Inductively Coupled Plasma Mass Spectrometry Research Articles

Infants' Exposure to Toxic Trace Elements in Teethers.

Infants are particularly vulnerable to exposure to toxic trace elements due to their developmental stage and behaviors such as mouthing and chewing on toys. Chemical exposure to heavy metals in infants' toys is a significant concern as it poses a threat to their health and well-being. Therefore, quality control measures are essential to prevent infants' exposure to potentially harmful metals. This study aimed to assess the presence of arsenic (As), cadmium (Cd), lead (Pb), and mercury (Hg) in infants' teethers and evaluate potential health risks associated with their use. Eighteen teethers were analyzed for heavy metal content using inductively coupled plasma mass spectrometry (ICPMS). Results showed varying concentrations of As, Cd, Pb, and Hg in the teethers, with none exceeding the safety limits for these heavy metals set by regulatory bodies such as ASTM F-963 and EN 71. Furthermore, calculated exposure levels, including Chronic Daily Intake (CDI) and Lifetime Average Daily Dose (LADD), as well as risk assessments covering Hazard Quotient (HQ), Hazard Index (HI), Margin of Exposure (MOE), and Incremental Lifetime Cancer Risk (ILCR), indicated that the overall health risks associated with teethers' use were non-existent. These findings highlight the importance of stringent regulations and ongoing monitoring of heavy metal levels in infants' products to ensure their safety.

Low Pt Loading on Wolframite-Type NiWO4 to Excel the Electrocatalytic Water Splitting and Ammonia Oxidation Reaction.

Hydrogen production via water-splitting or ammonia electrolysis using transition metal-based electrodes is one of the most cost-effective approaches. Herein, ca. 1-4% of Pt atoms are stuffed into a wolframite-type NiWO4 lattice to improve the electrocatalytic efficiency. The co-existence of atomically dilute quantities of Pt0 and PtIV atoms in the NiWO4 without altering the lattice structure is established via powder X-ray diffraction, inductively coupled plasma mass spectrometry (ICP-MS), core-level X-ray photoelectron spectroscopy, and other spectroscopic studies. While the undoped NiWO4 and a physical mixture of Pt0 (2 wt %) and NiWO4 exhibit poor oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and ammonia oxidation reaction (AOR) activities, 3-4% Pt-enriched NiWO4 depict improved electrocatalytic performances with at least 50 mV overpotential drop for both the OER and HER. The 3%Pt/NiWO4 electrode showcases a long-term (for 110 h) chronoamperometric/chronopotentiometric OER and HER performance, delivering high current at a low working potential. The bifunctional behavior of the material leads to the development of a water-splitting electrolyzer, 3%Pt/NiW/NF(-)/(+)3%Pt/NiW/NF, achieving >90% Faradaic efficiency for H2 production. The onset potential for the AOR is also cathodically shifted for 3%Pt/NiW and 4%Pt/NiW compared to the NiWO4 itself. Electrokinetic study through a rotating ring-disk electrode (RRDE) experiment and the Koutecký-Levich study provides an observed rate constant (kobs) of 1.68 × 10-3 cm s-1 of AOR with a 6e- count from the kinetic current region, highlighting [NO2]- as the major product. The electrolysis of 1 M NH3 using 4%Pt/NiW/NF as a working electrode produces predominantly [NO2]- (FE: 53%) and [NO3]- (FE: 30%). The improved electrocatalytic activity of 3-4% Pt-enriched NiWO4 can be due to the low Tafel slope and charge transfer resistance (Rct). Pt0 being electron-rich induces facile electronic conduction during electrocatalysis and enhances a better binding of the analytes such as H2O, [OH]-, and NH3. At the same time, the PtIV centers present adjacent to the NiII sites can polarize the electron density to stabilize NiIII species and enhance the possibility of OER and AOR. This study demonstrates the effect of hetero-metal doping to tune the electronic structure to improve the electrochemical activity. The low-Pt-doped NiWO4 material is presented here as a multimodal electrocatalyst that can efficiently electrolyze water or ammonia to produce hydrogen.

Ways to Measure Metals: From ICP-MS to XRF.

This review explores the use of Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and X-ray Fluorescence (XRF) for quantifying metals and metalloids in biological matrices such as hair, nails, blood, bone, and tissue. It provides a comprehensive overview of these methodologies, detailing their technological limitations, application scopes, and practical considerations for selection in both laboratory and field settings. By examining traditional and novel aspects of each method, this review aims to guide researchers and clinical practitioners in choosing the most suitable analytical tool based on their specific needs for sensitivity, precision, speed, and sample preparation. Recent studies highlight enhanced capabilities of both ICP-MS and XRF technologies, making them more adaptable to various analytical needs. ICP-MS is renowned for its unmatched sensitivity and precision in detecting ultra-trace metals and metalloids in complex biological samples, such as lead in plasma or seawater. XRF advancements include lower detection limits and reduced sample preparation time, enabling rapid, non-destructive analyses, ideal for quick field assessments. Portable XRF analyzers have revolutionized on-the-spot testing, providing robust data without traditional wet-lab constraints. Moreover, hybrid techniques combining ICP-MS and XRF features are emerging, offering rapid and precise metal analysis for environmental monitoring, clinical diagnostics, and epidemiological studies. Matching analytical methods to specific research demands is critical. ICP-MS is the gold standard for detailed quantitative analysis in laboratories, while XRF excels in non-destructive, immediate field applications. Selection should consider sample complexity, sensitivity, speed, and cost-efficiency. Integrating ICP-MS and XRF offers a versatile approach to metals analysis, transforming practices in environmental science and healthcare diagnostics. As these technologies evolve, they are promising to expand capabilities in detecting and understanding the roles of metals and metalloids in health and the environment.

Knock-out mouse models and single particle ICP-MS reveal that SP-D and SP-A deficiency reduces agglomeration of inhaled gold nanoparticles in vivo without significant changes to overall lung clearance

The role of surfactant proteins A and D (SP-A and SP-D) in lung clearance and translocation to secondary organs of inhaled nanoparticles was investigated by exposing SP-A and SP-D knockout (AKO and DKO) and wild type (WT) mice nose-only for 3 hours to an aerosol of 20 nm gold nanoparticles (AuNPs). Animals were euthanised at 0-, 1-, 7- and 28-days post-exposure. Analysis by inductively coupled plasma mass spectrometry (ICP-MS) of the liver and kidneys showed that extrapulmonary translocation was below the limits of detection. Imaging of the lungs by laser ablation ICP-MS confirmed the homogenous distribution of AuNPs. Coherent anti-Stokes Raman Scattering, Second Harmonic Generation and Two-Photon Fluorescence imaging were applied for semi-quantitative analysis of the uptake of AuNPs by alveolar macrophages and found uptake increased with time post-exposure, peaking after 7 days, and with the largest increase in uptake being in WT mice. Single particle ICP-MS allowed particle counting and sizing of AuNPs in the lungs showing that particle agglomeration following deposition within the lung was greater for the wildtype than the knockout models, indicating a role for SP-A and SP-D in agglomeration, however, any effect of this on overall lung clearance was minimal. For all groups, the Au (mass) lung burden initial clearance half-time was approximately 20–25 d, however, the AuNP (particle number) lung burden clearance half-time was shorter at approximately 10 days. In general terms, differences between the results for the three models were limited, indicating the preferential clearance of smaller particles from the lung.

A novel method for multi-matrix arsenic speciation analysis by anion-exchange HPLC-ICP-MS in the framework of the third (French) total diet study.

This study presents the development and validation of a precise analytical method for the speciation analysis of arsenic (As) compounds, including inorganic species [As(III) and As(V)] and organic species such as monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA). The method employs anion-exchange high-performance liquid chromatography (AE HPLC) coupled with inductively coupled plasma-mass spectrometry (ICP-MS). To optimize the sample preparation process, microwave-assisted extraction (MAE) and heat-assisted extraction (HAE) techniques were evaluated and compared. Separation of all four arsenic species was achieved with baseline resolution within 10 min, utilizing an anion-exchange column and a mobile phase gradient of 0.5 and 5 mM ammonium carbonate with 3% (v/v) methanol at a pH of 9.3. The method validation followed the accuracy profile approach, employing six different food matrices analyzed in duplicate over six separate days within a 6-week period. The method demonstrated good intermediate reproducibility, with coefficients of variation (CVR) ranging from 4.7% to 5.5%, while the bias was < 3%. The limit of quantification (LOQ) for the four species was 6.25 μg/kg (dry weight, dw), and the limit of detection (LOD) was 1.88 µg/kg (dw). These results confirm the robustness, accuracy, and suitability of the method for routine As speciation analysis across a variety of food matrices. The method is specifically intended to be applied to the analysis of a panel of food samples as part of the ongoing (French) third total diet study.

Ultrasound-Assisted Determination of Selenium in Organic Rice Using Deep Eutectic Solvents Coupled with Inductively Coupled Plasma Mass Spectrometry

As the focus on green chemistry intensifies, researchers are progressively looking to incorporate biodegradable and environmentally friendly solvents. Given the prevalent use of inorganic solvents in conventional methods for detecting selenium content, this study utilized a mixture design approach to create four deep eutectic solvents (DESs). The elements of the DESs consisted of six different compounds: guanidine hydrochloride, fructose, glycerol, citric acid, proline, and choline chloride. The synthesized deep eutectic solvents (DESs) exhibited a uniform and transparent appearance. The ideal ratios for each DES were established based on their density and viscosity measurements, leading to the formulations of DES1 (34% guanidine hydrochloride, 21% fructose, 45% water), DES2 (23% guanidine hydrochloride, 32% glycerol, 45% water), DES3 (27.5% citric acid, 27.5% proline, 45% water), and DES4 (30% choline chloride, 25% citric acid, 45% water). The characterization of the deep eutectic solvents (DESs) was performed using nuclear magnetic resonance (NMR) spectroscopy and infrared (IR) spectroscopy, which confirmed the molecular formation of each DES. Following this, the DESs were applied as extraction solvents in a process involving ultrasonic-assisted microextraction (UAE) combined with inductively coupled plasma mass spectrometry (ICP-MS) to assess the selenium levels in selenium-rich rice. The results were benchmarked against traditional microwave-assisted acid digestion (TM-AD), revealing selenium recovery rates ranging from 85.5% to 106.7%. These results indicate that UAE is an effective method for extracting selenium from selenium-rich rice, thereby establishing a solid data foundation for the environmentally friendly analysis of selenium content in rice.

Flow environment affects nutrient transport in soft plant roots.

This work estimates Michaelis-Menten kinetics parameters for nutrient transport under varying flow rates in the soft roots of Indian mustard (Brassica juncea) using a plant fluidic device. To find the metallic components within the roots, inductively coupled plasma mass spectrometry (ICP-MS) analysis was performed. The flow rate-dependent metabolic changes were examined using Raman spectral analysis. In addition, three-dimensional numerical simulations were conducted to assess mechanical stresses resulting from the concentration difference that enhances osmotic pressure and flow loading at the root-liquid interface. Convection, the primary mode of nutrient transport in flowing media, was observed to reduce nutrient uptake at higher flow rates. In contrast, diffusion became more prevalent in areas where the complex root structure restricted the flow field. The concentration gradient between the upstream and downstream regions of the root caused nutrient diffusion from downstream to upstream. As seen, an increase in flow rate resulted in a decrease in root length due to the reduction of advantageous metabolites, which led to lower average mechanical stress and osmotic pressure loading. Additionally, osmotic pressure at the root-liquid interface was found to increase over time. Numerical simulations revealed that the average internal mechanical stress was substantially greater when osmotic pressure was considered. This emphasizes the importance of accounting for osmotic pressure when assessing mechanical stress in roots. This study uses a fluidic device that replicates hydroponic conditions for the first time in order to evaluate the convection-dependent Michaelis-Menten kinetics of nutrient uptake in plant roots.

The effects of occupational aluminum exposure on blood pressure and blood glucose in workers - A longitudinal study in northern China.

Trace element and metal exposure is closely related to the occurrence of chronic diseases, particularly affecting blood pressure and blood glucose. Current studies suggest that heavy metal exposure is a risk factor for hypertension and diabetes. Aluminum can enter the human body through daily life and occupational exposure from food, environment, drugs, and other sources, affecting the cardiovascular, endocrine, and other systems. Therefore, it is significant to observe the effect of aluminum on blood pressure and blood glucose in workers with high concentration. In this study, electrolytic workers naturally exposed to high concentrations of aluminum were selected. The aim of the 5-year cohort study was to investigate the effects of continuous occupational aluminum exposure on blood pressure and blood glucose in workers and to assess the risk of potential cardiovascular and metabolic diseases due to heavy metal exposure. In 2014, 183 participants from an electrolysis workshop at an aluminum plant in Shanxi were enrolled. Inductively coupled plasma mass spectrometry (ICP-MS) was performed to determine the plasma aluminum (P-Al) concentration of the workers and measured their blood pressure and glucose levels. At the 2019 follow-up, all parameters were measured again in the same workers. The relationship of the P-Al concentration with blood pressure and glucose levels was assessed using generalized linear regression, and risks of developing hypertension and hyperglycemia (diabetes or pre-diabetes) due to Al exposure were assessed using binary logistic regression. Dose-response relationships between average annual rates of change in P-Al and average annual rates of change in blood pressure and blood glucose were analyzed using RCS. The relative risk (RR) and attributable risk (AR) were also calculated. Generalized linear regression showed that the average annual rate of change in P-Al concentration was positively correlated with the annual rates of change in SBP, DBP, and blood glucose levels, with each e-fold increase in P-Al concentration increasing the annual rates of change in SBP and DBP by 3.55 % (P < 0.01) and 3.43 % (P = 0.03), respectively. Binary logistic regression showed that as the average annual rate of change in P-Al concentration (categorical variable) increased, the risk of developing hypertension increased (Ptrend < 0.05). The RCS results showed that the relationship between the average annual rate of change in P-Al and the average annual rate of change in SBP was a showed a dose-response relationship (P for overall association<0.05). RR and AR increased with increasing P-Al concentration in both hypertensive and diabetic patients. Persistent occupational aluminum exposure is associated with elevated blood pressure levels in workers and increases the risk of developing hypertensive disorders.

Seasonal Changes in the Elemental Composition of Five Valuable Fish Species (Sparidae) from Bozcaada, North Aegean Sea: A Health Risk and Nutritional Benefit Assessment.

This study investigates the seasonal variations in the elemental composition of five economically valuable Sparidae fish species from Bozcaada, North Aegean: red seabream (Pagrus major), gilthead seabream (Sparus aurata), saddled seabream (Oblada melanura), white seabream (Diplodus sargus), and common dentex (Dentex dentex), with a focus on both essential minerals and toxic metals. Fish samples (n = 10 per species per season) were collected across four seasons, and their weights and lengths were recorded. The concentrations of elements such as calcium, potassium, magnesium, phosphorus, copper, iron, manganese, zinc, chromium, nickel, selenium, cadmium, and mercury were analyzed using Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The elemental concentrations varied as follows: Ca (11,388.46-55,470.76), K (17,230.83-27,594.86), Mg (1436.02-2326.73), Na (1962.30-7847.41), P (13,112.11-15,516.57), Fe (107.61-282.00), Cu (36.44-59.13), Mn (6.19-19.87), Zn (98.67-256.26), Cr (4.54-11.96), Ni (6.33-13.89), Se (0.82-7.33), Cd (0.08-0.32), and Hg (0.08-1.50) mg/kg. Health risk assessments, including Estimated Weekly Intake (EWI), Target Hazard Quotient (THQ), and Cancer Risk (CR), were calculated for both adult and child consumers. The results showed that while the essential minerals remained within safe limits, seasonal variations in the concentrations of toxic metals could pose potential health risks, particularly with frequent consumption. This research provides valuable insights into balancing the nutritional benefits and safety of fish from Bozcaada, offering recommendations for informed consumption and public health policies aimed at optimizing benefits while minimizing risks.

Use of laser-ablation inductively-coupled mass spectroscopy for analysis of selenosugars bound to proteins.

We previously used high pressure liquid chromatography (HPLC) coupled with Se-specific inductively coupled plasma mass spectrometry (ICP-MS) and molecule specific (ESI Orbitrap MS/MS) detection to study the increase in liver Se in turkeys and rats supplemented as selenite in high-Se (5 µg Se/g diet) and adequate-Se diets. We found that far more Se is present as selenosugar (seleno-N-acetyl galactosamine) than is present as selenocysteine (Sec) in true selenoproteins. In high-Se liver, the increase in liver Se was due to low molecular weight (LMW) selenometabolites as glutathione-, cysteine- and methyl-conjugates of the selenosugar, but also as high molecular weight (HMW) species as selenosugars decorating general proteins via mixed-disulfide bonds. To demonstrate selenosugar binding to proteins, aqueous liver extracts from animals fed Se-adequate and high-Se were subjected to SDS-PAGE and Native-PAGE with and without pretreatment with β-mercaptoethanol (βME). The separated proteins were then electrophoretically transferred to membranes, and the membranes subsequently were subjected to laser-ablation inductively-coupled mass spectroscopy (LA-ICP-MS) analysis of 78Se profiles. Without βME treatment, 78Se was widely distributed across the molecular weight profile for both SDS-PAGE and Native-PAGE, whereas βME pretreatment dramatically reduced 78Se binding, reducing the profile to true Sec-selenoproteins. This reduction was ∼50% for both high-Se rat and turkey extracts. The increased 78Se in non-βME treated samples was distributed across the full profile. The use of LA-ICP-MS indicates that selenosugar residues are bound to protein subunits of multiple sizes, and that targeted attachment of selenosugars to a single or limited number of protein subunits does not occur.

Mo and Sn exposure associated with the increased of bone mineral density.

Bone mineral density (BMD) measured by T-score is strongly associated with bone health, but research on its association with metals in humans body remains limited. To investigate the relationship between metal exposure and BMD, numbers of 159 participants in eastern China were studied. Urine and blood samples were collected and levels of 20 metals in the samples were measured using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). Binary Logistic Regression model (BLR) and Generalized Linear Models (GLM) were used to explore the relationship between metals and BMD. Bayesian Kernel Machine Regression (BKMR) model was further used to explore the effect of multiple metal interactions on BMD. Six metals (Mn, Co, As, Se, Mo, Cd) were selected and the concentrations in blood and urine were compared using Wilcoxon and Spearman tests. In the single-metal model, BLR and GLM commonly showed positive significant correlations between four metals (As, Mo, Se, Sn) in urine and BMD. Strong correlations between five metals (Mn, Co, As, Se, Mo) in blood and urine were observed (P ≤ 0.05). The BKMR model indicated a predominant synergistic effect of urine Mo and Sn, increased co-exposure to these metals is associated with a higher trend of BMD. These findings suggest that exposure to metals is associated with an increased level of BMD in humans. To better understand the impact of metalson bone health, further investigation into the common roles of these metals and their interactions is needed.

Optimised determination of arsenic and lead in tea samples using microwave-assisted digestion and ICP-MS: method validation and health risk assessment

ABSTRACT Heavy metal contamination in tea poses significant risks to consumer health, necessitating the development of accurate and efficient analytical methods for routine monitoring. This study aimed to optimise and validate a robust process for the simultaneous determination of arsenic (As) and lead (Pb) in dried tea samples using inductively coupled plasma mass spectrometry (ICP-MS) following microwave-assisted digestion. These toxic elements were selected due to their known health risks and their frequent detection in tea. The method was systematically optimised for digestion parameters and validated following EURACHEM guidelines to ensure accuracy and precision. Key validation metrics included linearity (R2 ≥0.9999), limits of quantification (LOQ) of 0.25 µg/kg for As and 1.5 µg/kg for Pb, sufficient for regulatory compliance. The method demonstrated excellent mean recoveries (75%–89%) and relative standard deviations (RSDs) below 15% across all fortification levels. Precision and accuracy were further verified through proficiency testing, yielding acceptable z-scores for both analytes. Application of the validated method to tea samples collected from Egypt revealed arsenic concentrations ranging from 0.018 ± 0.004 to 0.280 ± 0.070 mg/kg and lead concentrations from 0.083 ± 0.021 to 1.630 ± 0.407 mg/kg. Although detection rates were elevated, the calculated target hazard quotient (THQ) values for As and Pb were below the threshold of 1, suggesting no significant non-carcinogenic health risks associated with tea consumption. This study provides a reliable, cost-effective analytical framework for monitoring heavy metal contamination in tea products, supporting consumer safety and public health initiatives.

Intranasal iron administration induces iron deposition, immunoactivation, and cell-specific vulnerability in the olfactory bulb of C57BL/6 mice.

Iron is the most abundant transition metal in the brain and is essential for brain development and neuronal function; however, its abnormal accumulation is also implicated in various neurological disorders. The olfactory bulb (OB), an early target in neurodegenerative diseases, acts as a gateway for environmental toxins and contains diverse neuronal populations with distinct roles. This study explored the cell-specific vulnerability to iron in the OB using a mouse model of intranasal administration of ferric ammonium citrate (FAC). Olfactory function was assessed through olfactory discrimination tests, while iron levels in OB tissues, cerebrospinal fluid (CSF), and serum were quantified using inductively coupled plasma mass spectrometry (ICP-MS), immunohistochemical staining, and iron assays. Transcriptomic changes and immune responses were assessed using RNA sequencing and immune cell infiltration analysis. Results showed that intranasal FAC administration impaired olfactory function, accompanied by iron deposition in the olfactory mucosa and OB, as well as damage to olfactory sensory neurons. Notably, these effects occurred without elevations in CSF or serum iron levels. OB iron accumulation activated multiple immune cells, including microglia and astrocytes, but did not trigger ferroptosis. Spatial transcriptomic sequencing of healthy adult mouse OBs revealed significant cellular heterogeneity, with an abundance of neuroglia and neurons. Among neurons, GABAergic neurons were the most prevalent, followed by glutamatergic and dopaminergic neurons, while cholinergic and serotonergic neurons were sparsely distributed. Under iron-stressed conditions, oligodendrocytes, dopaminergic neurons, and glutamatergic neurons exhibited significant damage, while GABAergic neurons remained unaffected. These findings highlight the selective vulnerability of neuronal and glial populations to iron-induced stress, offering novel insights into the loss of specific cell types in the OB during iron dysregulation.

Evaluation of Bioactive Compounds and Chemical Elements in Herbs: Effectiveness of Choline Chloride-Based Deep Eutectic Solvents in Ultrasound-Assisted Extraction.

In this study, the effectiveness of three choline chloride (ChCl)-based deep eutectic solvents (DESs) formed using malonic acid (MalA), glycerol (Gly), and glucose (Glu) as hydrogen bond donors and two conventional solvents (50% methanol and 50% ethanol) for ultrasonic-assisted extraction (UAE) of antioxidant compounds from four herbs (chamomile, lemon balm, nettle, and spearmint) were estimated. The antioxidant capacity (AC) of the obtained herb extracts was determined by the modified 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), 2,2-diphenyl-1-picrylhydrazyl (DPPH), and cupric reducing antioxidant capacity (CUPRAC) methods. Profiles of phenolic acids, flavonoid aglycones, and flavonoid glycosides in the green and conventional herb extracts were quantitatively analyzed using ultra-performance liquid chromatography (UPLC). Among the prepared DESs, the highest antioxidant potential and total contents of phenolic acids, flavonoid aglycones, and flavonoid glycosides in herb extracts were achieved using ChCl:MalA (1:1). Unexpectedly, the selected green solvents extracted significantly lower amounts of total antioxidants from the investigated herbs than 50% alcohols. Additionally, macroelements (K, Na, Ca, Mg), micronutrients (Mn, Zn, Fe, Cu), and a toxic element (Cd) in four herbs were analyzed using inductively coupled plasma-mass spectrometry (ICP-MS). Determining the compositions of antioxidants and elements in herbs is essential for understanding their nutritive importance when applied in the food, cosmetic, and pharmaceutical industries.

Ultrasound-Assisted Extraction Followed by Inductively Coupled Plasma Mass Spectrometry and Multivariate Profiling of Rare Earth Elements in Coffee.

A rapid and efficient ultrasound-assisted extraction (UAE) procedure followed by inductively coupled plasma mass spectrometry (ICP-MS) was developed for the determination of 14 rare earth elements (REEs) (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), along with yttrium (Y) and scandium (Sc), in coffee samples. The method was validated using certified reference material (NIST SRM 1547), recovery tests at four fortification levels, and comparisons with microwave-assisted digestion (MAD). Excellent accuracy and precision were achieved, with recovery rates ranging from 80.1% to 112% and relative standard deviations (RSD%) below 14%. Limits of detection (LODs) ranged from 0.2 ng/kg (Yb) to 0.16 µg/kg (Nd). Total REE concentrations varied between 8.3 µg/kg and 1.1 mg/kg, with the highest individual mean concentrations (µg/kg) observed for Ce (11.7), La (6.0), and Sc (4.7). The lowest individual mean concentrations (µg/kg) were for Ho (0.16), Lu (0.066), and Tm (0.063). Multivariate analysis of REE profiles from 92 coffee samples collected in Serbia revealed clear distinctions between ground roasted and instant coffees, as well as between different surrogate blends. This study indicated that the determination of coffee's geographical origin was not possible due to the diverse types, blends, and additives. However, differences in REE profiles suggest potential classification based on variety. REEs pose a negligible health risk to coffee consumers, with HI values ranging from 4.7 × 10-8 to 6.3 × 10-6 and TCR ranging from 2.6 × 10-14 to 3.5 × 10-12.

Study of Ultrasound-Assisted Low-Pressure Closed Acid Digestion Method for Trace Element Determination in Rock Samples by Inductively Coupled Plasma Mass Spectrometry.

In this paper, a method of ultrasound-assisted low-pressure closed acid digestion followed by inductively coupled plasma mass spectrometry (ICP-MS) analysis was proposed for trace element quantification in rock samples. By using 1.5 mL of a binary acid mixture of HNO3-HF with a ratio of 2:1, rock powder samples of 50 mg were completely decomposed in 12 h at 140 °C after 4 h of ultrasonic treatment with or without pressure relief procedure. The element extraction efficiency of this method was evaluated via the yielded relative errors (REs) of the trace elements in a series of geological standard reference materials (SRMs) with compositions from basic to acidic. It was found that the contents of trace elements (i.e., 36 metal elements from Li to U) in basalt BCR-2, diabase W-2a, andesite AGV-2, granodiorite GSP-2, and granite GSR-1 were comparable with the reported reference values, giving REs with absolute values less than 10%. It was also found that clear solutions without sample powder residues by naked-eye observation can be obtained when using the low-pressure closed decomposition method without ultrasonic pretreatment. The quantification results, however, were found to be negatively biased for most of the studied trace elements, and, in particular, the content bias of Zr in SRM GSP-2 was down to -86.28% due to the low extraction efficiency of refractory minerals of the low-pressure closed digestion method. By applying this proposed digestion strategy, the decomposition property of the ternary combination of HNO3-HF-mannitol in terms of trace element quantification accuracy was also investigated. Results showed that the concentrations of trace elements in the studied SRMs were consistent with the reference values, giving REs within ±6.94%, which revealed that there was no deterioration of extraction efficiencies of trace elements and neglected mass interferences from mannitol. This study demonstrated the essential role of ultrasound irradiation in rock sample decomposition to achieve the high extraction efficiency of trace elements under a low-pressure environment, and the developed approach with promising future applications in geoscience exhibited considerable merits, including a high extraction efficiency, feasible digestion process, less time consumption, and lower safety associated risks.

Zinc, copper, copper-to-zinc ratio, and other biometals in blood serum and tumor tissue of patients with colorectal cancer.

The objective of the present study was to assess serum and cancerous tissue biometal levels in colorectal cancer (CRC) patients, and its relation to disease severity. A total of 90 CRC patients and 97 controls were involved in the present study. The level of biometals in blood serum and colon tissues (only in CRC cases) was evaluated by inductively-coupled plasma mass-spectrometry. CRC patients are characterized by lower serum Ca, Fe, Se, and Zn, as well as higher serum Co, Cu, Mg, V, and Cu/Zn ratio compared to healthy controls. The lowest serum Zn levels and the highest Cu concentration and Cu/Zn ratio were observed in patients with the largest tumor size. Regression analysis demonstrated that tumor size is a significant negative predictor of serum Se levels, being positively associated with serum Cu/Zn values. The degree of metastasis to regional lymph nodes was inversely associated with circulating Ca, Co, Mg, Zn, and Mn levels. Serum Mg and Mn levels were positively associated with the stage of the disease and tumor location, respectively. Cancerous tissue Ca and Mo levels were lower, while Mg content was higher compared to healthy adjacent tissues. In cancerous tissues a constant but non-significant trend to elevation of tissue Zn content with increasing tumor size was observed. In addition, serum Cu, Zn, and Cu/Zn values positively correlated with the respective tumor values. These findings demonstrate that altered biometal metabolism is associated with CRC, while systemic Cu/Zn ratio may be indicative of Cu and Zn imbalance in cancerous tissue.

Tempo-Spatial Tungsten Metallogeny in the Xing’an–Mongolia Orogenic Belt: Insights from the Early Cretaceous Shamai Tungsten Deposit Case Study in Northeastern China

The Xing’an–Mongolia Orogenic Belt (XMOB) is located in the eastern part of the Central Asian Orogenic Belt (CAOB). The region’s notable tectonic complexity and extensive tungsten mineralization offer a unique opportunity to explore metallogeny mechanisms in orogenic areas. This study focuses on the Shamai tungsten deposit as a case study, presenting results from LA–ICP–MS U–Pb dating of fine-grained, medium-grained, and porphyritic biotite monzogranite samples from the deposit, along with in situ zircon Hf isotopic and plagioclase Pb isotopic analyses. The fine-grained, medium-grained, and porphyritic biotite monzogranite were emplaced at 142.5, 141.9, and 140.2 Ma, respectively. These samples contain zircons with εHf(t) values ranging from 3.2 to 7.9 and 4.2 to 7.6, respectively, yielding TDM2 model ages from 996 to 692 Ma and 923 to 708 Ma. These findings suggest that the magmas in the Shamai deposit were produced by partial melting of juvenile crustal material mixed with mantle-derived components. The tungsten mineralization periods in the Eastern XMOB region can be divided into three stages: Early Paleozoic (ca. 520–475 Ma), Triassic (ca. 250–200 Ma), and Jurassic to Early Cretaceous (ca. 190–130 Ma). The highest concentration of tungsten mineralization in the XMOB occurs within the Xing’an Block during the Jurassic to Early Cretaceous period. Yanshanian magmatism and the most significant tungsten metallogenic events are likely influenced by an extensional setting and oceanic slab rollback, shaped by the tectonic evolution of the Mongol-Okhotsk Ocean and the Paleo-Pacific Ocean.

Exploring Nanoplastics Bioaccumulation in Freshwater Organisms: A Study Using Gold-Doped Polymeric Nanoparticles.

The evaluation of nanoplastics bioaccumulation in living organisms is still considered an emerging challenge, especially as global plastic production continues to grow, posing a significant threat to humans, animals, and the environment. The goal of this work is to advance the development of standardized methods for reliable biomonitoring in the future. It is crucial to employ sensitive techniques that can detect and measure nanoplastics effectively, while ensuring minimal impact on the environment. To understand nanoplastics retention by freshwater organisms, phyto- and zooplankton, and mussels were exposed to gold-doped polymeric nanoparticles synthesized in our laboratory. The results demonstrated that measuring gold content using inductively coupled plasma mass spectrometry (ICP-MS), along with confirmation of its presence through electron microscopy in selected exposed samples provides insight into the accumulation and release of nanoplastics by organisms playing a relevant ecological role at the early levels of aquatic food webs.

Chemical and in vivo analyses of calcium silicate-based materials in bone and connective tissues.

Calcium silicate-based cements have been widely used in dentistry mainly due to their physicochemical and biological properties. Commercially available materials use radiopacifiers containing metals (bismuth, tantalum, tungsten and/or zirconium). To investigate volumetric changes, in vivo biocompatibility and systemic migration from eight commercially available materials, including powder/liquid and 'ready-to-use' presentations. After characterization, tubes were implanted in healthy Wistar rats' alveolar bone and subcutaneous tissues. Micro-CT was used to evaluate volumetric change before/after 30 days of implantation. Histological and immunohistochemistry analysis were used to evaluate materials' biocompatibility. After euthanasia, kidney samples were retrieved, acidic digested and evaluated by inductively coupled plasma mass spectrometry (ICP-MS) for bismuth, tantalum, tungsten and zirconium mass fractions. Statistical analysis compared the results for normality and comparisons adopted a level of significance of 0.05. Characterization photomicrographs and spectroscopy analysis revealed calcium, silicon and radiopacifiers for tested cements. Volumetric changes after implantation showed higher alteration in subcutaneous tissues than alveolar bone indicating that Biodentine, EndoSequence BC RRM Putty and ProRoot MTA were the most stable materials. Histological analysis found intense inflammation for NeoPUTTY and moderate for the other materials; osteocalcin and osteopontin were positively marked for all materials. Despite its volumetric stability, ProRoot MTA showed a 1000-fold higher mass fraction of bismuth accumulation and MTA Repair HP a 37-fold higher tungsten accumulation in kidney samples when compared with the nonexposed controls. All tantalum-analysed samples indicated a similar mass fraction with the nonexposed controls. Biodentine exhibited a significant lower kidney mass fraction of zirconium accumulation when compared with this control. Volumetric analysis revealed that Bio-C Repair, NeoPUTTY and MTA Repair HP presented greater volumetric loss when implanted in the subcutaneous tissue. NeoPUTTY presented more intense inflammatory infiltrate. Systemic migration analysis highlighted the predominance of bismuth in the ProRoot MTA group. These results suggest that endodontic repair cements are affected by their chemical composition, the type of implant tissue and different clinical settings.