Compost amendment in urban gardens: elemental and isotopic analysis of soils and vegetable tissues.

Urban horticulture poses a sustainable form of food production, fosters community engagement and mitigates the impacts of climate change on cities. Yet, it can also be tied to health challenges related to soil contamination. This work builds on a previous study conducted on eleven urban gardens in the city of Vienna, Austria. Following the findings of elevated Pb levels in some soil and plant samples within that project, the present study investigates the elemental composition of soil and plants from two affected gardens 1 year after compost amendment. Inductively coupled plasma mass spectrometry (ICP-MS) analysis of skin, pulp and seeds of tomato fruits revealed minor variations in elemental composition which are unlikely to have an impact on food safety. In turn, a tendency of contaminant accumulation in root tips and leaves of radishes was found. Washing of lettuce led to a significant reduction in the contents of potentially toxic elements such as Be, Al, V, Ni, Ga and Tl, underscoring the significance of washing garden products before consumption. Furthermore, compost amendments led to promising results, with reduced Zn, Cd and Pb levels in radish bulbs. Pb isotope ratios in soil and spinach leaf samples taken in the previous study were assessed by multi-collector (MC-) ICP-MS to trace Pb uptake from soils into food. A direct linkage between the Pb isotopic signatures in soil and those in spinach leaves was observed, underscoring their effectiveness as tracers of Pb sources in the environment.

Metallomic analysis of brain tissues distinguishes between cases of dementia with Lewy bodies, Alzheimer's disease, and Parkinson's disease dementia.

Background: Dementia with Lewy bodies (DLB) can be difficult to distinguish from Alzheimer's disease (AD) and Parkinson's disease dementia (PDD) at different stages of its progression due to some overlaps in the clinical and neuropathological presentation of these conditions compared with DLB. Metallomic changes have already been observed in the AD and PDD brain-including widespread decreases in Cu levels and more localised alterations in Na, K, Mn, Fe, Zn, and Se. This study aimed to determine whether these metallomic changes appear in the DLB brain, and how the metallomic profile of the DLB brain appears in comparison to the AD and PDD brain. Methods: Brain tissues from ten regions of 20 DLB cases and 19 controls were obtained. The concentrations of Na, Mg, K, Ca, Zn, Fe, Mn, Cu, and Se were determined using inductively coupled plasma-mass spectrometry (ICP-MS). Case-control differences were evaluated using Mann-Whitney U tests. Results were compared with those previously obtained from AD and PDD brain tissue, and principal component analysis (PCA) plots were created to determine whether cerebral metallomic profiles could distinguish DLB from AD or PDD metallomic profiles. Results: Na was increased and Cu decreased in four and five DLB brain regions, respectively. More localised alterations in Mn, Ca, Fe, and Se were also identified. Despite similarities in Cu changes between all three diseases, PCA plots showed that DLB cases could be readily distinguished from AD cases using data from the middle temporal gyrus, primary visual cortex, and cingulate gyrus, whereas DLB and PDD cases could be clearly separated using data from the primary visual cortex alone. Conclusion: Despite shared alterations in Cu levels, the post-mortem DLB brain shows very few other similarities with the metallomic profile of the AD or PDD brain. These findings suggest that while Cu deficiencies appear common to all three conditions, metal alterations otherwise differ between DLB and PDD/AD. These findings can contribute to our understanding of the underlying pathogenesis of these three diseases; if these changes can be observed in the living human brain, they may also contribute to the differential diagnosis of DLB from AD and/or PDD.

Experimental design optimisation and validation by accuracy profile of a novel method for Hg speciation analysis by HPLC-ICP-MS and application to Total Diet Studies.

This study addresses the development and validation of an analytical method for speciation analysis of mercury (inorganic/Hg2+ and methylmercury/CH3Hg+) in fishery products. The Hg species are separated by reversed-phase (RP) high-performance liquid chromatography (HPLC) coupled to inductively coupled plasma mass spectrometry (ICP-MS). The effective separation of Hg2+ and CH3Hg+ was achieved in <8 min using a peptide mapping RP column and a mobile phase containing 2-mercaptoethanol at 0.25% (v/v) and methanol at 1% (v/v). The optimization was carried out using an experimental design through response surface methodology (RSM) with central composite design (CCD), addressing both the HPLC separation and the sample extraction. The method validation was carried out based on the accuracy profile approach. For this purpose, six series of measurements were carried out in duplicate over a time span of 2 months. The limits of quantification (LOQ) were 2.5 µg/kg (wet weight, ww) for CH3Hg+ and 1.2 µg/kg (ww) for Hg2+. The intermediate reproducibility in terms of coefficient of variation (CVR) was <6%. The bias (%) obtained for the analysis of four certified reference materials (CRMs), namely TORT-3 (lobster hepatopancreas), SRM 1566-b (oyster tissue), SQID-1 (cuttlefish) and NMIJ CRM 7402-a (cod fish tissue) was <7%. This demonstrates the method robustness and suitability for routine speciation analysis of CH3Hg+ and Hg2+ in fishery products. The method is intended to be applied for the analysis of the panel of fishery products and fish-based foods in the framework of the (ongoing) third French Total Diet Study.

Distribution and modes of occurrence of Nb in subbituminous coal: A case study from the Jungar Coalfield, Ordos Basin, China.

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.

Analytical strategies for sensitive and precise determination of 87Sr/86Sr in olive oil through ion extraction, chromatographic separation, and multicollector inductively-coupled plasma mass-spectrometry.

Several food regulatory bodies regard olive oil as highly susceptible to food fraud, largely due to its substantial economic worth. Precise analytical tools are being developed to uncover these types of fraud. This study examines an innovative approach to extract strontium (Sr) from the olive oil matrix (via EDTA complexation and ion-exchange chromatography) and to determine its isotope composition by MC-ICP-MS. This technique was compared to a commonly used technique (i.e. acid extraction and extraction chromatography), and then validated. Three olive oils that are sold in France were prepared and analyzed by two methods: 1) acid extraction prior to Sr purification by Sr-spec resin and 2) complexation by EDTA prior to Sr purification by AG50W-X8. These methods were applied for the determination of the 87Sr/86Sr isotope ratio of 23 olive oils from various countries. We also demonstrated the feasibility of the method for the detection of olive oil mixtures.

Aerosol exposure at air-liquid-interface (AE-ALI) in vitro toxicity system characterisation: Particle deposition and the importance of air control responses.

Experimental systems allowing aerosol exposure (AE) of cell cultures at the air-liquid-interface (ALI) are increasingly being used to assess the toxicity of inhaled contaminants as they are more biomimetic than standard methods using submerged cultures, however, they require detailed characterisation before use. An AE-ALI system combining aerosol generation with a CULTEX® exposure chamber was characterised with respect to particle deposition and the cellular effects of filtered air (typical control) exposures. The effect of system parameters (electrostatic precipitator voltage, air flowrate to cells and insert size) on deposition efficiency and spatial distribution were investigated using ICP-MS and laser ablation ICP-MS, for an aerosol of CeO2 nanoparticles. Deposition varied with conditions, but appropriate choice of operating parameters produced broadly uniform deposition at suitable levels. The impact of air exposure duration on alveolar cells (A549) and primary small airway epithelial cells (SAECs) was explored with respect to LDH release and expression of selected genes. Results indicated that air exposures could have a significant impact on cells (e.g., cytotoxicity and expression of genes, including CXCL1, HMOX1, and SPP1) at relatively short durations (from 10 mins) and that SAECs were more sensitive. These findings indicate that detailed system characterisation is essential to ensure meaningful results.

Multi-element Contamination and Health Risks in Green Leafy Vegetables from Ambagarh Chowki, Chhattisgarh, India.

Leafy plants are commonly consumed as vegetables in India due to their high nutrient and vitamin content. This study, conducted in Ambagarh Chowki (India), investigated the accumulation potential of 52 elements (including Al, As, Ba, Be, Bi, Ca, Cd, Ce, Co, Cr, Cu, Dy, Er, Eu, Fe, Ga, Gd, Ge, Ho, K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, Nd, Ni, P, Pb, Pr, Rb, Sb, Sc, Se, Sm, Sn, Sr, Tb, Te, Th, Ti, Tl, Tm, U, V, W, Y, Yb, and Zn) in seven leafy vegetable species, namely Amaranthus tricolor L., Corchorus olitorius L., Cordia myxa L., Hibiscus sabdariffa L., Ipomoea batatas (L.) Lam., Moringa oleifera Lam., and Spinacia oleracea L. Technique: Inductively coupled plasma mass spectrometry (ICP-MS) was employed for analysis. The maximum concentrations of elements such as Al, Ba, Be, Bi, Cd, Co, Cr, Fe, Ga, Ge, Li, Mn, Ni, Pb, Sb, Th, Tl, U, V, W, and REEs were observed in S. oleracea leaves, indicating their highest accumulation potential. In contrast, the maximum concentrations of As were found in H. sabdariffa leaves; Ca and Si in M. oleifera leaves; Mg, Sr, and Mo in A. tricolor leaves; and P, K, Cu, and Zn in C. myxa leaves, respectively. Twenty-one elements (Cr, Cd, Pb, Ni, Co, V, Cu, Zn, Fe, Mn, Th, Sb, Ba, Be, Li, Sr, Tl, U, Se, Sn, and REEs) exceeded permissible limits set by the WHO. The elevated hazard index values indicated significant non-carcinogenic effects. The sources of these elements could be attributed to a combination of geological factors and agricultural practices. This study highlights the need for further investigation into the potential health implications of consuming these vegetables in the aforementioned region.

Accurate Boron Determination in Tourmaline by Inductively Coupled Plasma Mass Spectrometry: An Insight into the Boron-Mannitol Complex-Based Wet Acid Digestion Method.

Tourmaline, a boron-bearing mineral, has been extensively applied as a geothermometer, provenance indicator, and fluid-composition recorder in geological studies. In this paper, the decomposition capability of an HF-HNO3-mannitol mixture for a tourmaline sample was investigated in detail for the first time, and a wet acid digestion method based on the boron-mannitol complex for accurate boron determination in tourmaline by inductively coupled plasma mass spectrometry (ICP-MS) was proposed. With a digestion temperature of 140 °C, tourmaline samples of 25 mg (±0.5 mg) can be completely decomposed by a ternary mixture, which consisted of 0.6 mL of HF, 0.6 mL of HNO3, and 0.7 mL of 2% mannitol (wt.), via a continuous heating treatment of 36 h. Following gentle evaporation at 100 °C, the sample residues were re-dissolved using 2 mL of 40% HNO3 solution (wt.) and diluted to about 2.0 × 105-fold by a two-step method using 2% HNO3 solution (wt.). The boron contents in a batch of parallel tourmaline samples were then determined by ICP-MS, and results showed that the boron concentration levels were in a range of 3.20-3.44% with determination RSDs less than 4.0% (n = 5). It was found that the boron concentrations obtained at the mass of 10B were comparable with results from the measurements at the mass of 11B. This revealed that the usage of 2% mannitol with a quantity as high as 0.7 mL in this developed approach did not exhibit significant effect on the quantification accuracy of boron at the mass of 11B. It was also found that the processes including fluoride-forming prevention and fluoride decomposition deteriorated the boron-reserving efficiency of mannitol for tourmaline, causing the averaged boron contents to vary from 2.25% to 3.57% (n = 5). Furthermore, the stability of the boron-mannitol complex under 185 °C by applying the laboratory high pressure-closed digestion method was evaluated, which showed that there existed a 60.36% loss of boron compared to that under 140 °C by using this proposed approach. For this ternary mixture, the tourmaline decomposing efficiency was found to be weakened prominently using 100 °C as the digestion temperature, and tourmaline powders can be observed even after 72 h of continuous heating with B contents within 1.09-1.23% (n = 5). To assess the accuracy of this developed method, the boron recovery of anhydrous lithium tetraborate was studied. It was found that the boron recoveries were within 96.59-102.12% (RSD < 1%, n = 5), demonstrating the accuracy and reliability of this proposed method, which exhibits advantages of high B preserving efficiency, and giving concentration information of both B and trace elements simultaneously. By applying such a boron-mannitol complex-based wet acid digestion method, the chemical composition of boron and trace elements in three tourmaline samples from different pegmatites were quantified, which provided valuable information to distinguish regional deposits and the associated evolution stages.

The undetected murder? Evaluation and validation of a practicable and rapid inductively coupled plasma-mass spectrometry method for the detection of arsenic, lead, and thallium intoxications in postmortem blood.

Homicide, suicide, or accident - elemental intoxication may be a cause in each of these types of deaths. Inductively coupled plasma mass spectrometry (ICP-MS) has emerged as the gold standard analytical method for toxic metal analysis in both clinical and forensic settings. An ICP-MS method was developed using a modified acidic workup for the quantitative determination of arsenic, lead, and thallium. Method validation focused on the assessment of linearity, between- and within-day precisions, limits of detection (LoD) and lower limits of quantification (LLoQ), and carryover. The method was applied to analysis of postmortem peripheral blood samples from 279 forensic cases for which orders for chemical-toxicological examination had been received from the public prosecutor's office. Using six-point and one-point calibrations (latter for rapid screening purposes), precisions and accuracies ranged from -4.8 to 5.8% and -6.4 to 7.5%. Analytical sensitivities for As, Pb, and Tl were 0.08, 0.18, and 0.01 µg/l (LoD) and 0.23, 0.66, and 0.03 µg/l (LLoQ), respectively. Observed postmortem peripheral blood concentrations were As, 1.31 ± 3.42 µg/L; Pb, 17.4 ± 13.1 µg/L; and Tl, 0.11 ± 0.07 µg/L (mean ± standard deviation [SD]). Elemental concentrations, determined in additional quality control samples, were in good agreement to those obtained with an external ICP-MS method based on alkaline sample processing. The current method is practicable and compatible with an ICP-MS system used for trace element analysis in an accredited medical laboratory. It allows for implementation of low-threshold investigations when metal intoxications are suspected in forensic routine.

Tracing isotopically labeled selenium nanoparticles in plants via single-particle ICP-mass spectrometry.

Agronomic biofortification using selenium nanoparticles (SeNPs) shows potential for addressing selenium deficiency but further research on SeNPs-plants interaction is required before it can be effectively used to improve nutritional quality. In this work, single-particle inductively coupled plasma-mass spectrometry (SP-ICP-MS) was used for tracing isotopically labeled SeNPs (82SeNPs) in Oryza sativa L. tissues. For this purpose, SeNPs with natural isotopic abundance and 82SeNPs were synthesized by a chemical method. The NPs characterization by transmission electron microscopy (TEM) confirmed that enriched NPs maintained the basic properties of unlabeled NPs, showing spherical shape, monodispersity, and sizes in the nano-range (82.8 ± 6.6 nm and 73.2 ± 4.4 nm for SeNPs and 82SeNPs, respectively). The use of 82SeNPs resulted in an 11-fold enhancement in the detection power for ICP-MS analysis, accompanied by an improvement in the signal-to-background ratio and a reduction of the size limits of detection from 89.9 to 39.9 nm in SP-ICP-MS analysis. This enabled 82SeNPs to be tracked in O. sativa L. plants cultivated under foliar application of 82SeNPs. Tracing studies combining SP-ICP-MS and TEM-energy-dispersive X-ray spectroscopy data confirmed the uptake of intact 82SeNPs by rice leaves, with most NPs remaining in the leaves and very few particles translocated to shoots and roots. Translocation of Se from leaves to roots and shoots was found to be lower when applied as NPs compared to selenite application. From the size distributions, as obtained by SP-ICP-MS, it can be concluded that a fraction of the 82SeNPs remained within the same size range as that of the applied NP suspension, while other fraction underwent an agglomeration process in the leaves, as confirmed by TEM images. This illustrates the potential of SP-ICP-MS analysis of isotopically enriched 82SeNPs for tracing NPs in the presence of background elements within complex plant matrices, providing important information about the uptake, accumulation, and biotransformation of SeNPs in rice plants.

Feasibility of Matrix-Matched Material for Determining Elements in Rice Flour by SN-ICP-MS and LA-ICP-MS.

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.

Assessment of Heavy Metals and Trace Elements in the Human Milk of Women Living in Latvia and an Evaluation of Influencing Factors.

During lactation, heavy metals and trace elements can be mobilised from the maternal body stores and excreted via human milk. A total of 66 mature human milk samples were collected from lactating women in Latvia between 2016 and 2017 to analyse the content of As, Cd, Pb, Al, Sn, and Ni. Additionally, 50 mature human milk samples were collected between 2022 and 2023 to analyse the content of Cd and Pb. The content of heavy metals and trace elements in human milk was determined using ICP-MS. Only two individual human milk samples contained heavy metals above the method's detection limit-one with an arsenic content of 0.009 mg kg-1 and one with a lead content of 0.047 mg kg-1. The preliminary data show that human milk among lactating women in Latvia contains only insignificant amounts of heavy metals and trace elements. Concern over such content should not be a reason to choose formula feeding over breastfeeding. Nevertheless, heavy metals, trace elements and other pollutants in human milk should be continuously monitored.

Application of microwave digestion for complete dissolution of igneous silicate rock samples: A simple and quick sample preparation procedure.

In the area of geochemical analyses of rock solutions, achieving a complete sample dissolution is a fundamental prerequisite for obtaining accurate, precise and reliable analytical results. The challenge posed by the presence of resistant minerals such as zircon, rutile, corundum, spinel, tourmaline, beryl, chromite, and cassiterite in different silicate rocks is a well-recognized challenge in geological studies. These minerals, due to their resilient nature, demand additional efforts to ensure complete dissolution during sample preparation. The prevailing conventional sample digestion methods require several days of laboratory work and the handling of large amounts of multiple types of acids, which also increase sample blanks. Until recently, there was a widely held belief that microwave-assisted digestion, where microwave radiation is transformed to heat, faced limitations in achieving complete dissolution of refractory minerals. This prevailing opinion led to skepticism about the applicability of microwave-assisted digestion for sample preparation of e.g. igneous rock samples containing these minerals. This study introduces a novel, universal and quick closed-vessel (pressurized) high-temperature microwave-assisted digestion method appropriate for dissolution of all major types of igneous silicate rock samples, including rocks containing refractory minerals. This streamlined and expeditious procedure, comprising three steps, requires only a total time of ∼9 h. The method proves its versatility by successfully dissolving both, mafic igneous samples (e.g., basalt) with low-content of resistant minerals, and felsic igneous samples (e.g., granite) with relatively high-content of resistant minerals. To validate the reliability of this procedure, 36 trace elements were analyzed: Li, Be, Sc, V, Cr, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, Pb, Th and U in several geological Certified Reference Materials (CRMs). The CRMs including basalts JB-3, BCR-2, BHVO-2; andesites JA-2, AGV-2; granodiorite GSP-2; granite JG-2 and alkaline granite MGL-OShBO, were digested and analyzed using triple quadrupole Inductively Coupled-Plasma-Mass Spectrometer (ICP-QQQ). The results of the analysis demonstrate remarkable consistency, closely aligning with both certified and literature values.

Influence of geographical location on the distribution of heavy metals in dairy cattle feeds sourced from two South African provinces.

The contamination of feed and food by heavy metals represents a significant concern for the health of both animals and humans. This study investigates the impact of geographical location on heavy metal distribution in dairy cattle feeds sourced from Free State and Limpopo, South Africa (SA). A total of 70 feed samples (40 from Free State and 30 from Limpopo) were collected from 2018 to 2019 and analyzed for heavy metals, including cadmium (Cd), arsenic (As), copper (Cu), zinc (Zn), lead (Pb), and chromium (Cr), using inductively coupled plasma mass spectrometry (ICP-MS). Our findings revealed the presence of Cr, Cu, and Zn in the feeds, but at levels below the FAO/WHO permissible limits. Additionally, As, Cd, and Pb concentrations in the feeds were below the Limit of Detections (LODs). Generally, Cr concentrations (0.032-0.454 mg/kg) identified in the Free State samples were lower than those found in Limpopo (0.038-1.459 mg/kg), while the levels of Cu (0.092-4.898 mg/kg) and Zn (0.39-13.871 mg/kg) recorded in the Free State samples were higher than those from Limpopo [(0.126-3.467 mg/kg) and (0.244-13.767 mg/kg), respectively]. According to independent sample t-tests, Cu and Zn levels were substantially higher (p ≤ .05) in Free State feeds compared to Limpopo, while Limpopo feeds exhibited significantly higher (p ≤ .05) Cr concentrations than Free State feeds. Despite the low recorded heavy metal levels, regular monitoring of these elements in cow diets across all SA provinces is essential for ensuring the well-being of animals and humans.

A multi-platform approach for the comprehensive analysis of per- and polyfluoroalkyl substances (PFAS) and fluorine mass balance in commercial ski wax products.

The unique properties of per- and polyfluoroalkyl substances (PFAS) have led to their extensive use in consumer products, including ski wax. Based on the risks associated with PFAS, and to align with PFAS regulations, the international ski federation (FIS) implemented a ban on products containing "C8 fluorocarbons/perfluorooctanoate (PFOA)" at all FIS events from the 2021/2022 season, leading manufactures to shift their formulations towards short-chain PFAS chemistries. To date, most studies characterising PFAS in ski waxes have measured a suite of individual substances using targeted analytical approaches. However, the fraction of total fluorine (TF) in the wax accounted for by these substances remains unclear. In this study, we sought to address this question by applying a multi-platform, fluorine mass balance approach to a total of 10 commercially available ski wax products. Analysis of TF by combustion ion chromatography (CIC) revealed concentrations of 1040-51700 µg F g-1 for the different fluorinated waxes. In comparison, extractable organic fluorine (EOF) determined in methanol extracts by CIC (and later confirmed by inductively-coupled plasma-mass spectrometry and 19F- nuclear magnetic resonance spectroscopy) ranged from 92 to 3160 µg g-1, accounting for only 3-8.8 % of total fluorine (TF). Further characterisation of extracts by cyclic ion mobility-mass spectrometry (IMS) revealed 15 individual PFAS with perfluoroalkyl carboxylic acid concentrations up to 33 µg F g-1, and 3 products exceeding the regulatory limit for PFOA (0.025 µg g-1) by a factor of up to 100. The sum of all PFAS accounted for only 0.01-1.0 % of EOF, implying a high percentage of unidentified PFAS, thus, pyrolysis gas chromatography-mass spectrometry was used to provide evidence of the nature of the non-extractable fluorine present in the ski wax products.

The Development of a Rapid, Cost-Effective, and Green Analytical Method for Mercury Speciation.

Mercury is a naturally occurring metal found in various inorganic and organic forms within the environment. Due to its high toxicity, there is global concern regarding human exposure to this element. The combination of high-performance liquid chromatography and inductively coupled plasma mass spectrometry (HPLC-ICP-MS) is commonly used to analyze the different forms of mercury in a sample due to its high sensitivity and ability to selectively detect mercury. However, the traditional HPLC-ICP-MS methods are often criticized for their lengthy analysis times. In this study, we have refined the conventional approach by transitioning to ultra-high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry (UHPLC-ICP-MS). This modification has resulted in significant reductions in runtime as well as reagent and argon usage, thereby offering a more rapid, environmentally friendly, and cost-effective method. We successfully adapted an HPLC-ICP-MS method to UHPLC-ICP-MS, achieving the analysis of Hg2+ and MeHg+ within 1 min with a mobile phase consumption of only 0.5 mL and a sample volume of 5.0 µL; this is a major advance compared to HPLC analysis with run times generally between 5 and 10 min. The method's performance was assessed by analyzing muscle and liver tissue samples (serving as reference material) from fish, demonstrating the versatility of the method in relation to different complex matrices.

Past progress in environmental nanoanalysis and a future trajectory for atomic mass-spectrometry methods.

The development of engineered nanotechnology has necessitated a commensurate maturation of nanoanalysis capabilities. Building off a legacy established by electron microscopy and light-scattering, environmental nanoanalysis has now benefited from ongoing advancements in instrumentation and data analysis, which enable a deeper understanding of nanomaterial properties, behavior, and impacts. Where once environmental nanoparticles and colloids were grouped into broad 'dissolved or particulate' classes that are dependent on a filter size cut-off, now size distributions of submicron particles can be separated and characterized providing a more comprehensive examination of the nanoscale. Inductively coupled plasma-quadrupole mass spectrometry (ICP-QMS), directly coupled to field flow fractionation (FFF-ICP-QMS) or operated in single particle mode (spICP-MS) have spearheaded a revolution in nanoanalysis, enabling research into nanomaterial behavior in environmental and biological systems at expected release concentrations. However, the complexity of the nanoparticle population drives a need to characterize and quantify the multi-element composition of nanoparticles, which has begun to be realized through the application of time-of-flight MS (spICP-TOFMS). Despite its relative infancy, this technique has begun to make significant strides in more fully characterizing particulate systems and expanding our understanding of nanoparticle behavior. Though there is still more work to be done with regards to improving instrumentation and data processing, it is possible we are on the cusp of a new nanoanalysis revolution, capable of broadening our understanding of the size regime between dissolved and bulk particulate compartments of the environment.

Degree of conversion of dual-cured composite luting agents: The effect of transition metal-based touch-cure activators.

PURPOSE: The aim of the study was (a) to assess the effect of universal adhesives and tooth primers with novel touch-cure activators on the conversion of dual-cured resin composite luting agents (RLAs) polymerized under the self-curing mode, and (b) to investigate the source of the catalytic effect exerted by the activators. MATERIALS AND METHODS: The materials selected were the adhesive RLAs Panavia V5/Tooth Primer (PV5/TP5), Variolink Esthetic DC/Adhese Universal DC (VLE/ADC), and the self-adhesive RLAs GCem ONE/AE Primer (GCO/AEP), RelyX Universal/Scotchbond Universal Plus (RXU/SUP) and Panavia SA Universal/Clearfil Universal Bond Quick (PSU/CUQ), the later serving as a control with an aryl-sulfinate activator. Coronal dentin specimens were prepared (n = 5/material), treated with the corresponding primers/adhesives (non-irradiated) and covered with a 100 µm-thick RLA layer (SC+A group). Three specimen series were additionally prepared (n = 3 × 5/material): A self-cured without the primers/adhesives (SC group), a dual-cured (20 s irradiation) with the corresponding primers/adhesives (DC+A group) and a dual-cured without primers/adhesives (DC group). All specimens were stored for 15 min (37 °C/dark/60 %RH). After demolding the degree of C = C conversion (DC%, top RLA surfaces) was measured by ATR-FTIR spectroscopy. The primer/adhesive liquids were further analyzed by ICP-MS and the microbrush tips of ADC by SEM-EDS. RESULTS: The touch-cure activators increased the DC% in all self-cured RLAs but failed to reach the values of the corresponding dual-cured RLAs. The effect of the activators in dual-cured specimens was negligible. The ICP-MS analysis showed the presence of V (AEP, TP5, ADC) and Cu (SUP) transitional metals in the activators, with V been located at the free ends of ADC tip bristles. The V activators demonstrated the highest DC% improvement in self-cured specimens. CONCLUSION: The new touch-cure activators significantly increased the conversion of the self-cured RLAs. Therefore, this step should be considered as universally applicable and not selective, as currently proposed for the self-adhesive luting agents by the manufacturers.

Plasma Ionomic Profile and Interaction Patterns in Coronary Artery Disease Patients.

Humans are exposed to various chemical elements that have been associated with the development and progression of diseases such as coronary artery disease (CAD). Unlike previous research, we employed a multi-element approach to investigate CAD patients and those with comorbid conditions such as diabetes (CAD-DM2), high blood pressure (CAD-HBP), or high blood lipids (CAD-HBL). Plasma concentrations of 21 elements, including lithium (Li), boron (B), aluminum (Al), calcium (Ca), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), arsenic (As), selenium (Se), strontium (Sr), cadmium (Cd), tin (Sn), stibium (Sb), barium (Ba), and lead (Pb), were measured in CAD patients (n = 201) and healthy subjects (n = 110) using inductively coupled plasma-mass spectrometry (ICP-MS). Principal component analysis (PCA) and orthogonal partial least squares discriminant analysis (OPLS-DA) models were utilized to analyze the ionomic profiles. Spearman correlation analysis was employed to identify the interaction patterns among individual elements. We found that levels of Ba, Li, Ni, Zn and Pb were elevated in the CAD group compared to the healthy group, while Sb, Ca, Cu, Ti, Fe, and Se were lower. Furthermore, the CAD-DM2 group exhibited higher levels of Ni and Cd, while the CAD-HBP group showed lower levels of Co and Mn. In the CAD-HBL group, Ti was increased, whereas Ba, Cr, Cu, Co, Mn, and Ni were reduced. In conclusion, ionomic profiles can be utilized to differentiate CAD patients from healthy individuals, potentially providing insights for future treatment or dietary interventions.

Assessing Mineral Content and Heavy Metal Exposure in Abruzzo Honey and Bee Pollen from Different Anthropic Areas.

Honey and bee pollen offer potential health benefits due to their nutrient and bioactive molecules, but they may also harbor contaminants such as heavy metals. This study aimed to assess the content of different metals, including Mg, Al, K, Ca, V, Cr, Mn, Fe, Co, Ni, Zn, Cu, As, Rb, Sr, Cd, Cs, Tl, Pb and U, in honey and bee pollen collected from different Abruzzo region (Italy) areas (A1, A2, A3, A4), characterized by different anthropic influences described by Corine Land Cover maps. Differences were observed in the mineral and heavy metal content associated with the influence of biotic and abiotic factors. Honeys were found to be safe in regard to non-carcinogenic risk in all the consumer categories (THQm < 1). A particular carcinogenic risk concern was identified for toddlers associated with Cr (LCTR > 1 × 10-4) in A1, A2 and A3 apiaries. Pb and Ni represent potential non-carcinogenic and carcinogenic health risks in children and adults due to bee pollen consumption, showing high values of THQm and LCTR. The results suggest the advantages of utilizing bee products to screen mineral and heavy metal content, providing valuable insights into environmental quality and potential health risks.