© 2024. The Author(s), under exclusive licence to Springer Nature America, Inc.)

Accurate determination of rare earth element (REE) concentrations in CaF 2 crystals using UV-LA-ICP-MS is important but challenging due to the lack of matrix-matched reference materials. In this study, a REE-doped CaF 2 single crystal (CaF 2 -05), prepared via the Bridgman-Stockbarger technique, was systematically characterized to assess its optical properties, homogeneity, and stability. Analyses using portable laser irradiation, UV-vis spectroscopy, back scatter electron (BSE) imaging, and cathodoluminescence (CL) demonstrated that the crystal possesses high optical quality and exhibits distinct optical adsorption properties compared to the silicate reference material NIST SRM 610. The within-unit variation (S r ) ranged from 3.82 % to 9.86 %, the between-unit S r varied from 3.94 % to 7.85 %, and the mean square weighted deviation (MSWD) was close to 1, indicating minimal chemical heterogeneity. These results are comparable to those of certified reference materials and other home-made calibration standards. Femtosecond LA-ICP-MS mapping further confirmed the homogeneous distribution of REEs within the CaF 2 crystal. Stability tests conducted from April to November 2024 demonstrated the crystal's good long-term stability. The method's accuracy was validated by calibrating REE concentrations in another CaF 2 single crystal (CaF 2 -005), with measured REE concentrations closely matching reference values. The relative deviations (D r ) primarily ranged from -10.10 % to 12.79 %, which is significantly more accurate than the non-matrix-matched calibration using NIST SRM 610. These findings demonstrate that this method provides reliable accuracy and holds promise for application in the accurate determination of REE concentrations in CaF 2 -matrix samples, such as CaF 2 luminescent materials and natural fluorite ores., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

This study investigates the influence of multistrain probiotics and iron supplementation on the distribution and interaction of trace elements in the kidneys of Wistar rats using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) bioimaging. Forty 6-week-old female Wistar rats were divided into five groups, each fed an AIN-93 M diet with varying additions or deficiencies of iron and probiotics, which included a control, an iron-deficient diet, an iron-deficient diet with probiotics, an iron-deficient diet with iron supplementation, and an iron-deficient diet with both probiotics and iron supplementation. The obtained two-dimensional maps of the distribution of elements reveal distinct locations of Cu, Fe, Mn, and Zn in specific tissues of rat kidneys. Specifically, Cu and Fe were co-localized in the renal cortex, while Zn was mostly absent from regions where Cu and Fe accumulated. Fe supplementation alone increased Fe in the renal cortex, while probiotics enhanced this effect, suggesting a synergistic role in Fe absorption. The total content of elements in the kidneys of all groups was determined after digestion: Cu 13.3-24.7 mg kg - 1 , Fe 218-509 mg kg - 1 , Mn 0.87-1.29 mg kg - 1 , and Zn 28.6-40.1 mg kg - 1 . Competitive interactions among Cu, Fe, and Zn were observed, with probiotics modulating their concentrations and distribution, highlighting their role in trace element homeostasis. Our research provides insights into the interactions between dietary supplements, probiotics, and trace element distribution in kidneys, paving the way for targeted nutritional interventions. This study highlights the need for further research on trace element functions in organisms and their impact on health., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Rare Earth Elements (REE) are present in acid mine drainage (AMD) in micromolar concentrations and AMD discharge may lead to an environmental risk. Alkaline Passive Treatment Systems (PTS) are often used to treat AMD and trap toxic trace elements. This study was set up to identify mechanisms by which REE are trapped in or on secondary phases formed in a PTS. Batch alkalinization experiments were performed to simulate PTS by sequentially increasing the pH of AMD collected from the Tharsis mining area inside the Iberian Pyrite Belt and synthetic AMD water samples via CaCO 3 addition. The solids that precipitated up to pH ~4 and between pH 4-6 were collected and characterized by Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) in combination with Scanning Electron Microscope/Energy Dispersive X-ray spectroscopy (SEM/EDX) and synchrotron-based X-ray Absorption Spectroscopy (XAS) and synchrotron-based Micro-X-ray Fluorescence (μ-XRF). Results reveal that REE are mostly scavenged between pH 4-6 in association with Al and Fe phases, whereas a smaller fraction is scavenged at pH ~4 by association with gypsum. Synchrotron-based analysis evidences the incorporation of La 3+ into the gypsum structure by substituting Ca 2+ , indicating a co-precipitation mechanism with gypsum occurring mainly at low pH. Results from parallel adsorption and co-precipitation tests suggest that the REE scavenging between pH 4-6 could be due to a combination of adsorption and co-precipitation on Al(OH) 3 and ferrihydrite. This implies that in PTS, REE would be mainly found in Al- (and Fe-) oxyhydroxides occurring in deeper layers of the PTS, i.e., where higher pH-values occur, though a small fraction, especially the light REE, could also be found incorporated into gypsum in the upper layers., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier B.V. All rights reserved.)

Niobium has been considered to be enriched in high-Al-Ga in north China coal and coal-hosted Nb(Ta)-Zr(Hf)-REY-Ga polymetallic deposits in the southwestern region of China. However, modes of occurrence and influencing factors of Nb in Al-Ga-rich coal in North China are rarely reported. This study investigated the distribution characteristics of Nb in the No.6 high-Al-Ga coal of the Jungar Coalfield in North China. The in-situ Nb concentration of selected minerals, including kaolinite, Ti-oxides, boehmite, and zircon, is further quantitatively characterized based on multiscale in-situ elemental analyses, including SEM-EDS and LA-ICP-MS spot and mapping analyses. The results showed that Nb is rich in the tonstein and mudstone partings among bulk samples and is highly concentrated in Ti-oxides, followed by zircon among the minerals. A certain amount of Nb is associated with kaolinite and boehmite with different modes of occurrence: vermicular kaolinite (65.94 ppm) > clastic kaolinite (25.43 ppm) > altered K-bearing kaolinite (18.11 ppm) > cryptocrystalline kaolinite (17.03 ppm) > clastic boehmite (9.08 ppm) > cryptocrystalline boehmite (7.97 ppm). The Nb-Nb/Ta and Zr/Hf-Nb/Ta ratios suggest that the primary source of Nb in the No.6 coal is the altered felsic volcanic ash and bauxite deposit. The high-Fe concentration in Ti-bearing minerals indicates that anatase may originate from the alteration of ilmenite with a process of Fe depletion and Nb enrichment. The enrichment of Nb in coal is attributed to the substitution of Nb for Ti in isomorphism in all Ti-oxides, high-Ti, and Ti-bearing minerals., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Internal inhomogeneity of the zircon crystals makes it difficult to date succedent geological processes. To overcome this limitation, a four-step pre-examination method is suggested before LA-ICP-MS based in situ U-Pb age determination of zircon crystals: 1. determination of morphology types of zircon, 2. description of internal textural patterns of zircon, 3. identification of mineral inclusions in zircon, 4. characterization of the structural state and chemical composition of zircon zones/areas. The novel four-step pre-examination protocol integrates established and partially established methods into comprehensive analytical techniques approach that enhances U-Pb dating. The paper demonstrates the effectiveness of this method using examples of zircons derived from granitoid rocks of the Variscan collision zone from the Mórágy Complex in southern Hungary and the Rastenberg Pluton in northern Austria. The study revealed that the areas of the primary textures within zircon crystals (growth zoning ± xenocrystic core, sector zoning) represent the effect of the primary magmatic event from both locations. The xenocrystic core suggests antecedent crustal origin. The secondary texture (convolute zoning) of zircon crystals reflects the post-magmatic event. It causes an overprinting of age data, highlighting the importance of a four-step pre-examination methodology in clarifying and separating nearly coeval geological processes. For age dating, 80 % of the core, 90 % of growth, sector zoning, and 100 % of convolute zoning of studied zircon crystals were appropriate. The suggested method can also be applied to U-Pb age dating of other mineral phases (allanite, apatite, titanite, rutile, xenotime, monazite) separated from igneous and sedimentary or metamorphic rocks., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2024 The Author.)

External contamination of hair is the most significant challenge to it becoming an accepted matrix for monitoring endogenous metal exposure and nutritional deficiency. Here we use laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to quantify elemental concentrations in hair strands below and above the scalp in the cuticle and cortex layers to determine the extent of external contamination in a reference population. Evidence of hair strand contamination occurred for barium, calcium, iron, magnesium, and strontium in both the outer cuticle and the inner cortex layers, with increasing concentrations from root to tip. Aluminum, boron, copper, lead, and manganese showed significant contamination in the cuticle layer only, suggesting some protection of the inner cortex. Phosphorus and potassium decreased outside the scalp suggesting loss by washing, while chromium, mercury, selenium, sodium, titanium, and zinc showed no evidence of loss or external contamination above the scalp. The results clearly show that for most elements, hair chemistry above the scalp is unreliable for use in interpretation of endogenous exposures or deficiencies, and that the below-scalp portion provides a more accurate monitoring tool. This is the first paper to provide a reference range of elemental hair chemistry that is not impacted by the external environment., (© 2023. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

A referencing strategy based on the element P is presented to compensate for cryosectioning tissue artifacts in laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) data. The study examines how the gadolinium-based contrast agent Gadofosveset is distributed in murine cancer tissue, and illustrates how referenced images can compensate for tissue artifacts like folds, overlaps, and density variations. Compared to non-referenced images that provide information on the absolute distribution of the analyte, referenced images allow for the representation of the analyte distribution relative to the amount of material introduced into the instrument, which in this case is correlated to the P signal. Tissue artifacts were corrected in referenced images for both Gadofosveset and endogenous elements, such as Fe and Zn. Additionally, the referencing approach provides valuable information on the Gd uptake relative to the tissue density in necrotic compared to vital tumor areas, which is not obtained from in vivo magnetic resonance imaging (MRI) data. However, validation of in vivo MRI and ex vivo LA-ICP-MS methods was possible by establishing a mean ratio of necrotic to vital tumor areas in the T1-weighted image post Gadofosveset injection and the non-referenced LA-ICP-MS image of Gd. In summary, P-based correction of LA-ICP-MS imaging data allows for a more accurate spatial representation of certain elements, including endogenous and exogenous elements such as injected contrast agents., (© The Author(s) 2024. Published by Oxford University Press.)

A simple and reliable external calibration strategy of LA-ICP-MS for fresh plant soft tissues was developed. The prepared plant suspension was frozen by the designed cryogenic ablation cell and used as external standard for quantitative elemental imaging analysis of fresh plant tissues. The controllable water content of the prepared external standards provides a similar matrix with fresh soft tissues, and a homogeneous elemental distribution could be ensured due to the fine grinding particle sizes. More interestingly, the presence of water increased the signal intensity produced by the suspension by a factor of 1.6 (Pb) to 66.6 (La) compared to that of the pressed cake. The excellent dispersing property and advantage of long-term use were achieved owing to the employment of 0.1% PAANa as suspending agent. A series of plant reference materials were analyzed, and the relative errors of most elements were less than 10 %, indicating that there is a reliable accuracy of the proposed method. The limits of detection (LODs) ranged from 0.1 ng·g -1 (La) to 1279 ng·g -1 (S). This method was used for elemental imaging analysis in rice leaves under arsenic stress, and the results were consistent with previous studies, which mean that the proposed method could provide technical support for researchers in the fields of agriculture and environment., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.)

Banded iron formations (BIFs) archive the relationship between Earth's lithosphere, hydrosphere, and atmosphere through time. However, constraints on the origin of Earth's largest ore deposits, hosted by BIFs, are limited by the absence of direct geochronology. Without this temporal context, genetic models cannot be correlated with tectono-thermal and atmospheric drivers responsible for BIF upgrading through time. Utilizing in situ iron oxide U-Pb geochronology, we provide a direct timeline of events tracing development of all the giant BIF-hosted hematite deposits of the Hamersley Province (Pilbara Craton, Western Australia). Direct dating demonstrates that the major iron ore deposits in the region formed during 1.4 to 1.1 Ga. This is one billion to hundreds of millions of years later than previous age constraints based upon 1) the presence of hematite ore clasts in conglomerate beds deposited before ~1.84 Ga, and 2) phosphate mineral dating, which placed the onset of iron mineralization in the Province at ~2.2 to 2.0 Ga during the great oxidation event. Dating of the hematite clasts verified the occurrence of a ~2.2 to 2.0 Ga event, reflecting widespread, but now largely eroded iron mineralization occurring when the Pilbara and Kaapvaal cratons were proximal. No existing phosphate mineral dates overlap with obtained hematite dates and therefore cannot be related to hematite crystallization and ore formation. New geochronology conclusively links all major preserved hematite deposits to a far younger (1.4 to 1.1 Ga) formation period, correlated with the amalgamation of Australia following breakup of the Columbia supercontinent., Competing Interests: Competing interests statement:The authors declare no competing interest.

Elemental bioimaging of low abundant elements via laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) is hampered by a lack of sensitivity. Novel solutions for specific applications have been developed, however there is a need for more universal approaches. Here we investigated the addition of N 2 to the ICP carrier gas to increase sensitivity, defined as signal-to-background, for the majority of biologically relevant elements. A gelatine standard that contained 38 elements across the mass range was ablated with increasing amounts of N 2 added to the carrier gas post-ablation. The results show that while all elements examined had an increase in signal intensity, some elements did not have a resultant increase in signal-to-background. Sc, V, Mn, Fe, and Se all exhibited a reduction in signal-to-background ratios across all N 2 flow rates examined, with the remaining elements experiencing signal-to-background increases from 1.2-7.8x, depending on the N 2 flow rate and element. A compromised optimum N 2 flow rate was determined for the analysis all elements and used to image endogenous elements in a mouse brain, and antibody-conjugated elements in a quadriceps muscle section. These images confirmed that the addition of N2 to the carrier gas increased the signal-to-background of the analysis, improving image resolution for endogenous elements and low abundant analytes used for immuno-mass spectrometry imaging of biomarkers. These findings offer a promising avenue for advancing the capabilities of LA-ICP-MS in bio-imaging applications.

Toxic heavy metals have been the focus of many investigations into chronic kidney disease of unknown aetiology (CKDu) within Sri Lanka. It has been hypothesised that exposure to nephrotoxic arsenic, cadmium and lead could play a role in the development of CKDu, and these metals have previously been found in unsafe concentrations in Sri Lankan rice. Traditional varieties of Sri Lankan rice remain popular due to their perceived health benefits, but their uptake of trace and toxic heavy metals remained unexplored. Here, we report a one-time, cross-sectional dataset on the concentrations of essential and toxic elements present in eleven samples of polished and unpolished traditional rice varieties, all regularly grown and sold in the Anuradhapura district, a CKDu hotspot. All rice was sourced from the same farm, with the exception of one store bought sample grown on another, unidentified farm. Cadmium concentrations varied significantly between varieties, and potentially unsafe concentrations of cadmium were detected in the store-bought sample (Suwadel, 113±13 μg kg -1 ). Elemental imaging of the grains revealed lead to be stored mainly in the rice bran, which is removed during polishing, while cadmium was distributed in the edible portion of the grain. Essential elements were generally higher in the traditional rice varieties than those reported for non-traditional varieties and are a potential source of trace elements for nutrient-deficient communities. The concentration of selenium, an element that plays a protective role in the kidneys, was too low to provide the minimum recommended intake. The methods developed in this study could be applied to a more comprehensive study of elemental uptake of rice under controlled growing conditions., (© 2023. The Author(s).)

The preparation of matrix-matched material for elemental quantitative analysis in rice flour matrix is proposed here for the first time as part of a feasibility study using the SN-ICP-MS and LA-ICP-MS methods. It was prepared via the spiking process in colloidal solution of rice flour with different levels of arsenic (As), cadmium (Cd) and lead (Pb), followed by drying in a climatic chamber. Comparative studies of the results on external calibration and gravimetric standard addition ICP-MS approaches through the use of calibration standard solutions were discussed. Method bias from the external calibration method was investigated, demonstrating the systematic effect arising from the sample matrix. Characterizing the concentration of measurands was then reasonably proposed using the gravimetric standard addition ICP-MS. Using powdered rice matrix reference material for ICP-MS calibration following acid digestion, the study showed a good agreement of recovery studies. A feasibility study of the LA-ICP-MS method as a direct solid analysis performed on the matrix-matched standard was then discussed. In the study, large fluctuation of signals was found for constructing calibration curve, generating poor linearity, especially for As and Pb, although yttrium (Y) as internal standard was applied. This might be ascribed to a limited microscale of homogeneity, and particularly laser-induced preferential evaporation of volatile elements. Using a number of measured data points, the mean and median were statistically recommended to improve precision. An attempt to use of similar matrix in both standard and sample is a critical point to consider to minimize the elemental fractionation effect. The proposed approach to prepare matrix-matched material could be a potential means for achieving elemental quantitation.

This study explored the uptake of lead in the epigeic earthworm Dendrobaena veneta exposed to 0, 1000, and 2500 μg Pb/g soil. The soil metal content was extracted using strong acid digestion and water leaching, and analysed by means of Inductively Coupled Plasma Mass Spectrometry (ICP-MS) to estimate absolute and bioavailable concentrations of metals in the soil. The guts and heads of lead-exposed earthworms were processed into formalin-fixed and paraffin embedded sections for high-resolution multi-element metallomic imaging via Laser Ablation ICP-MS (LA-ICP-MS). Metallomic maps of phosphorus, zinc, and lead were produced at 15-μm resolution in the head and gut of D. veneta. Additional 4-μm resolution metallomic maps of the earthworm brains were taken, revealing the detailed localisation of metals in the brain. The Pb bioaccumulated in the chloragogenous tissues of the earthworm in a dose-dependent manner, making it possible to track the extent of soil contamination. The bioaccumulation of P and Zn in earthworm tissues was independent of Pb exposure concentration. This approach demonstrates the utility of LA-ICP-MS as a powerful approach for ecotoxicology and environmental risk assessments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

The aim of this work is to evaluate two quantitative methods, based on the external calibration applied in laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis, known as (i) analytical curve and (ii) one-point calibration, using the concept of matrix matching to quantify three potentially toxic elements (PTEs) in wood samples. These can biologically register changes in the abiotic environment and be applied to monitoring climate change or environmental toxicity. In this case, standard sample preparation was evaluated to prepare the standard pellets using Pinus taeda species as a matrix-matching concept. Six pellets of P. taeda, with different Pb, Cd, and Ba concentrations, were prepared to build the analytical curve and one-point calibration strategies. The LA-ICP-MS parameters were optimised for 206 Pb, 208 Pb, 112 Cd, 114 Cd, 137 Ba, and 138 Ba isotope analysis in wood samples. The two calibration strategies provided 74-110% analytical recovery from certified reference materials and similar results to those obtained by ICP-MS through the acid digestion of environmental wood samples from São Paulo City (Brazil). This demonstrated the applicability of the one-point calibration strategy in quantifying PTEs in wood samples, which could be used with environmental analyses. Differences observed between the Ba isotope results obtained via LA-ICP-MS and ICP-MS quantification were related to sampling by LA-ICP-MS and the ICP-MS sample introduction, as well as to laser matrix and transport effects because of the difference between the wood species evaluated., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.)

Innate immune systems alter the concentrations of trace elements in host niches in response to invading pathogens during infection. This work reports the interplay between d-block metal ions and their associated biomolecules using hyphenated elemental techniques to spatially quantify both elemental distributions and the abundance of specific transport proteins. Here, lung tissues were collected for analyses from naïve and Streptococcus pneumoniae-infected mice fed on a zinc-restricted or zinc-supplemented diet. Spatiotemporal distributions of manganese ( 55 Mn), iron ( 56 Fe), copper ( 63 Cu), and zinc ( 66 Zn) were determined by quantitative laser ablation-inductively coupled plasma-mass spectrometry. The murine transport proteins ZIP8 and ZIP14, which are associated with zinc transport, were also imaged by incorporation of immunohistochemistry techniques into the analytical workflow. Collectively, this work demonstrates the potential of a single instrumental platform suitable for multiplex analyses of tissues and labelled antibodies to investigate complex elemental interactions at the host-pathogen interface. Further, these methods have the potential for broad application to investigations of biological pathways where concomitant measurement of elements and biomolecules is crucial to understand the basis of disease and aid in development of new therapeutic approaches., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.)

Multiple sclerosis (MS) is a prevalent immune-mediated inflammatory disease of the central nervous system inducing a widespread degradation of myelin and resulting in neurological deficits. Recent advances in molecular and atomic imaging provide the means to probe the microenvironment in affected brain tissues at an unprecedented level of detail and may provide new insights. This study showcases state-of-the-art spectroscopic and mass spectrometric techniques to compare distributions of molecular and atomic entities in MS lesions and surrounding brain tissues. MS brains underwent post-mortem magnetic resonance imaging (MRI) to locate and subsequently dissect MS lesions and surrounding white matter. Digests of lesions and unaffected white matter were analysed via ICP-MS/MS revealing significant differences in concentrations of Li, Mg, P, K, Mn, V, Rb, Ag, Gd and Bi. Micro x-ray fluorescence spectroscopy (μXRF) and laser ablation - inductively coupled plasma - time of flight - mass spectrometry (LA-ICP-ToF-MS) were used as micro-analytical imaging techniques to study distributions of both endogenous and xenobiotic elements. The essential trace elements Fe, Cu and Zn were subsequently calibrated using in-house manufactured gelatine standards. Lipid distributions were studied using IR-micro spectroscopy and matrix assisted laser desorption/ionisation mass spectrometry imaging (MALDI-MSI). MALDI-MSI was complemented with high-resolution tandem mass spectrometry and trapped ion mobility spectroscopy for the annotation of specified phospho- and sphingolipids, revealing specific lipid species decreased in MS lesions compared to surrounding white matter. This explorative study demonstrated that modern molecular and atomic mapping techniques provide high-resolution imaging for relevant bio-indicative entities which may complement our current understanding of the underlying pathophysiological processes., Competing Interests: Declaration of competing interest Marten Seeba works for Bruker Corporation., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Objectives: Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has considerable applicative potential for both qualitative and quantitative analyses of elemental spatial distribution and concentration. It provides high resolutions at pg-level detection limits. These qualities make it very useful for analyzing biological samples. The present study responds to the growing demand for adequate analytical methods which would allow to assess the distribution of nanostructured molybdenum(IV) disulfide (MoS 2 ) in organs. It was also motivated by an apparent lack of literature on the biological effects of MoS 2 in living organisms. The study was aimed at using LA-ICP-MS for comparing micro- and nanosized MoS 2 ditribution in selected rat tissue samples (lung, liver, brain and spleen tissues) after the intratracheal instillation (7 administrations) of MoS 2 nano- and microparticles vs. controls., Material and Methods: The experimental study, approved by the Ethics Committee for Animal Experiments was performed using albino Wistar rats. This was performed at 2-week intervals at a dose of 5 mg/kg b.w., followed by an analysis after 90 days of exposure. The MoS 2 levels in control tissues were determined with the laser ablation system at optimized operating conditions. The parameter optimization process for the LA system was conducted using The National Institute of Standards and Technology (NIST) glass standard reference materials., Results: Instrument parameters were optimized. The study found that molybdenum (Mo) levels in the lungs of microparticle-exposed rats were higher compared to nanoparticle-exposed rats. The opposite results were found for liver and spleen tissues. Brain Mo concentrations were below the detection limit., Conclusions: The LA-ICP-MS technique may be used as an important tool for visualizing the distribution of Mo on the surface of soft samples through quantitative and qualitative elemental mapping. Int J Occup Med Environ Health. 2024;37(1):18-33., (This work is available in Open Access model and licensed under a CC BY-NC 3.0 PL license.)

Quantification in 2D LA-ICP-MS mapping generally requires matrix-matched standards to minimize issues related to elemental fractionation. In addition, internal standardization is commonly applied to correct for instrumental drift and fluctuation, whereas also differences in ablated mass can be rectified for samples that cannot be sectioned and subjected to total ablation. However, it is crucial that the internal standard element is homogeneously distributed in the sample and that the laser light absorptivity is uniform over the surface. As in practice these requirements are often not met, this work will focus on correction of ablation rate differences within/between samples and standards by normalizing the element maps using the associated ablation volume per pixel as measured by optical profilometry. Due to the volume correction approach the element concentrations are no longer defined as mass per mass concentrations (in μg g -1 ) but by mass per volume concentrations (in μg cm -3 ), which can be interconverted in case matrix densities are known. The findings show that ablation volume-aided calibration yields more accurate element concentrations in 2D LA-ICP-MS maps for a decorative glass with highly varying elemental concentrations (murrina). This research presents a warning that if there are variations in ablation rates between samples and standards within and across matrices, even when their sensitivities are the same, generic LA-ICP-MS calibration protocols may not accurately depict the actual element concentrations., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Alzheimer's disease (AD) is a prevalent neurodegenerative disorder characterized by cognitive decline and neuropathological hallmarks, including β-amyloid (Aβ) plaques, Tau tangles, synaptic dysfunction and neurodegeneration. Emerging evidence suggests that abnormal iron (Fe) metabolism plays a role in AD pathogenesis, but the precise spatial distribution of the Fe and its transporters, such as ferroportin (FPN), within affected brain regions remains poorly understood. This study investigates the distribution of Fe and FPN in the CA1 region of the human hippocampus in AD patients with a micrometer lateral resolution using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). For this purpose, we visualized and quantified Fe and FPN in three separated CA1 layers: stratum molecular-radial (SMR), stratum pyramidal (SP) and stratum oriens (SO). Additionally, chromogenic immunohistochemistry was used to examine the distribution and colocalization with Tau and Aβ proteins. The results show that Fe accumulation was significantly higher in AD brains, particularly in SMR and SO. However, FPN did not present significantly changes in AD, although it showed a non-uniform distribution across CA1 layers, with elevated levels in SP and SO. Interestingly, minimal overlap was observed between Fe and FPN signals, and none between Fe and areas rich in neurofibrillary tangles (NFTs) or neuritic plaques (NP). In conclusion, the lack of correlation between Fe and FPN signals suggests complex regulatory mechanisms in AD Fe metabolism and deposition. These findings highlight the complexity of Fe dysregulation in AD and its potential role in disease progression.

Background: Metals are pervasive throughout biological processes, where they play essential structural and catalytic roles. Metals can also exhibit deleterious effects on human health. Powerful analytical techniques, such as mass spectrometry imaging (MSI), are required to map metals due to their low concentrations within biological tissue., Scope of Review: This Mini Review focuses on key MSI technology that can image metal distributions in situ, describing considerations for each technique (e.g., resolution, sensitivity, etc.). We highlight recent work using MSI for mapping trace metals in tissues, detecting metal-based drugs, and simultaneously imaging metals and biomolecules., Major Conclusions: MSI has enabled significant advances in locating bioactive metals at high spatial resolution and correlating their distributions with that of biomolecules. The use of metal-based immunochemistry has enabled simultaneous high-throughput protein and biomolecule imaging., General Significance: The techniques and examples described herein can be applied to many biological questions concerning the important biological roles of metals, metal toxicity, and localization of metal-based drugs., Competing Interests: Declaration of Competing Interest The authors declare that they have no competing interests., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Toenails are a common monitoring tool for arsenic exposure, but the risk of external contamination of toenails has cast doubt on its usefulness. The main objective of this study is to investigate the micro-distribution of arsenic through the dorsoventral plane of nail clippings to understand endogenous vs exogenous sources. We used laser-ablation inductively coupled plasma mass spectrometry to measure arsenic through a dorsoventral cross-section of the nail plate collected from reference (N = 17) and exposed individuals (N = 35). Our main results showed (1) bulk toenail concentrations measured using ICP-MS in this study ranged from 0.54 to 4.35 µg/g; (2) there was a double-hump pattern in arsenic concentrations, i.e., dorsal and ventral layers had higher arsenic than the inner layer; (3) the double-hump was more pronounced in the exposed group (ventral: 6.25 μg/g; inner: 0.75 μg/g; dorsal: 0.95 μg/g) than the reference group (ventral: 0.58 μg/g; inner: 0.15 μg/g; dorsal: 0.29 μg/g) on average; (4) the distribution was, in part, associated with different binding affinity of nail layers (i.e., ventral > dorsal > inner); (5) most individuals in the higher exposure group showed > 25% contamination in ventral and dorsal nail layers; and (6) there were no statistically significant correlations between LA-ICP-MS arsenic with either bulk toenail arsenic or urine arsenic from the same individuals. Our results on micro-distribution and binding affinity provide insight into the impact of external contamination on arsenic concentrations and show how LA-ICP-MS can access the protected inner nail layer to provide a more accurate result., (© 2024. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

Human hair is a biomarker that is crucial in investigating toxic metal exposures. Thirteen elements (Li, Mg, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Ag, Ba, and Hg) commonly found in hair strands from dentistry environments were investigated using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Previous studies have employed partial ablation along hair strands to avoid contamination from mounting materials. The partial ablation can be problematic if element chemistry within the hair is not homogeneous. In this study, element variations along cross-sections of human hair strands were investigated. A number of elements showed internal variations with most elements enriched at the cuticle, emphasizing the importance of complete ablation for the characterization of human hair element chemistry. Complete and partial ablation LA-ICP-MS results were verified against solution nebulization SN-ICP-MS. Complete LA-ICP-MS showed a better agreement with SN-ICP-MS. Therefore, the developed LA-ICP-MS method can be applied to monitor the health of dental workers and students exposed to dental environments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The cellular accumulation and the underlying mechanisms for the two ruthenium-based anticancer complexes [Ru II (cym)(HQ)Cl] 1 (cym = η 6 -p-cymene, HQ = 8-hydroxyquinoline) and [Ru II (cym)(PCA)Cl]Cl 2 (PCA = N-fluorophenyl-2-pyridinecarbothioamide) were investigated in HCT116 human colorectal carcinoma cells. The results showed that the cellular accumulation of both complexes increased over time and with higher concentrations, and that 2 accumulates in greater quantities in cells than 1. Inhibition studies of selected cellular accumulation mechanisms indicated that both 1 and 2 may be transported into the cells by both passive diffusion and active transporters, similar to cisplatin. Efflux experiments indicated that 1 and 2 are subjected to efflux through a mechanism that does not involve p-glycoprotein, as addition of verapamil did not make any difference. Exploring the influence of the Cu transporter by addition of CuCl 2 resulted in a higher accumulation of 1 and 2 whilst the amount of Pt detected was slightly reduced when cells were treated with cisplatin. Complexes 1 and 2 were further explored in zebrafish where accumulation and distribution were determined with ICP-MS and LA-ICP-MS. The results correlated with the in vitro observations and zebrafish treated with 2 showed higher Ru contents than those treated with 1. The distribution studies suggested that both complexes mainly accumulated in the intestines of the zebrafish., (© 2023. The Author(s), under exclusive licence to Society for Biological Inorganic Chemistry (SBIC).)

Determination of trace element concentrations in continuously growing biological structures such as otoliths, whiskers, and teeth can provide important insight into physiological and ontogenetic processes. We examined concentrations of 11 trace elements (Li, Mg, Mn, Cu, Zn, Se, Rb, Sr, Cs, Ba, Pb) in the annual dentine growth layer groups (GLGs) of teeth of 66 Eastern Canadian Arctic belugas (Delphinapterus leucas). Several of these trace elements displayed clear and consistent patterns in early life, though few longer term trends or signals were present in trace element data for either females or males. Large changes in Sr and Ba concentrations in fetal dentine reflected in utero shifts in element deposition in the teeth of developing belugas. Marked changes in these elements during the first years after birth were likely associated with the onset of nursing and subsequent weaning. Mg, Mn, and Zn also displayed clear and consistent patterns in early life that correlated strongly with dentine stable nitrogen isotope (δ 15 N) data, suggesting these elements merit further study as potential tools for studying nursing and weaning. Depositional patterns of Zn and Pb, which have been linked to sexual maturation in female Pacific walruses (Odobenus rosmarus divergens), were inconsistent in beluga teeth. Some individuals (including males) displayed patterns strongly resembling those observed in female walruses, whereas many animals did not, perhaps because they had not yet reached sexual maturity. The lack of clear patterns in trace element deposition after the first few years of life may have resulted from pooling samples from multiple populations/regions collected across more than two decades, but may also indicate that elemental concentrations are primarily driven by other, extrinsic processes later in life, and might be useful as biomonitors of environmental element concentrations or tools for delineating population structure., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

The gadolinium-based contrast agent Gadoxetic acid and the platinum-based antitumor agent Cisplatin were quantitatively imaged in liver and liver cancer (hepatocellular carcinoma, HCC) tissue of rats by means of laser ablation-inductively coupled plasma-mass spectrometry. HCC bearing rats simultaneously received a tail vein injection of the hepatocyte-specific magnetic resonance imaging contrast agent Gadoxetic acid and a transarterial injection of Cisplatin 15 min before sacrifice and liver removal. Resecting HCC with adjacent liver tissue allows the comparison of Gd, Pt, and endogenous elements like Fe, Cu, and Zn in the various tissue types. Region of interest analysis reveals lower concentrations of Gd in HCC and higher Gd content in the adjacent liver, fitting the selective uptake of Gadoxetic acid into hepatocytes. Furthermore, two malignancy grades and their possible impact on the Gadoxetic acid and Cisplatin uptake are compared. For this, four high grade (G3) and two moderate grade (G2) HCCs were analysed, including a control sample each. Gd concentrations were lower in HCC irrespective of the grade of dedifferentiation (G2, G3) compared to adjacent liver. Despite local arterial Cisplatin injection, concentrations of Pt were similar or also reduced in HCC compared to liver tissue. In addition, endogenous Fe, Cu, and Zn were quantified. While Zn was homogenously distributed, higher Fe concentrations were determined in liver tissue compared to HCC. Hotspots of Cu suggest a deregulated copper homeostasis in certain liver lesions. The Gd and Fe distributions are compared in detail with cellular alterations examined by hematoxylin and eosin staining., (© The Author(s) 2023. Published by Oxford University Press.)

This work presents an indirect method of investigating the elemental diversity of historical inks. The manuscript of Fryderyk Chopin's Impromptu in A flat major, Op. 29 was examined as an example of the proposed approach for testing documents containing different inks. Preliminary in situ X-ray fluorescence (XRF) measurements carried out it the museum storage room provided qualitative reference data for the object. Then, selected areas on the item were examined with indicator papers soaked in 4,7-diphenyl-1,10-phenanthroline (Bphen). The reaction with the ligand enabled the immediate colorimetric detection of Fe(II) in the form of magenta Fe(Bphen) 3 complex. The overall condition of the manuscript with regard to the risk of ink corrosion was assessed in this way. More chemical information were obtained by the proposed elemental imaging-based approach to evaluate chemical heterogeneity of the used indicator paper samples using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The recorded data were visualised in the form of elemental distribution maps. The Fe enriched areas indicated Regions of Interest (ROIs) to approximate composition of the inks from the manuscript. All calculations were done solely for the data mathematically singled out from these areas. The varying proportions of AI, Mn, Co and Cu relative to Fe correlated with the ROIs of the composer's handwriting, editor's notes and stave lines, demonstrating the applicability of the proposed approach for comparative studies., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Barbara Wagner reports financial support was provided by National Science Centre, Poland. Magdalena Kulig reports financial support and administrative support were provided by European Regional Development Fund. Tadeusz Tomaszewski reports financial support and administrative support were provided by European Regional Development Fund., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

A novel method for direct high-throughput analysis of multi-elements in cerebrospinal fluid (CSF) samples by laser ablation inductively coupled plasma mass spectrometry with an aerosol local extraction cryogenic ablation cell (ALEC-LA-ICP-MS) was developed. Microliter-level CSF samples were frozen by a designed cryogenic ablation cell and directly analyzed by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) without time-consuming pretreatment. Compared with the precision obtained at room temperature (20℃), that obtained at low temperature (- 25℃) was significantly improved; the RSDs were reduced from 8.3% (Zn) to 32.6% (Mn) to 2.2% (Pb) to 6.5% (Mn) with six times parallel determination. To meet the analytical requirement of the micro-volume CSF samples, the laminar flow aerosol local extraction strategy was adopted to improve the transmission efficiency of aerosols, and the signal intensity was increased by four times compared with the standard commercial ablation cell. The standard solution with 0.4% bovine serum albumin (BSA) matrix was used as matrix-match external standard, and Rh was added into the samples as internal standard. The limits of detection (LODs) ranged from 0.17 μg·L -1 (Mn) to 8.67 μg·L -1 (Mg). Standard addition recovery experiments and the determination of CRM serum L-1 and L-2 were carried out to validate the accuracy of the method; all results indicated there were excellent accuracy and precision in the proposed method. The matrix-scanning function in the GeoLas software combined with the microwell plate realizes the high-throughput automatic analysis. Twenty-four CSF samples from different patients were determined; the results showed that there might be a correlation between the metal elements in CSF and the diseases, which means that the proposed method has potential in the diagnosis of neurological diseases., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.)

Isotope dilution (ID) analysis is considered one of the most accurate quantitative methods. However, it has not been widely applied to the quantitative imaging of trace elements in biological samples using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), mainly because of difficulties in homogeneously mixing enriched isotopes (the spike) with the sample (e.g., a tissue section). In this study, we present a novel method for the quantitative imaging of trace elements (copper and zinc) in mouse brain sections using ID-LA-ICP-MS. We used an electrospray-based coating device (ECD) to evenly distribute a known amount of the spike ( 65 Cu and 67 Zn) on the sections. The optimal conditions for this process involved evenly distributing the enriched isotopes on mouse brain sections mounted on indium tin oxide (ITO) glass slides using the ECD with the 10 mg g -1 ɑ-cyano-4-hydroxycinnamic acid (CHCA) in methanol at 80 °C. The mass of the spiked isotopes and the tissue sections on the ITO slides was calculated by weighing them on an analytical balance. Quantitative images of Cu and Zn in Alzheimer's disease (AD) mouse brain sections were obtained using ID-LA-ICP-MS. These imaging results showed that Cu and Zn concentrations in various brain regions typically ranged from 10 to 25 μg g -1 and 30-80 μg g -1 , respectively. But it is worth noting that the hippocampus contained up to 50 μg g -1 of Zn, while the cerebral cortex and hippocampus had Cu contents as high as 150 μg g -1 . These results were validated by acid digestion and solution analysis with ICP-MS. The novel ID-LA-ICP-MS method provides an accurate and reliable means for quantitative imaging of biological tissue sections., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Background: Nanoparticles (NPs) are currently found in the world in the form of natural colloids and volcanic ash, as well as in anthropogenic sources, such as nanofertilizers; however, in the literature, there is still a lack of toxicological evidence, risk assessment, and regulations about the use and environmental impact of NPs in the agroindustrial system. Therefore, the aim of this work was to evaluate alterations caused by the presence of AgNPs during the development of soybean plants., Methods: The BRS232 non-transgenic (NT) soybean plant and 8473RR (T RR ) and INTACTA RR2 PRO (T Intacta ) transgenic soybean plants were irrigated for 18 days under controlled conditions with deionized water (control), AgNPs, and AgNO 3 . The isotopes 107 Ag + , 55 Mn + , 57 Fe + , 63 Cu + , and 64 Zn + were mapped in leaves, using 13 C + as an internal standard (IS), and carried out using a laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) technique with a Nd:YAG (213 nm) laser source in the imagagin mode using the LA-iMageS software and also Mathlab., Results: Leaf images showed a low Ag translocation, indicated by the basal signal of this ion. Additionally, the presence of Ag in the ionic form and as NPs altered the homeostasis of 112 Cd + , 64 Zn + , 55 Mn + , 63 Cu + , and 57 Fe + in different ways. Quantitative image analysis was performed for Cu., Conclusion: The behavior of T RR and T Intacta plants was different in the presence of ionic silver or AgNPs, confirming that the metabolism of these two plants, despite both being transgenic, are different. Through the images, it was observed that the response of plants was different in the face of the same stress conditions during their development., Competing Interests: Declaration of Competing Interest The authors declare that they have no competing interests. The funders had no role in the design of the study, the collection, analyses, or interpretation of data, in the writing of the manuscript, or in the decision to publish the results., (Copyright © 2023 Elsevier GmbH. All rights reserved.)

The pigments used by artists since ancient times play an important role in historical, artistic, and cultural investigations. They allow the acquisition of useful information for the study of human and technological development. This research aims at differentiating the various sources of azurite exploited in antiquity, based on the study of minor and trace elements. Azurite is one of the most important blue pigments in art history, widely used during the Middle Age and Renaissance. However, very few studies investigated the provenance of the pigment, so today it is still not possible to clearly identify the sources of azurite exploited in the past. This study is based on the analysis of several samples of azurite belonging to the MUST collection (Museum of Earth Sciences, Sapienza University of Rome, Italy) and coming from different historical localities: UK, Italy, Germany, France, Romania and Slovakia (both representative of the resources within the ancient Kingdom of Hungary), Greece and Russia. The samples were analysed by electron microscopy (EMPA and SEM-EDX) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), with the aim of detecting chemical features that are specific to the different azurite ore deposits. Among the trace elements analysed, Zn, As, Sn, Ca and Sr prove the most suitable for discriminating the origin of the samples, as well as rare earth elements. In particular, Ce and Eu anomalies are suggested as markers for the German and Hungarian localities., Competing Interests: The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Michela Botticelli reports financial support was provided by University of Rome La Sapienza., (© 2023 The Authors.)

The forensic comparison of glass aims to compare a glass sample of an unknown source with a control glass sample of a known source. In this work, we use multi-elemental features from Laser Ablation Inductively Coupled Plasma with Mass Spectrometry (LA-ICP-MS) to compute a likelihood ratio. This calculation is a complex procedure that generally requires a probabilistic model including the within-source and between-source variabilities of the features. Assuming the within-source variability to be normally distributed is a practical premise with the available data. However, the between-source variability is generally assumed to follow a much more complex distribution, typically described with a kernel density function. In this work, instead of modeling distributions with complex densities, we propose the use of simpler models and the introduction of a data pre-processing step consisting on the Gaussianization of the glass features. In this context, to obtain a better fit of the features with the Gaussian model assumptions, we explore the use of different normalization techniques of the LA-ICP-MS glass features, namely marginal Gaussianization based on histogram matching, marginal Gaussianization based on Yeo-Johnson transformation and a more complex joint Gaussianization using normalizing flows. We report an improvement in the performance of the Likelihood Ratios computed with the previously Gaussianized feature vectors, particularly relevant in their calibration, which implies a more reliable forensic glass comparison., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Objectives: The aim of this study was to assess laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) as a tool for measuring concentrations and determining accumulation of copper in frozen liver specimens from cats., Methods: Six frozen liver specimens were evaluated by qualitative copper staining and quantitative flame atomic absorption spectroscopy. Tissue specimens were cryo-sectioned and quantitative bioimaging of copper was performed using LA-ICP-MS. Results were compared with those obtained using conventional methods., Results: Of the six specimens, only one showed positive staining for copper with rhodanine. Using flame atomic absorption spectroscopy (FAAS), one specimen showed a deficient copper level (<100 µg/g dry weight), two specimens had copper within the reference interval (RI; 150-180 µg/g) and three specimens had copper concentrations above the RI. Bioimaging from LA-ICP-MS showed inhomogeneous distribution of hepatic copper. The areas with dense copper accumulation were represented as hotspots in the liver specimens. Hepatic copper quantification by LA-ICP-MS correlated well with copper quantified by FAAS ( r  = 0.96, P  = 0.002)., Conclusions and Relevance: Our findings suggest that quantitative bioimaging by LA-ICP-MS could be used to demonstrate the distribution and concentration of copper in frozen liver specimens from cats. The distribution of copper in these specimens was inhomogeneous with dense accumulation represented as hotspots on tissue sections. A positive correlation of hepatic copper concentrations determined by LA-ICP-MS and FAAS was found. Further studies to establish an RI for hepatic copper using this technique and to further determine its clinical utility are warranted.

Ecologists have long been interested in relevant techniques to track the field movement patterns of fish. The elemental composition of otoliths represents a permanent record of the growing habitats experienced by a fish throughout its lifetime and is increasingly used in the literature. The lack of a predictive and mechanistic understanding of the individual kinematics underlying ion incorporation/depletion limits our fine-scale temporal interpretation of the chemical signal recorded in the otolith. In particular, the rate at which elements are incorporated into otoliths is hypothesized to depend on fish physiology. However, to date, time lags have mostly been quantified on a population scale. Here, we report results from controlled experiments (translocation and artificially enriched environment) on individual trace element incorporation/depletion rates in Salmo trutta (Salmonidae). We reported significant lags (i.e. weeks to months) between changes in water chemistry and the subsequent change in otolith composition and highlighted substantial inter-individual variations in the timing and magnitude of Sr/Ca and Ba/Ca responses. These differences are partially linked to the energetic status (i.e. metabolic rate) of the individuals. It therefore appears that individuals with the highest metabolic rate are more likely to record detailed (i.e. brief) temporal changes than individuals having lower metabolic values. The time taken for environmental changes to be reflected in the growing otolith thus can no longer be assumed to remain a constant within populations. Results from the current study are a step towards the fine reconstruction of environmental histories in dynamic environments., Competing Interests: Competing interests The authors declare no competing or financial interests., (© 2023. Published by The Company of Biologists Ltd.)

Introduction: Common variants in the SLC30A8 gene, encoding the secretory granule zinc transporter ZnT8 (expressed largely in pancreatic islet alpha and beta cells), are associated with altered risk of type 2 diabetes. Unexpectedly, rare loss-of-function (LoF) variants in the gene, described in heterozygous individuals only, are protective against the disease, even though knockout of the homologous SLC30A8 gene in mice leads to unchanged or impaired glucose tolerance. Here, we aimed to determine how one or two copies of the mutant R138X allele in the mouse SLC30A8 gene impacts the homeostasis of zinc at a whole-body (using non-invasive 62 Zn PET imaging to assess the acute dynamics of zinc handling) and tissue/cell level [using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to map the long-term distribution of zinc and manganese in the pancreas]., Methods: Following intravenous administration of [ 62 Zn]Zn-citrate (~7 MBq, 150 μl) in wild-type (WT), heterozygous (R138X +/- ), and homozygous (R138X +/+ ) mutant mice (14-15 weeks old, n = 4 per genotype), zinc dynamics were measured over 60 min using PET. Histological, islet hormone immunohistochemistry, and elemental analysis with LA-ICP-MS (Zn, Mn, P) were performed on sequential pancreas sections. Bulk Zn and Mn concentration in the pancreas was determined by solution ICP-MS., Results: Our findings reveal that whereas uptake into organs, assessed using PET imaging of 62 Zn, is largely unaffected by the R138X variant, mice homozygous of the mutant allele show a substantial lowering (to 40% of WT) of total islet zinc, as anticipated. In contrast, mice heterozygous for this allele, thus mimicking human carriers of LoF alleles, show markedly increased endocrine and exocrine zinc content (1.6-fold increase for both compared to WT), as measured by LA-ICP-MS. Both endocrine and exocrine manganese contents were also sharply increased in R138X +/- mice, with smaller increases observed in R138X +/+ mice., Discussion: These data challenge the view that zinc depletion from the beta cell is the likely underlying driver for protection from type 2 diabetes development in carriers of LoF alleles. Instead, they suggest that heterozygous LoF may paradoxically increase pancreatic β-cell zinc and manganese content and impact the levels of these metals in the exocrine pancreas to improve insulin secretion., Competing Interests: Authors HO and DG are employees of the company Regeneron. GR has received grant funding from and is a consultant for Sun Pharmaceuticals Inc.; however, Sun Pharmaceuticals Inc. was not involved in the study design, collection, analysis, interpretation of data, the writing of this article, or the decision to submit it for publication. The remaining authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Firth, Georgiadou, Griffiths, Amrahli, Kim, Yu, Hu, Stewart, Leclerc, Okamoto, Gomez, Blower and Rutter.)

Sample preparation is a crucial point for quantitative multi-elemental analses by LA-ICP-MS of powdered geological materials. Four different methods are compared in this study with respect to signal stability and intensity as follows: the preparation of glass beads (GlassB) by alkaline fusion method and three grinding and pelletizing methods relying on the use of an organic binder (VanBind, vanillic acid), an adhesive binder (MixGlue, methyl methacrylate) and a sol-gel process for glass formation (SolGel, chemical reaction of tetraethoxysilane), respectively. Sixty elements were analyzed by means of a ns-UV (213 nm) laser ablation system coupled to a single collector sector field ICP-MS with a low or medium mass resolution. Signal stability was found to strongly depend on the sample homogeneity provided by the preparation method. These methods were applied to three geological standard materials (CRM). The following criteria were used to evaluate and compare the methods: (1) proportion of the measurement cycles which are above a given signal intensity threshold (defined here as signal average ± 3 times the standard deviation), (2) signal stability of the analyzed nuclides (internal precision estimated by the relative standard deviations on raw count rates), (3) signal stability of the internal standards added to the samples, (4) external precision estimated by the relative standard deviation over five preparations for each geological CRM. For the majority of the analyzed elements, signals measured for samples prepared with the four methods are reproducible. Specific contamination in one or several elements (Cr, Fe, Co, Ni, Cu, Mo, W, Au and Bi) was observed depending on the sample preparation method. In addition, compared to grinding made with PTFE material, grinding performed with tungsten carbide material was found to produce better homogeneity, especially for the sol-gel and mixing with glue protocols, although some metallic contamination (W and Co) was observed. Thanks to the suppression of grain effects by alkaline melting, the glass bead method systematically provided signal stability and percentage of "over the threshold" close to those of the NIST glasses. This may be explained by the preparation of more homogeneous samples by alkaline melting. Finally, the described methods were found to be reproducible for the majority of the analyzed elements., (© 2023. The Author(s), under exclusive licence to The Japan Society for Analytical Chemistry.)

Zinc is an important component of cellular antioxidant defenses and dysregulation of zinc homeostasis is a risk factor for coronary heart disease and ischemia/reperfusion injury. Intracellular homeostasis of metals, such as zinc, iron and calcium are interrelated with cellular responses to oxidative stress. Most cells experience significantly lower oxygen levels in vivo (2-10 kPa O 2 ) compared to standard in vitro cell culture (18kPa O 2 ). We report the first evidence that total intracellular zinc content decreases significantly in human coronary artery endothelial cells (HCAEC), but not in human coronary artery smooth muscle cells (HCASMC), after lowering of O 2 levels from hyperoxia (18 kPa O 2 ) to physiological normoxia (5 kPa O 2 ) and hypoxia (1 kPa O 2 ). This was paralleled by O 2 -dependent differences in redox phenotype based on measurements of glutathione, ATP and NRF2-targeted protein expression in HCAEC and HCASMC. NRF2-induced NQO1 expression was attenuated in both HCAEC and HCASMC under 5 kPa O 2 compared to 18 kPa O 2 . Expression of the zinc efflux transporter ZnT1 increased in HCAEC under 5 kPa O 2 , whilst expression of the zinc-binding protein metallothionine (MT) decreased as O 2 levels were lowered from 18 to 1 kPa O 2 . Negligible changes in ZnT1 and MT expression were observed in HCASMC. Silencing NRF2 transcription reduced total intracellular zinc under 18 kPa O 2 in HCAEC with negligible changes in HCASMC, whilst NRF2 activation or overexpression increased zinc content in HCAEC, but not HCASMC, under 5 kPa O 2 . This study has identified cell type specific changes in the redox phenotype and metal profile in human coronary artery cells under physiological O 2 levels. Our findings provide novel insights into the effect of NRF2 signaling on Zn content and may inform targeted therapies for cardiovascular diseases., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

In the last years, LA-ICP-MS has become an attractive technique for analyzing solid samples from various research fields. However, application in material science is often hampered by the limited availability of appropriate certified reference materials, which are a precondition for accurate quantification. Thus, frequently in-house prepared standards are used, which match the sample's composition and include all elements of interest at the required concentration levels. However, preparing and characterizing such standards is often labor-intensive and time-consuming. This work proposes a new approach for the fabrication of matrix-matched standards based on the concept of standard addition. In the first step, the analytes of interest are homogeneously deposited onto the sample surface using liquid standards and a spraying device. For analysis, the generated thin layer is ablated simultaneously with the underlying sample. Thereby deviations in the ablation process and particle transport can be avoided. It could be shown that the developed method is highly versatile and could be easily adapted to the actual needs. Using silicon, silicon carbide, copper, aluminum, and glass as a matrix, excellent linear correlations between observed signal intensities and deposited amounts were found for the elements Zn, Ag, In, and Pb (R 2 - values greater than 0.99). The method was applied to determine the content of sulfur, zinc, silver, indium, and lead in a commercial Kapton® polyimide film. The obtained results could be verified based on the homogeneously distributed sulfur by conventional liquid ICP-MS analysis after sample digestion, showing similar precision and accuracy. Lead was found to show a very inhomogeneous distribution in the Kapton® film, with concentration below the LOD at most measured locations and irregularly occurring spots with significantly higher concentrations. Finally, a quantitative depth profile of sulfur in a Kapton® film has been measured to assess the uptake of SO 2 after a weathering experiment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

In this study, a laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) method for in-situ determination of yttrium and trace elements in yttrium-doped barium fluoride (BaF 2 : Y) crystals was proposed. A facile, micro-damage procedure for quantifying the segregation coefficient of doping elements was investigated, and it was found that the actual yttrium doping concentration increases from the seed end to the tail end in BaF 2 : Y crystals. In micro-area analysis, this method has higher mass sensitivity which was applied to quantify the impurity content and distribution during the growth of BaF 2 : Y crystals. Regression coefficient of calibration curve for each element ranged from 0.9918 to 0.9995. Detection limits (DLs) were 0.05, 0.03, 0.01 and 0.01 μg g -1 for Mg, Zn, Sr and Pb, respectively. The accuracy of the proposed method was verified by inductively coupled plasma mass spectrometry/atomic emission spectroscopy (ICP-MS/AES) with wet-chemical pretreatment. The objective of the presented work was to provide a less damaging and more novelty approach for crystal sample analysis., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) studies on trace element concentration and their spatial distribution in CaC 2 O 4 -matrix urinary stones are important but powerfully rely on matrix-matched external calibration. In this work, CaC 2 O 4 precipitate CaOx-1 which was doped with Mg, Cr, Mn, Fe, Co, Cu, Zn, and Sr was prepared by the homogeneous co-precipitation method. It had a homogeneous distribution of major (RSD of 0.46%) and trace elements (RSD of 1.83-6.92%) due to the negligible concentration difference compared with that prepared by the heterogeneous co-precipitation method. Based on this, an analytical method for quantitative determination of elemental concentration in CaC 2 O 4 -matrix samples was established using CaOx-1 as a calibration standard, and the accuracy of this method was assessed by calibrating the elemental concentration in another synthetic CaC 2 O 4 precipitate CaOx-2 with relative deviation (D r ) from - 11.43% (Mn) to 9.76% (Mg). Finally, a methodology for quantitative imaging of Mg, Cr, Mn, Fe, Co, Cu, Zn, and Sr in urinary stones via LA-ICP-MS was developed. From the elemental distributional maps, an annular texture can be found for Mg, Cu, Zn, and Sr, which corresponds to the annular white and brown texture in the real urinary stone. A homogeneous distribution of Fe and low concentrations of Cr and Co were found throughout the stone, while Mn was highly concentrated in the margin of the stone. All these results demonstrate that quantitative distribution patterns of Mg, Cr, Mn, Fe, Co, Cu, Zn, and Sr can be obtained by LA-ICP-MS using CaOx-1 as a calibration standard, which can provide potential evidence for urological and other medical studies., (© 2023. Springer-Verlag GmbH Germany, part of Springer Nature.)

Different jadeites have different characteristics. In this paper, the La-ICP-MS test is used to compare and analyze the elemental characteristics of jadeite in Guatemala and the Qing dynasty. The test results show that the highest value of Guatemalan jadeite Ca can reach 2.5 apfu, while the highest value of Qing dynasty jadeite is 0.73 apfu. The highest value of Na is the same for both. The concentration distribution range and highest value of Guatemalan jadeite and Qing dynasty jadeite Mg/(Mg + Fe) are the same. Guatemalan jadeite and Qing dynasty jadeite have a very wide content of trace elements. Qing dynasty Ca/(Mg + Fe) distribution is wider. Concentrations of Guatemalan and Qing dynasty jadeite Sr/Ba, which is a marine sediment, are greater than 1. The Ba in the Qing dynasty jadeite sediments contains a large amount of clay, resulting in higher levels than the average amount in Guatemalan jadeite Ba. The standard distribution map is similar, showing a "horn" shape. The Sr distribution is uneven. Guatemalan jadeite is heavily enriched in rare earths. Eu shows positive and negative abnormalities. The total rare earth value is 8.15 ppm. Qing Dynasty jadeite shows light rare earth enrichment, and Eu is a positive anomaly. The total rare earth value is 7.07 ppm. The characteristics of the two elements are somewhat similar, but different, which does not rule out the possibility that Qing dynasty jadeite came from Guatemala.

The goal of accurately quantifying trace elements in ultrapure silicon carbide (SiC) with a purity target of 5N (99.999% purity) was addressed. The unsuitability of microwave-assisted acid digestion followed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) analysis was proved to depend mainly on the contamination induced by memory effects of PTFE microwave vessels and by the purity levels of acids, even if highly pure ones were used in a clean environment. A new analytical protocol for the direct analysis of the solid material by laser ablation coupled with ICP-MS (LA-ICP-MS) was then exploited. Different samples were studied; the best results were obtained by embedding SiC (powders or grains) in epoxy resin. This technique has the great advantage of avoiding any source of external contamination, as grinding, pressing and sintering pretreatments are totally unnecessary. Two different laser wavelengths (266 and 193 nm) were tested, and best results were obtained with the 266 nm laser. The optimized protocol allows the determination of elements down to the sub-mg/kg level with a good accuracy level.

Cold seep is characterized by methane-rich fluids released from subsurface reservoirs, and it sustains the chemosynthetic ecosystems on the seafloor. Previous studies suggest that the activity of cold seep could affect the seawater chemistry and ambient temperature. However, the short-term seep activity was hardly reconstructed due to the focus of studies on carbonate or sediment. Vent macrofauna provide such an opportunity by recording in shells the immediate environment in which they grow. The carbonate skeleton of organisms could theoretically preserve environmental variation. Therefore, high-resolution archives are urgently required to understand the influence of cold seep activity on biogeochemistry. In this study, SEM, EDS mapping, EBSD mapping, and LA-ICP-MS analyses were conducted on a clam (Calyptogena sp.) shell collected alive in 2018 from the Haima cold seep in South China Sea. The CaCO 3 , Na, Mg, Sr, and Ba contents and the Sr/Ca, Ba/Ca, and Na/Ca ratios in the hinge plate were measured on LA-ICP-MS by spot analysis and line scanning. The element contents in the hinge are as follows: Mg (38.5-109 μg/g), Na (3117-5246 μg/g), Sr (970-5371 μg/g), and Ba (2.9-11.5 μg/g). The results show that Sr, Re, and Ba content vary synchronously along the direction of growth, but Na has an opposite trend. The element analyses indicate that the eruption of the Haima cold seep was irregular, causing temperature, redox state, and pH changes in the cold seep ecosystem. These findings show that the irregular cold seep activities exert vital influences on the biogeochemistry of the cold seep ecosystem, which shed a light on cold seep biomonitoring., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Single cell-inductively coupled plasma-mass spectrometry (sc-ICP-MS) and laser ablation (LA)-ICP-MS have been complementary employed to develop a comprehensive study of APOE and claudin-1 expression in ARPE-19 cells submitted to a glucose treatment (100 mM, 48 h) that induces oxidative stress conditions. Results were compared with control cells. The determination of the two proteins by ICP-MS was sequentially carried out using specific immunoprobes labelled with IrNCs that offer a huge amplification (1760 ± 90 atoms of Ir on average). A novel sample introduction system, the microFAST Single Cell set-up, was employed for sc-ICP-MS analysis. This introduction system resulted in a cellular transport efficiency of 85 ± 9% for ARPE-19 cells (91 ± 5% using a PtNPs standard). After the proper immunocytochemistry protocol with the specific IrNCs immunoprobes in cell suspensions (sc-ICP-MS), the mass of APOE and claudin-1 in individual ARPE-19 cells was obtained. Average detection limits per cell by sc-ICP-MS were 0.02 fg of APOE and 3 ag of claudin-1. The results of sample analyses obtained by sc-ICP-MS were validated with commercial ELISA kits. The distribution of both target proteins in individual cells (fixated in the chamber wall) was unveiled by LA-ICP-MS. The high amplification provided by the IrNCs immunoprobes allowed the identification of APOE and claudin-1 within individual ARPE-19 cells. High resolution images were obtained using a laser spot of 2 × 2 μm., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:Co-author C. Derrick Quarles Jr. works for Elemental Scientific which manufactures and sells the microFAST Single Cell system used in this work. The authors declare that the reported experimental results are not influenced by competing financial interests or personal relationships., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

The elemental composition of marine mollusk shells can offer valuable information about environmental conditions experienced by a mollusk during its lifespan. Previous studies have shown significant correlations between Mg/Ca concentration ratios measured on biogenic carbonate of mollusk shells and sea surface temperature (SST). Here we propose the use of Laser-Induced Breakdown Spectroscopy (LIBS) and the validation of the Calibration-Free LIBS (CF-LIBS) approach for the rapid measurement and estimation of Mg/Ca molar concentration profiles within Patella depressa Pennant, 1777 limpet shells. To achieve these objectives, results derived from CF-LIBS methodology are compared with those obtained from an established analytical technique for this purpose, such as Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). Concentration series obtained with both methodologies show defined temporal patterns and reflect the season-of-capture in each specimen. The results evidence a significant correlation (R 2  = 0.63-0.81) between CF-LIBS and LA-ICP-MS Mg/Ca molar concentration profiles within four live-collected P. depressa shells. Averaged error for the molar concentration estimated with CF-LIBS was lower than 10% in every specimen. The comparison between the results obtained from two techniques used in this study has allowed us to demonstrate for the first time that Mg/Ca molar concentration measured in biogenic carbonates were accurately inferred using CF-LIBS technique. The CF-LIBS approach validation represents great potential for the rapid and large-scale paleoenvironmental and archaeological analysis of this mollusk species, which is frequently found in archaeological sites., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)